This application is a § 371 National Stage Application of PCT/EP2014/072645, filed Oct. 22, 2014, which claims priority to European 13190182.9 filed Oct. 25, 2013.
Field of the Invention
The present invention relates to agrochemically active herbicidal compositions, to processes for production thereof and to the use thereof for control of harmful plants.
Description of Related Art
WO 2012/126932 A1 discloses particular N-(1,3,4-oxadiazol-2-yl)arylcarboxamides having herbicidal properties. However, these active ingredients do not always exhibit sufficient efficacy against harmful plants and/or some of them are not fully compatible with some important crop plants such as cereal species, corn or rice.
It is therefore an object of the present invention to provide herbicidal compositions in which efficacy against harmful plants and/or selectivity of the abovementioned herbicides with respect to important crop plants is increased. This object is achieved by the inventive herbicidal compositions described hereinafter, comprising particular N-(1,3,4-oxadiazol-2-yl)arylcarboxamides, further herbicides and optionally safeners.
The present invention provides herbicidal compositions comprising (A) one or more compounds of the formula (I) (component A) or salts thereof
in which the substituents are defined as follows:
A is N or CY,
R is hydrogen, (C1-C6)-alkyl, R1O—(C1-C6)-alkyl, CH2R6, (C3-C7)-cycloalkyl, halo-(C1-C6)-alkyl, (C2-C6)-alkenyl, halo-(C2-C6)-alkenyl, (C2-C6)-alkynyl, halo-(C2-C6)-alkynyl, OR1, NHR1, methoxycarbonyl, ethoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, methylcarbonyl, trifluoromethylcarbonyl, dimethylamino, acetylamino, methylsulfenyl, methylsulfinyl, methylsulfonyl, or heteroaryl, heterocyclyl, benzyl or phenyl each substituted by s radicals from the group of halogen, nitro, cyano, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, (C3-C6)-cycloalkyl, S(O)n—(C1-C6)-alkyl, (C1-C6)-alkoxy, halo-(C1-C6)-alkoxy, (C1-C6)-alkoxy-(C1-C4)-alkyl,
X is nitro, halogen, cyano, formyl, thiocyanato, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, (C2-C6)-alkenyl, halo-(C2-C6)-alkenyl, (C2-C6)-alkynyl, halo-(C3-C6)-alkynyl, (C3-C6)-cycloalkyl, halo-(C3-C6)-cycloalkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, halo-(C3-C6)-cycloalkyl-(C1-C6)-alkyl, COR1, COOR1, OCOOR1, NR1COOR1, C(O)N(R1)2, NR1C(O)N(R1)2, OC(O)N(R1)2, C(O)NR1OR1, OR1, OCOR1, OSO2R2, S(O)nR2, SO2OR1, SO2N(R1)2, NR1SO2R2, NR1COR1, (C1-C6)-alkyl-S(O)nR2, (C1-C6)-alkyl-OR1, (C1-C6)-alkyl-OCOR1, (C1-C6)-alkyl-OSO2R2, (C1-C6)-alkyl-CO2R1, (C1-C6)-alkyl-SO2OR1, (C1-C6)-alkyl-CON(R1)2, (C1-C6)-alkyl-SO2N(R1)2, (C1-C6)-alkyl-NR1COR1, (C1-C6)-alkyl-NR1SO2R2, NR1R2, P(O)(OR5)2, CH2P(O)(OR5)2, (C1-C6)-alkylheteroaryl, (C1-C6)-alkylheterocyclyl, where the two latter radicals are each by s halogen, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, S(O)n—(C1-C6)-alkyl, (C1-C6)-alkoxy, halo-(C1-C6)-alkoxy radicals, and where heterocyclyl bears n oxo groups,
Y is hydrogen, nitro, halogen, cyano, thiocyanato, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, (C2-C6)-alkenyl, halo-(C2-C6)-alkenyl, (C2-C6)-alkynyl, halo-(C2-C6)-alkynyl, (C3-C6)-cycloalkyl, (C3-C6)-cycloalkenyl, halo-(C3-C6)-cycloalkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, halo-(C3-C6)-cycloalkyl-(C1-C6)-alkyl, COR1, COOR1, OCOOR1, NR1COOR1, C(O)N(R1)2, NR1C(O)N(R1)2, OC(O)N(R1)2, CO(NOR1)R1, NR1SO2R2, NR1COR1, OR1, OSO2R2, S(O)nR2, SO2OR1, SO2N(R1)2, (C1-C6)-alkyl-S(O)nR2, (C1-C6)-alkyl-OR1, (C1-C6)-alkyl-OCOR1, (C1-C6)-alkyl-OSO2R2, (C1-C6)-alkyl-CO2R1, (C1-C6)-alkyl-CN, (C1-C6)-alkyl-SO2OR1, (C1-C6)-alkyl-CON(R1)2, (C1-C6)-alkyl-SO2N(R1)2, (C1-C6)-alkyl-NR1COR1, (C1-C6)-alkyl-NR1SO2R2, N(R1)2, P(O)(OR5)2, CH2P(O)(OR5)2, (C1-C6)-alkylphenyl, (C1-C6)-alkylheteroaryl, (C1-C6)-alkylheterocyclyl, phenyl, heteroaryl or heterocyclyl, where the 6 latter radicals are each substituted by s radicals from the group of halogen, nitro, cyano, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, (C3-C6)-cycloalkyl, S(O)n—(C1-C6)-alkyl, (C1-C6)-alkoxy, halo-(C1-C6)-alkoxy, (C1-C6)-alkoxy-(C1-C4)-alkyl and cyanomethyl, and where heterocyclyl bears n oxo groups,
Z is hydrogen, halogen, cyano, thiocyanato, (C1-C6)-alkyl, (C1-C6)-alkoxy, halo-(C1-C6)-alkyl, (C2-C6)-alkenyl, halo-(C2-C6)-alkenyl, (C2-C6)-alkynyl, halo-(C2-C6)-alkynyl, (C3-C6)-cycloalkyl, halo-(C3-C6)-cycloalkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, halo-(C3-C6)-cycloalkyl-(C1-C6)-alkyl, COR1, COOR1, OCOOR1, NR1COOR1, C(O)N(R1)2, NR1C(O)N(R1)2, OC(O)N(R1)2, C(O)NR1OR1, OSO2R2, S(O)nR2, SO2OR1, SO2N(R1)2, NR1SO2R2, NR1COR1, (C1-C6)-alkyl-S(O)nR2, (C1-C6)-alkyl-OR1, (C1-C6)-alkyl-OCOR1, (C1-C6)-alkyl-OSO2R2, (C1-C6)-alkyl-CO2R1, (C1-C6)-alkyl-SO2OR1, (C1-C6)-alkyl-CON(R1)2, (C1-C6)-alkyl-SO2N(R1)2, (C1-C6)-alkyl-NR1COR1, (C1-C6)-alkyl-NR1SO2R2, N(R1)2, P(O)(OR5)2, heteroaryl, heterocyclyl or phenyl, where the last three radicals are each substituted by s radicals from the group of halogen, nitro, cyano, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, (C3-C6)-cycloalkyl, S(O)n—(C1-C6)-alkyl, (C1-C6)-alkoxy and halo-(C1-C6)-alkoxy, and where heterocyclyl bears n oxo groups,
R1 is hydrogen, (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C2-C6)-alkenyl, (C2-C6)-haloalkenyl, (C2-C6)-alkynyl, (C2-C6)-haloalkynyl, (C3-C6)-cycloalkyl, (C3-C6)-cycloalkenyl, (C3-C6)-halocycloalkyl, (C1-C6)-alkyl-O—(C1-C6)-alkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, phenyl, phenyl-(C1-C6)-alkyl, heteroaryl, (C1-C6)-alkylheteroaryl, heterocyclo, (C1-C6)-alkylheterocyclyl, (C1-C6)-alkyl-O-heteroaryl, (C1-C6)-alkyl-O-heterocyclyl, (C1-C6)-alkyl-NR3-heteroaryl, (C1-C6)-alkyl-NR3-heterocyclyl, where the 21 latter radicals are substituted by s radicals from the group consisting of cyano, halogen, nitro, thiocyanato, OR3, S(O)nR4, N(R3)2, NR3OR3, COR3, OCOR3, SCOR4, NR3COR3, NR3SO2R4, CO2R3, COSR4, CON(R3)2 and (C1-C4)-alkoxy-(C2-C6)-alkoxycarbonyl, and where heterocyclyl bears n oxo groups,
R2 is (C1-C6)-alkyl, (C1-C6)-haloalkyl, (C2-C6)-alkenyl, (C2-C6)-haloalkenyl, (C2-C6)-alkynyl, (C2-C6)-haloalkynyl, (C3-C6)-cycloalkyl, (C3-C6)-cycloalkenyl, (C3-C6)-halocycloalkyl, (C1-C6)-alkyl-O—(C1-C6)-alkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, phenyl, phenyl-(C1-C6)-alkyl, heteroaryl, (C1-C6)-alkylheteroaryl, heterocyclyl, (C1-C6)-alkylheterocyclyl, (C1-C6)-alkyl-O-heteroaryl, (C1-C6)-alkyl-O-heterocyclyl, (C1-C6)-alkyl-NR3-heteroaryl, (C1-C6)-alkyl-NR3-heterocyclyl, where the 21 latter radicals are substituted by s radicals from the group consisting of cyano, halogen, nitro, thiocyanato, OR3, S(O)nR4, N(R3)2, NR3OR3, COR3, OCOR3, SCOR4, NR3COR3, NR3SO2R4, CO2R3, COSR4, CON(R3)2 and (C1-C4)-alkoxy-(C2-C6)-alkoxycarbonyl, and where heterocyclyl bears n oxo groups,
R3 is hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C3-C6)-cycloalkyl or (C3-C6)-cycloalkyl-(C1-C6)-alkyl,
R4 is (C1-C6)-alkyl, (C2-C6)-alkenyl or (C2-C6)-alkynyl,
R5 is methyl or ethyl,
R6 is acetoxy, acetamido, N-methylacetamido, benzoyloxy, benzamido, N-methylbenzamido, methoxycarbonyl, ethoxycarbonyl, benzoyl, methylcarbonyl, piperidinylcarbonyl, morpholinylcarbonyl, trifluoromethylcarbonyl, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, (C1-C6)-alkoxy, (C3-C6)-cycloalkyl, or heteroaryl, heterocyclyl or phenyl each substituted by s radicals from the group of methyl, ethyl, methoxy, trifluoromethyl and halogen,
n is 0, 1 or 2,
s is 0, 1, 2 or 3,
and
(B) one or more herbicides (component B) selected from groups (B1) to (B11):
B1 1,3-diketo compounds comprising
prohexadione, prohexadione-calcium, trinexapac-ethyl, alloxydim, alloxydim-sodium, butroxydim, clethodim, cycloxydim, ketospiradox, profoxydim, sethoxydim, tepraloxydim, tralkoxydim, mesotrione, sulcotrione, tefuryltrione, tembotrione, bicyclopyrone, pinoxaden,
B2 (sulfon)amides comprising
beflubutamide, bromobutide, dimethenamide, dimethenamide-P, diphenamide, napropamide, pethoxamid, N-[3-chloro-4-(1-methylethyl)-phenyl]-2-methylpentanamide, propyzamide, diflufenican, etobenzanid, flufenacet, mefenacet, mefluidide, picolinafen, propanil, N-phenylphthalamic acid, acetochlor, alachlor, amidochlor, butachlor, butenachlor, dimethachlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor, propisochlor, (2-chloro-6′-ethyl-N-isopropoxymethylaceto-o-toluidide), thenylchlor, asulam, carbaryl, carbetamide, chlorpropham, desmedipham, phenmedipham, propham, butylate, cycloate, dimepiperate, EPTC, esprocarb, methasulfocarb, molinate, orbencarb, pebulate, prosulfocarb, pyributicarb, thiobencarb, tri-allate, vernolate, amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, mesosulfuron, mesosulfuron-methyl, metazosulfuron, methiopyrsulfuron, metsulfuron, metsulfuron-methyl, monosulfuron, monosulfuron-ester, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, trifloxysulfuron (sodium), triflusulfuron, triflusulfuron-methyl, tritosulfuron, (benzoic acid, 2-[[[[[4-methoxy-6-(methylthio)-2-pyrimidinyl]amino]carbonyl]amino]sulfonyl]methyl ester), flucarbazone, flucarbazone-sodium, ipfencarbazone, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone, thiencarbazone-methyl, cloransulam, cloransulam-methyl, diclosulam, florasulam, flumetsulam, metosulam, penoxsulam, pyroxsulam, 3-chloro-N-[(4,6-dimethoxypyrimidin-2-yl)carbamoyl]-1-methyl-4-(5-methyl-5,6-dihydro-1,4,2-dioxazin-3-yl)-1H-pyrazole-5-sulfonamide,
B3 arylnitriles comprising
bromoxynil, bromoxynil-butyrate, bromoxynil-potassium, bromoxynil-heptanoate, bromoxynil-octanoate, detosyl-pyrazolate (DTP), dichlobenil, ioxynil, ioxynil-octanoate, ioxynil-potassium, ioxynil-sodium, pyraclonil,
B4 azoles comprising
benzofenap, pyrazolynate (pyrazolate), pyrazoxyfen, pyroxasulfone, topramezone, pyrasulfotole, 3-(3-chloro-5-{[1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy}phenoxy)-1-methyl-5-(trifluoromethyl)-1H-pyrazole, 3-(3-iodo-5-{[1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy}phenoxy)-1-methyl-5-(trifluoromethyl)-1H-pyrazole, 1-ethyl-3-(3-fl uoro-5-{[1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy}phenoxy)-5-(trifluoromethyl)-1H-pyrazole, pyraflufen, pyraflufen-ethyl, fenoxasulfone, isouron, isoxaben, isoxaflutole, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropyl-ammonium, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-immonium, azafenidin, oxadiargyl, oxadiazon, amicarbazone, carfentrazone, carfentrazone-ethyl, sulfentrazone, amitrole, paclobutrazol, uniconazole, uniconazole-P, cafenstrole, fentrazamide,
B5 other herbicides comprising
allidochlor, aminocyclopyrachlor, aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, N-acetylthiazolidine-4-carboxylic acid, aminopyralid, ammonium pelargonate, ammonium sulfamate, aviglycine, benazolin, benazolin-ethyl, benfluralin, benfuresate, bentazone, benzobicyclon, 6-benzylaminopurine, brassinolide, bromofenoxim, butralin, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlormequat chloride, chlorphthalim, chlorthal-dimethyl, cinidon, cinidon-ethyl, cinmethylin, clofencet, clomazone, cloxyfonac, cyanamide, cyclanilide, cyclopyrimorate, 6-isopentylaminopurine, kinetin, zeatin, dalapon, daminozide, dazomet, n-decanol, difenzoquat metilsulfate, 2,6-diisopropylnaphthalene, dikegulac, dikegulac-sodium, dimethipin, dinitramine, dinoterb, diquat, diquat dibromide, dithiopyr, DNOC, endothal, endothal-dipotassium, endothal-disodium, endothal-mono(N,N-dimethylalkylammonium), ethafluralin, ethofumesate, ethylchlozate, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, fluchloralin, flufenpyr, flufenpyr-ethyl, flumetralin, flumichlorac, flumiclorac-pentyl, flumioxazin, flupropanate, flurenol, flurenol-butyl, flurenol-dimethylammonium-methyl, fluridone, flurochloridone, flurtamone, fluthiacet, fluthiacet-methyl, gibberillic acid, halauxifen, indanofan, isoprothiolane, maleic hydrazide, mepiquat chloride, metam, methiozolin, methylarsonic acid, 1-methylcyclopropene, methyl isothiocyanate, nitrophenolate mixture, nonanoic acid, norflurazon, oleic acid, oryzalin, oxaziclomefone, paraquat, paraquat dichloride, pendimethalin, pentachlorophenol, pentoxazone, petroleum oils, prodiamine, n-propyl dihydrojasmonate, pyridafol, pyridate, quinoclamine, sintofen, TCA, TCA sodium, tecnazene, thiazopyr, triacontanol, triafamone, trifluralin, urea sulfate,
B6 (het)arylcarboxylic acids comprising
chloramben, dicamba, 2,3,6-TBA, clopyralid, fluroxypyr, fluroxypyr-meptyl, inabenfide, picloram, triclopyr, quinclorac, quinmerac, indol-3-ylacetic acid, 4-indol-3-yl-butyric acid, 2-(1-naphthyl)acetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid,
B7 organic phosphorus compounds comprising
anilofos, bensulide, bilanafos, bilanafos-sodium, butamifos, clacyfos, fosamine, glufosinate, glufosinate salts, glufosinate-ammonium, glufosinate-sodium, glufosinate-P, L-glufosinate-ammonium, L-glufosinate-sodium, glyphosate, glyphosate salts, glyphosate-isopropyl-ammonium, glyphosate-ammonium, glyphosate-dimethylammonium, glyphosate-trimesium (=sulfosate), glyphosate-diammonium, glyphosate-potassium, glyphosate-sodium, piperophos, ethephon, tribufos,
B8 phenyl ethers comprising
acifluorfen-sodium, aclonifen, fluoroglycofen, fluoroglycofen-ethyl, fomesafen, fomesafen-sodium, halosafen, lactofen, oxyfluorfen, acifluorfen, bifenox, ethoxyfen-ethyl, clomeprop, cloprop, dichlorprop, dichlorprop-P, mecoprop, mecoprop-sodium, mecoprop-butotyl, mecoprop-P, mecoprop-P-butotyl, mecoprop-P-dimethylammonium, mecoprop-P-2-ethylhexyl, mecoprop-P-patassium, 4-CPA, 2,4-D, 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-dimethylammonium, 2,4-D-diolamine, 2,4-D-ethyl, 2,4-D-2-ethylhexyl, 2,4-D-isobutyl, 2,4-D-isooctyl, 2,4-D-isopropylammonium, 2,4-D-potassium, 2,4-D-triisopropanolammonium, 2,4-D-trolamine, MCPA, MCPA-butotyl, MCPA-dimethylammonium, MCPA-2-ethylhexyl, MCPA-isopropylammonium, MCPA-potassium, MCPA-sodium, 2,4-DB, MCPB, MCPB-methyl, MCPB-ethyl-sodium, clodinafop-ethyl, clodinafop-propargyl, cyhalofop, cyhalofop-butyl, diclofop, diclofop-P, diclofop-methyl, diclofop-P-methyl, fenoxaprop, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, haloxyfop, haloxyfop-P, metamifop, propaquizafop quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl,
B9 pyrimidines, comprising
ancymidol, flurprimidol, pyrimisulfan, bispyribac, bispyribac-sodium, pyribenzoxim, pyriminobac, pyriminobac-methyl, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyriftalid, pyrithiobac, pyrithiobac-sodium, bromacil, butafenacil, lenacil, saflufenacil, terbacil, tifenacil, 2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1 (2H)-yl]-N-[methyl(1-methylethyl)sulfamoyl]benzamide, ethyl [(3-{2-chloro-5-[2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1 (2H)-yl]-4-fluorophenoxy}pyridin-2-yl)oxy]acetate,
B10 (thio)ureas comprising
cumyluron, chlorbromuron, chlorotoluron, daimuron, diflufenzopyr, diflufenzopyr-sodium, dimefuron, diuron, fluometuron, forchlorfenuron, isoproturon, karbutilate, linuron, metobromuron, metoxuron, monolinuron, neburon, siduron, terbucarb, thidiazuron, tebuthiuron, methabenzthiazuron,
B11 triazines comprising
triaziflam, indaziflam, atrazine, cyanazine, cyprazine, propazine, simazine, terbumeton, terbuthylazine, trietazine, prometon, ametryn, dimethametryn, prometryn, simetryn, terbutryn, ethiozin, hexazinon, metamitron, metribuzin.
In a further embodiment, these herbicidal compositions comprise (C) one or more safeners (component C) from the group consisting of benoxacor (C1), cloquintocet-mexyl (C2), cyprosulfamide (C3), dichlormid (C4), fenclorim (C5), fenchlorazole (C6), furilazole (C7), isoxadifen-ethyl (C8), mefenpyr-diethyl (C9), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (CAS 71526-07-3) (C10), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (CAS 52836-31-4) (C11), 2-methoxy-N-({4-[(methylcarbamoyl)amino]phenyl}sulfonyl)benzamide (CAS 129531-12-0) (C12).
Components B) and C) are known, for example, from “The Pesticide Manual”, 16th edition, 2012, The British Crop Protection Council and the Royal Soc. of Chemistry.
The inventive herbicidal compositions may comprise or be used together with additional further components, for example other kinds of active crop protection ingredients and/or additives and/or formulation auxiliaries customary in crop protection.
The herbicides (A), (B) and optionally the safeners (C) can be applied in a known manner, for example together (for example as a co-formulation or as a tank-mix) or else at different times in short succession (splitting), for example to the plants, plant parts, plant seeds or the area on which the plants grow. It is possible, for example, to apply the individual active ingredients or the herbicide-safener combination in several portions (sequential application), for example by pre-emergence applications followed by post-emergence applications, or by early post-emergence applications followed by post-emergence applications at an intermediate or late stage. Preference is given to the joint or immediately successive application of the active ingredients in the respective combination. It is also possible to use the individual active ingredients or the herbicide-safener combination for seed treatment.
Preference is given to those inventive compositions which comprise, as herbicide (A), compounds of the general formula (I) and salts thereof in which
A is N or CY,
R is hydrogen, (C1-C6)-alkyl, (C3-C7)-cycloalkyl, halo-(C1-C6)-alkyl, (C3-C7)-cycloalkylmethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, acetylmethyl, methoxymethyl, methoxyethyl, benzyl, pyrazin-2-yl, furan-2-yl, tetrahydrofuran-2-yl, morpholine, dimethylamino, or phenyl substituted by s radicals from the group of methyl, methoxy, trifluoromethyl and halogen;
X is nitro, halogen, cyano, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, (C3-C6)-cycloalkyl, OR1, S(O)nR2, (C1-C6)-alkyl-S(O)nR2, (C1-C6)-alkyl-OR1, (C1-C6)-alkyl-CON(R1)2, (C1-C6)-alkyl-SO2N(R1)2, (C1-C6)-alkyl-NR1COR1, (C1-C6)-alkyl-NR1SO2R2, (C1-C6)-alkylheteroaryl, (C1-C6)-alkylheterocyclyl, where the two latter radicals are each substituted by s halogen, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, S(O)n—(C1-C6)-alkyl, (C1-C6)-alkoxy, halo-(C1-C6)-alkoxy radicals, and where heterocyclyl bears n oxo groups,
Y hydrogen, nitro, halogen, cyano, (C1-C6)-alkyl, (C1-C6)-haloalkyl, OR1, S(O)nR2, SO2N(R1)2, N(R1)2, NR1SO2R2, NR1COR1, (C1-C6)-alkyl-S(O)nR2, (C1-C6)-alkyl-OR1, (C1-C6)-alkyl-CON(R1)2, (C1-C6)-alkyl-SO2N(R1)2, (C1-C6)-alkyl-NR1COR1, (C1-C6)-alkyl-NR1SO2R2, (C1-C6)-alkylphenyl, (C1-C6)-alkylheteroaryl, (C1-C6)-alkylheterocyclyl, phenyl, heteroaryl or heterocyclyl, where the 6 latter radicals are each substituted by s radicals from the group consisting of halogen, nitro, cyano, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, (C3-C6)-cycloalkyl, S(O)n—(C1-C6)-alkyl, (C1-C6)-alkoxy, halo-(C1-C6)-alkoxy, (C1-C6)-alkoxy-(C1-C4)-alkyl and cyanomethyl, and where heterocyclyl bears n oxo groups,
Z is halogen, cyano, nitro, methyl, halo-(C1-C6)-alkyl, (C3-C6)-cycloalkyl, S(O)nR2, 1,2,4-triazol-1-yl, pyrazol-1-yl, or
Z may also be hydrogen if Y is the S(O)nR2 radical,
R1 is hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C3-C6)-cycloalkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, (C1-C6)-alkyl-O—(C1-C6)-alkyl, phenyl, phenyl-(C1-C6)-alkyl, heteroaryl, (C1-C6)-alkylheteroaryl, heterocyclyl, (C1-C6)-alkylheterocyclyl, (C1-C6)-alkyl-O-heteroaryl, (C1-C6)-alkyl-O-heterocyclyl, (C1-C6)-alkyl-NR3-heteroaryl or (C1-C6)-alkyl-NR3-heterocyclyl, where the 16 latter radicals are substituted by s radicals from the group consisting of cyano, halogen, nitro, OR3, S(O)nR4, N(R3)2, NR3OR3, COR3, OCOR3, NR3COR3, NR3SO2R4, COO2R3, CON(R3)2 and (C1-C4)-alkoxy-(C2-C6)-alkoxycarbonyl, and where heterocyclyl bears n oxo groups,
R2 is (C1-C6)-alkyl, (C3-C6)-cycloalkyl or (C3-C6)-cycloalkyl-(C1-C6)-alkyl, where these three aforementioned radicals are each substituted by s radicals from the group consisting of halogen and OR3,
R3 is hydrogen or (C1-C6)-alkyl,
R4 is (C1-C6)-alkyl,
n is 0, 1 or 2,
s is 0, 1, 2 or 3.
Particular preference is given to inventive compositions which comprise, as herbicide (A), compounds of the general formula (I) and salts thereof in which
A is N or CY,
R is hydrogen, (C1-C4)-alkyl, cyclopropyl, halo-(C1-C4)-alkyl, (C3-C6)-cycloalkylmethyl, methoxymethyl, methoxyethyl, benzyl,
X is nitro, halogen, cyano, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, cyclopropyl, OR1, S(O)nR2, (C1-C6)-alkyl-S(O)nR2, (C1-C5)-alkyl-OR1, (C1-C2)-alkylheteroaryl, (C1-C2)-alkylheterocyclyl, where the two latter radicals are each substituted by s halogen, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, S(O)n—(C1-C6)-alkyl, (C1-C6)-alkoxy, halo-(C1-C6)-alkoxy radicals, and where heterocyclyl bears n oxo groups,
Y hydrogen, nitro, halogen, cyano, (C1-C6)-alkyl, (C1-C6)-haloalkyl, OR1, S(O)nR2, SO2N(R1)2, N(R1)2, NR1SO2R2, NR1COR1, (C1-C6)-alkyl-S(O)nR2, (C1-C6)-alkyl-OR1, (C1-C6)-alkyl-CON(R1)2, (C1-C6)-alkyl-SO2N(R1)2, (C1-C6)-alkyl-NR1COR1, (C1-C6)-alkyl-NR1SO2R2, (C1-C6)-alkylphenyl, (C1-C6)-alkylheteroaryl, (C1-C6)-alkylheterocyclyl, phenyl, heteroaryl or heterocyclyl, where the 6 latter radicals are each substituted by s radicals from the group consisting of halogen, nitro, cyano, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, (C3-C6)-cycloalkyl, S(O)n—(C1-C6)-alkyl, (C1-C6)-alkoxy, halo-(C1-C6)-alkoxy, (C1-C6)-alkoxy-(C1-C4)-alkyl and cyanomethyl, and where heterocyclyl bears n oxo groups,
Z is halogen, cyano, nitro, methyl, halo-(C1-C6)-alkyl, (C3-C6)-cycloalkyl, S(O)nR2, 1,2,4-triazol-1-yl, pyrazol-1-yl, or
R1 is hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C3-C6)-cycloalkyl, (C3-C6)-cycloalkyl-(C1-C6)-alkyl, (C1-C6)-alkyl-O—(C1-C6)-alkyl, phenyl, phenyl-(C1-C6)-alkyl, heteroaryl, (C1-C6)-alkylheteroaryl, heterocyclyl, (C1-C6)-alkylheterocyclyl, (C1-C6)-alkyl-O-heteroaryl, (C1-C6)-alkyl-O-heterocyclyl, (C1-C6)-alkyl-NR3-heteroaryl or (C1-C6)-alkyl-NR3-heterocyclyl, where the 16 latter radicals are substituted by s radicals from the group consisting of cyano, halogen, nitro, OR3, S(O)nR4, N(R3)2, NR3OR3, COR3, OCOR3, NR3COR3, NR3SO2R4, CO2R3, CON(R3)2 and (C1-C4)-alkoxy-(C2-C6)-alkoxycarbonyl, and where heterocyclyl bears n oxo groups,
R2 is (C1-C6)-alkyl, (C3-C6)-cycloalkyl or (C3-C6)-cycloalkyl-(C1-C6)-alkyl, where these three aforementioned radicals are each substituted by s radicals from the group consisting of halogen and OR3,
R3 is hydrogen or (C1-C6)-alkyl,
R4 is (C1-C6)-alkyl,
n is 0, 1 or 2,
s is 0, 1, 2 or 3.
In the formula (I) and all the formulae which follow, alkyl radicals having more than two carbon atoms may be straight-chain or branched. Alkyl radicals are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls such as n-hexyl, i-hexyl and 1,3-dimethylbutyl. Analogously, alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl. Alkynyl is, for example, propargyl, but-2-yn-1-yl, but-3-ynl-yl, 1-methylbut-3-yn-1-yl. The multiple bond may be in any position in each unsaturated radical. Cycloalkyl is a carbocyclic saturated ring system having three to six carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Analogously, cycloalkenyl is a monocyclic alkenyl group having three to six carbon ring members, for example cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, where the double bond may be in any position.
Halogen is fluorine, chlorine, bromine or iodine.
Heterocyclyl is a saturated, partly saturated or fully unsaturated cyclic radical which contains 3 to 6 ring atoms, of which 1 to 4 are from the group of oxygen, nitrogen and sulfur, and which may additionally be fused by a benzo ring. For example, heterocyclyl is piperidinyl, pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl and oxetanyl.
Heteroaryl is an aromatic cyclic radical which contains 3 to 6 ring atoms, of which 1 to 4 are from the group of oxygen, nitrogen and sulfur, and which may additionally be fused by a benzo ring. Heteroaryl represents, for example, benzimidazol-2-yl, furanyl, imidazolyl, isoxazolyl, isothiazolyl, oxazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridinyl, benzisoxazolyl, thiazolyl, pyrrolyl, pyrazolyl, thiophenyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl, 1,2,5-triazolyl, 1,3,4-triazolyl, 1,2,4-triazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3-thiadiazolyl, 1,2,5-thiadiazolyl, 2H-1,2,3,4-tetrazolyl, 1H-1,2,3,4-tetrazolyl, 1,2,3,4-oxatriazolyl, 1,2,3,5-oxatriazolyl, 1,2,3,4-thiatriazolyl and 1,2,3,5-thiatriazolyl.
When a group is polysubstituted by radicals, this means that this group is substituted by one or more identical or different radicals from those mentioned. The same applies to the formation of ring systems by different atoms and elements. At the same time, the scope of the claims shall exclude those compounds known by the person skilled in the art to be chemically unstable under standard conditions.
The present invention also provides herbicidal compositions comprising stereoisomers and mixtures thereof which are encompassed by formula (I) or by the formulae of component B. Such compounds of the formula (I) or of the formulae of component B contain, for example, one or more asymmetrically substituted carbon atoms or sulfoxides. The possible stereoisomers defined by the specific three-dimensional shape thereof, such as enantiomers and diastereomers, are all encompassed by the formula (I) or by components (B) and (C); especially also the racemic mixtures and—where enantiomers are possible—both enantiomers and especially the respective biologically active enantiomer. The individual stereoisomers can be obtained by customary methods from mixtures of the stereoisomers or else be prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials or auxiliaries.
Examples of compounds very particularly preferred as herbicide (A) are listed in the tables which follow.
In these tables, the abbreviations used mean:
Preferred herbicides of group B1 are clethodim, sethoxydim, tepraloxydim, mesotrione, sulcotrione, tefuryltrione, tembotrione, bicyclopyrone, pinoxaden, tralkoxydim. Particularly preferred herbicides of group B1 are clethodim (B1-1), sulcotrione (B1-2), tefuryltrione (B1-3), tembotrione (B1-4), bicyclopyrone (B1-5), pinoxaden (B1-6).
Preferred herbicides of group B2 are dimethenamide, dimethenamide-P, napropamide, pethoxamid, propyzamide, diflufenican, flufenacet, mefenacet, picolinafen, propanil, acetochlor, alachlor, butachlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, thenylchlor, asulam, carbetamide, desmedipham, phenmedipham, esprocarb, molinate, prosulfocarb, thiobencarb, amidosulfuron, chlorimuron-ethyl, cyclosulfamuron, ethoxysulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, iodosulfuron-methyl-sodium, mesosulfuron-methyl, nicosulfuron, orthosulfamuron, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, trifloxysulfuron (sodium), flucarbazone-sodium, propoxycarbazone-sodium, thiencarbazone-methyl, florasulam, metosulam, penoxsulam, metsulfuron-methyl, sulfosulfuron, thifensulfuron-methyl, tribenuron-methyl, tritosulfuron, pyroxsulam.
Particularly preferred herbicides of group B2 are dimethenamide-P (B2-1), napropamide (B2-2), diflufenican (B2-3), flufenacet (B2-4), mefenacet (B2-5), acetochlor (B2-6), metazachlor (B2-7), S-metolachlor (B2-8), asulam (B2-9), desmedipham (B2-10), phenmedipham (B2-11), molinate (B2-12), prosulfocarb (B2-13), amidosulfuron (B2-14), ethoxysulfuron (B2-15), foramsulfuron (B2-16), iodosulfuron-methyl-sodium (B2-17), mesosulfuron-methyl (B2-18), flucarbazone-sodium (B2-19), propoxycarbazone-sodium (B2-20), thiencarbazone-methyl (B2-21), florasulam (B2-22), metosulam (B2-23), metsulfuron-methyl (B2-24), sulfosulfuron (B2-25), thifensulfuron-methyl (B2-26), tribenuron-methyl (B2-27), tritosulfuron (B2-28), pyroxsulam (B2-29).
Preferred herbicides of group B3 are bromoxynil (B3-1) and ioxynil (B3-2).
Preferred herbicides of group B4 are benzofenap, topramezone, pyrasulfotole, isoxaflutole, imazamox, imazethapyr, oxadiargyl, oxadiazon, amicarbazone, carfentrazone-ethyl, sulfentrazone, uniconazole, cafenstrole, fentrazamide, 3-(3-chloro-5-{[1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy}phenoxy)-1-methyl-5-(trifluoromethyl)-1H-pyrazole, 3-(3-iodo-5-{[1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy}phenoxy)-1-methyl-5-(trifluoromethyl)-1H-pyrazole, 1-ethyl-3-(3-fluoro-5-{[1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy}phenoxy)-5-(trifluoromethyl)-1H-pyrazole, pyraflufen-ethyl.
Particularly preferred herbicides of group B4 are pyrasulfotole (B4-1), isoxaflutole (B4-2), oxadiargyl (B4-3), oxadiazon (B4-4), amicarbazone (B4-5), fentrazamide (B4-6), 3-(3-chloro-5-{[1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy}phenoxy)-1-methyl-5-(trifluoromethyl)-1H-pyrazole (B4-7), 3-(3-iodo-5-{[1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy}phenoxy)-1-methyl-5-(trifluoromethyl)-1H-pyrazole (B4.8), 1-ethyl-3-(3-fluoro-5-{[1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy}phenoxy)-5-(trifluoromethyl)-1H-pyrazole (B4-9), pyraflufen-ethyl (B4-10), imazamox (B4-11).
Preferred herbicides of group B5 are aminopyralid, benazolin, benfuresate, bentazone, cinidon-ethyl, clomazone, diquat dibromide, ethofumesate, flumiclorac-pentyl, flumioxazin, flurtamone, oxaziclomefone, pendimethalin, pyridate and trifluralin. Particularly preferred herbicides of group B5 are aminopyralid (B5-1), benfuresate (B5-2), ethofumesate (B5-3), flurtamone (B5-4) and oxaziclomefone (B5-5). Preferred herbicides of group B6 are dicamba (B6-1), clopyralid (B6-2), fluroxypyr (B6-3), picloram (B6-4), triclopyr (B6-5), quinclorac (B6-6).
Preferred herbicides of group B7 are anilofos (B7-1), glufosinate-ammonium (B7-2), L-glufosinate-ammonium (B7-3), glyphosate (B7-4), glyphosate-isopropyl-ammonium (B7-5), glyphosate-ammonium (B7-6), glyphosate-trimesium (=sulfosate (B7-7)), glyphosate-diammonium (B7-7), glyphosate-potassium (B7-8).
Preferred herbicides of group B8 are acifluorfen-sodium, aclonifen, fluoroglycofen-ethyl, oxyfluorfen, bifenox, dichlorprop-P, mecoprop-P, 2,4-D, MCPA, clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, diclofop-P-methyl, fenoxaprop-P-ethyl, fluazifop-P-butyl, quizalofop-P.
Particularly preferred herbicides of group B8 are aclonifen (B8-1), diclofop-methyl (B8-2), diclofop-P-methyl (B8-3), fenoxaprop-P-ethyl (B8-4), MCPA (B8-5), 2,4-D (B8-6), clodinafop-ethyl (B8-7).
Preferred herbicides of group B9 are bispyribac (sodium), pyriftalid, bromacil, lenacil, 2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1 (2H)-yl]-N-[methyl(1-methylethyl)sulfamoyl]benzamide. Particularly preferred herbicides of group B9 are bispyribac (sodium) (B9-1), bromacil (B9-2).
Preferred herbicides of group B10 are cumyluron (B10-1), daimuron (B10-2), diuron (B10-3), isoproturon (B10-4), diflufenzopyr (B10-5).
Preferred herbicides of group B11 are atrazine, simazine, terbuthylazine, ametryn, terbutryn, metamitron, metribuzin.
Particularly preferred herbicides of group B11 are metamitron (B11-1), metribuzin (B11-2), terbuthylazine (B11-2).
Examples of preferred compositions of herbicides (A) and herbicides (B) are given below.
(A1-1)+(B1-1), (A1-1)+(B1-2), (A1-1)+(B1-3), (A1-1)+(B1-4), (A1-1)+(B1-5), (A1-1)+(B1-6), (A1-1)+(B2-1), (A1-1)+(B2-2), (A1-1)+(B2-3), (A1-1)+(B2-4), (A1-1)+(B2-5), (A1-1)+(B2-6), (A1-1)+(B2-7), (A1-1)+(B2-8), (A1-1)+(B2-9), (A1-1)+(B2-10), (A1-1)+(B2-11), (A1-1)+(B2-12), (A1-1)+(B2-13), (A1-1)+(B2-14), (A1-1)+(B2-15), (A1-1)+(B2-16), (A1-1)+(B2-17), (A1-1)+(B2-18), (A1-1)+(B2-19), (A1-1)+(B2-20), (A1-1)+(B2-21), (A1-1)+(B2-22), (A1-1)+(B2-23), (A1-1)+(B2-24), (A1-1)+(B2-25), (A1-1)+(B2-26), (A1-1)+(B2-27), (A1-1)+(B2-28), (A1-1)+(B2-29), (A1-1)+(B3-1), (A1-1)+(B3-2), (A1-1)+(B4-1), (A1-1)+(B4-2), (A1-1)+(B4-3), (A1-1)+(B4-4), (A1-1)+(B4-5), (A1-1)+(B4-6), (A1-1)+(B4-7), (A1-1)+(B4-8), (A1-1)+(B4-9), (A1-1)+(B4-10), (A1-1)+(B4-11), (A1-1)+(B5-1), (A1-1)+(B5-2), (A1-1)+(B5-3), (A1-1)+(B5-4), (A1-1)+(B5-5), (A1-1)+(B6-1), (A1-1)+(B6-2), (A1-1)+(B6-3), (A1-1)+(B6-4), (A1-1)+(B6-5), (A1-1)+(B6-6), (A1-1)+(B7-1), (A1-1)+(B7-2), (A1-1)+(B7-3), (A1-1)+(B7-4), (A1-1)+(B7-5), (A1-1)+(B7-6), (A1-1)+(B7-7)), (A1-1)+(B7-7), (A1-1)+(B7-8), (A1-1)+(B8-1), (A1-1)+(B8-2), (A1-1)+(B8-3), (A1-1)+(B8-4), (A1-1)+(B8-5), (A1-1)+(B8-6), (A1-1)+(B8-7), (A1-1)+(B9-1), (A1-1)+(B9-2), (A1-1)+(B10-1), (A1-1)+(B10-2), (A1-1)+(B10-3), (A1-1)+(B10-4), (A1-1)+(B10-5), (A1-1)+(B11-1), (A1-1)+(B11-2), (A1-1)+(B11-2),
(A1-2)+(B1-1), (A1-2)+(B1-2), (A1-2)+(B1-3), (A1-2)+(B1-4), (A1-2)+(B1-5), (A1-2)+(B1-6), (A1-2)+(B2-1), (A1-2)+(B2-2), (A1-2)+(B2-3), (A1-2)+(B2-4), (A1-2)+(B2-5), (A1-2)+(B2-6), (A1-2)+(B2-7), (A1-2)+(B2-8), (A1-2)+(B2-9), (A1-2)+(B2-10), (A1-2)+(B2-11), (A1-2)+(B2-12), (A1-2)+(B2-13), (A1-2)+(B2-14), (A1-2)+(B2-15), (A1-2)+(B2-16), (A1-2)+(B2-17), (A1-2)+(B2-18), (A1-2)+(B2-19), (A1-2)+(B2-20), (A1-2)+(B2-21), (A1-2)+(B2-22), (A1-2)+(B2-23), (A1-2)+(B2-24), (A1-2)+(B2-25), (A1-2)+(B2-26), (A1-2)+(B2-27), (A1-2)+(B2-28), (A1-2)+(B2-29), (A1-2)+(B3-1), (A1-2)+(B3-2), (A1-2)+(B4-1), (A1-2)+(B4-2), (A1-2)+(B4-3), (A1-2)+(B4-4), (A1-2)+(B4-5), (A1-2)+(B4-6), (A1-2)+(B4-7), (A1-2)+(B4-8), (A1-2)+(B4-9), (A1-2)+(B4-10), (A1-2)+(B4-11), (A1-2)+(B5-1), (A1-2)+(B5-2), (A1-2)+(B5-3), (A1-2)+(B5-4), (A1-2)+(B5-5), (A1-2)+(B6-1), (A1-2)+(B6-2), (A1-2)+(B6-3), (A1-2)+(B6-4), (A1-2)+(B6-5), (A1-2)+(B6-6), (A1-2)+(B7-1), (A1-2)+(B7-2), (A1-2)+(B7-3), (A1-2)+(B7-4), (A1-2)+(B7-5), (A1-2)+(B7-6), (A1-2)+(B7-7)), (A1-2)+(B7-7), (A1-2)+(B7-8), (A1-2)+(B8-1), (A1-2)+(B8-2), (A1-2)+(B8-3), (A1-2)+(B8-4), (A1-2)+(B8-5), (A1-2)+(B8-6), (A1-2)+(B8-7), (A1-2)+(B9-1), (A1-2)+(B9-2), (A1-2)+(B10-1), (A1-2)+(B10-2), (A1-2)+(B10-3), (A1-2)+(B10-4), (A1-2)+(B10-5), (A1-2)+(B11-1), (A1-2)+(B11-2), (A1-2)+(B11-2),
(A1-3)+(B1-1), (A1-3)+(B1-2), (A1-3)+(B1-3), (A1-3)+(B1-4), (A1-3)+(B1-5), (A1-3)+(B1-6), (A1-3)+(B2-1), (A1-3)+(B2-2), (A1-3)+(B2-3), (A1-3)+(B2-4), (A1-3)+(B2-5), (A1-3)+(B2-6), (A1-3)+(B2-7), (A1-3)+(B2-8), (A1-3)+(B2-9), (A1-3)+(B2-10), (A1-3)+(B2-11), (A1-3)+(B2-12), (A1-3)+(B2-13), (A1-3)+(B2-14), (A1-3)+(B2-15), (A1-3)+(B2-16), (A1-3)+(B2-17), (A1-3)+(B2-18), (A1-3)+(B2-19), (A1-3)+(B2-20), (A1-3)+(B2-21), (A1-3)+(B2-22), (A1-3)+(B2-23), (A1-3)+(B2-24), (A1-3)+(B2-25), (A1-3)+(B2-26), (A1-3)+(B2-27), (A1-3)+(B2-28), (A1-3)+(B2-29), (A1-3)+(B3-1), (A1-3)+(B3-2), (A1-3)+(B4-1), (A1-3)+(B4-2), (A1-3)+(B4-3), (A1-3)+(B4-4), (A1-3)+(B4-5), (A1-3)+(B4-6), (A1-3)+(B4-7), (A1-3)+(B4-8), (A1-3)+(B4-9), (A1-3)+(B4-10), (A1-3)+(B4-11), (A1-3)+(B5-1), (A1-3)+(B5-2), (A1-3)+(B5-3), (A1-3)+(B5-4), (A1-3)+(B5-5), (A1-3)+(B6-1), (A1-3)+(B6-2), (A1-3)+(B6-3), (A1-3)+(B6-4), (A1-3)+(B6-5), (A1-3)+(B6-6), (A1-3)+(B7-1), (A1-3)+(B7-2), (A1-3)+(B7-3), (A1-3)+(B7-4), (A1-3)+(B7-5), (A1-3)+(B7-6), (A1-3)+(B7-7)), (A1-3)+(B7-7), (A1-3)+(B7-8), (A1-3)+(B8-1), (A1-3)+(B8-2), (A1-3)+(B8-3), (A1-3)+(B8-4), (A1-3)+(B8-5), (A1-3)+(B8-6), (A1-3)+(B8-7), (A1-3)+(B9-1), (A1-3)+(B9-2), (A1-3)+(B10-1), (A1-3)+(B10-2), (A1-3)+(B10-3), (A1-3)+(B10-4), (A1-3)+(B10-5), (A1-3)+(B11-1), (A1-3)+(B11-2), (A1-3)+(B11-2),
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(A1-5)+(B1-1), (A1-5)+(B1-2), (A1-5)+(B1-3), (A1-5)+(B1-4), (A1-5)+(B1-5), (A1-5)+(B1-6), (A1-5)+(B2-1), (A1-5)+(B2-2), (A1-5)+(B2-3), (A1-5)+(B2-4), (A1-5)+(B2-5), (A1-5)+(B2-6), (A1-5)+(B2-7), (A1-5)+(B2-8), (A1-5)+(B2-9), (A1-5)+(B2-10), (A1-5)+(B2-11), (A1-5)+(B2-12), (A1-5)+(B2-13), (A1-5)+(B2-14), (A1-5)+(B2-15), (A1-5)+(B2-16), (A1-5)+(B2-17), (A1-5)+(B2-18), (A1-5)+(B2-19), (A1-5)+(B2-20), (A1-5)+(B2-21), (A1-5)+(B2-22), (A1-5)+(B2-23), (A1-5)+(B2-24), (A1-5)+(B2-25), (A1-5)+(B2-26), (A1-5)+(B2-27), (A1-5)+(B2-28), (A1-5)+(B2-29), (A1-5)+(B3-1), (A1-5)+(B3-2), (A1-5)+(B4-1), (A1-5)+(B4-2), (A1-5)+(B4-3), (A1-5)+(B4-4), (A1-5)+(B4-5), (A1-5)+(B4-6), (A1-5)+(B4-7), (A1-5)+(B4-8), (A1-5)+(B4-9), (A1-5)+(B4-10), (A1-5)+(B4-11), (A1-5)+(B5-1), (A1-5)+(B5-2), (A1-5)+(B5-3), (A1-5)+(B5-4), (A1-5)+(B5-5), (A1-5)+(B6-1), (A1-5)+(B6-2), (A1-5)+(B6-3), (A1-5)+(B6-4), (A1-5)+(B6-5), (A1-5)+(B6-6), (A1-5)+(B7-1), (A1-5)+(B7-2), (A1-5)+(B7-3), (A1-5)+(B7-4), (A1-5)+(B7-5), (A1-5)+(B7-6), (A1-5)+(B7-7)), (A1-5)+(B7-7), (A1-5)+(B7-8), (A1-5)+(B8-1), (A1-5)+(B8-2), (A1-5)+(B8-3), (A1-5)+(B8-4), (A1-5)+(B8-5), (A1-5)+(B8-6), (A1-5)+(B8-7), (A1-5)+(B9-1), (A1-5)+(B9-2), (A1-5)+(B10-1), (A1-5)+(B10-2), (A1-5)+(B10-3), (A1-5)+(B10-4), (A1-5)+(B10-5), (A1-5)+(B11-1), (A1-5)+(B11-2), (A1-5)+(B11-2),
(A1-6)+(B1-1), (A1-6)+(B1-2), (A1-6)+(B1-3), (A1-6)+(B1-4), (A1-6)+(B1-5), (A1-6)+(B1-6), (A1-6)+(B2-1), (A1-6)+(B2-2), (A1-6)+(B2-3), (A1-6)+(B2-4), (A1-6)+(B2-5), (A1-6)+(B2-6), (A1-6)+(B2-7), (A1-6)+(B2-8), (A1-6)+(B2-9), (A1-6)+(B2-10), (A1-6)+(B2-11), (A1-6)+(B2-12), (A1-6)+(B2-13), (A1-6)+(B2-14), (A1-6)+(B2-15), (A1-6)+(B2-16), (A1-6)+(B2-17), (A1-6)+(B2-18), (A1-6)+(B2-19), (A1-6)+(B2-20), (A1-6)+(B2-21), (A1-6)+(B2-22), (A1-6)+(B2-23), (A1-6)+(B2-24), (A1-6)+(B2-25), (A1-6)+(B2-26), (A1-6)+(B2-27), (A1-6)+(B2-28), (A1-6)+(B2-29), (A1-6)+(B3-1), (A1-6)+(B3-2), (A1-6)+(B4-1), (A1-6)+(B4-2), (A1-6)+(B4-3), (A1-6)+(B4-4), (A1-6)+(B4-5), (A1-6)+(B4-6), (A1-6)+(B4-7), (A1-6)+(B4-8), (A1-6)+(B4-9), (A1-6)+(B4-10), (A1-6)+(B4-11), (A1-6)+(B5-1), (A1-6)+(B5-2), (A1-6)+(B5-3), (A1-6)+(B5-4), (A1-6)+(B5-5), (A1-6)+(B6-1), (A1-6)+(B6-2), (A1-6)+(B6-3), (A1-6)+(B6-4), (A1-6)+(B6-5), (A1-6)+(B6-6), (A1-6)+(B7-1), (A1-6)+(B7-2), (A1-6)+(B7-3), (A1-6)+(B7-4), (A1-6)+(B7-5), (A1-6)+(B7-6), (A1-6)+(B7-7)), (A1-6)+(B7-7), (A1-6)+(B7-8), (A1-6)+(B8-1), (A1-6)+(B8-2), (A1-6)+(B8-3), (A1-6)+(B8-4), (A1-6)+(B8-5), (A1-6)+(B8-6), (A1-6)+(B8-7), (A1-6)+(B9-1), (A1-6)+(B9-2), (A1-6)+(B10-1), (A1-6)+(B10-2), (A1-6)+(B10-3), (A1-6)+(B10-4), (A1-6)+(B10-5), (A1-6)+(B11-1), (A1-6)+(B11-2), (A1-6)+(B11-2),
(A1-7)+(B1-1), (A1-7)+(B1-2), (A1-7)+(B1-3), (A1-7)+(B1-4), (A1-7)+(B1-5), (A1-7)+(B1-6), (A1-7)+(B2-1), (A1-7)+(B2-2), (A1-7)+(B2-3), (A1-7)+(B2-4), (A1-7)+(B2-5), (A1-7)+(B2-6), (A1-7)+(B2-7), (A1-7)+(B2-8), (A1-7)+(B2-9), (A1-7)+(B2-10), (A1-7)+(B2-11), (A1-7)+(B2-12), (A1-7)+(B2-13), (A1-7)+(B2-14), (A1-7)+(B2-15), (A1-7)+(B2-16), (A1-7)+(B2-17), (A1-7)+(B2-18), (A1-7)+(B2-19), (A1-7)+(B2-20), (A1-7)+(B2-21), (A1-7)+(B2-22), (A1-7)+(B2-23), (A1-7)+(B2-24), (A1-7)+(B2-25), (A1-7)+(B2-26), (A1-7)+(B2-27), (A1-7)+(B2-28), (A1-7)+(B2-29), (A1-7)+(B3-1), (A1-7)+(B3-2), (A1-7)+(B4-1), (A1-7)+(B4-2), (A1-7)+(B4-3), (A1-7)+(B4-4), (A1-7)+(B4-5), (A1-7)+(B4-6), (A1-7)+(B4-7), (A1-7)+(B4-8), (A1-7)+(B4-9), (A1-7)+(B4-10), (A1-7)+(B4-11), (A1-7)+(B5-1), (A1-7)+(B5-2), (A1-7)+(B5-3), (A1-7)+(B5-4), (A1-7)+(B5-5), (A1-7)+(B6-1), (A1-7)+(B6-2), (A1-7)+(B6-3), (A1-7)+(B6-4), (A1-7)+(B6-5), (A1-7)+(B6-6), (A1-7)+(B7-1), (A1-7)+(B7-2), (A1-7)+(B7-3), (A1-7)+(B7-4), (A1-7)+(B7-5), (A1-7)+(B7-6), (A1-7)+(B7-7)), (A1-7)+(B7-7), (A1-7)+(B7-8), (A1-7)+(B8-1), (A1-7)+(B8-2), (A1-7)+(B8-3), (A1-7)+(B8-4), (A1-7)+(B8-5), (A1-7)+(B8-6), (A1-7)+(B8-7), (A1-7)+(B9-1), (A1-7)+(B9-2), (A1-7)+(B10-1), (A1-7)+(B10-2), (A1-7)+(B10-3), (A1-7)+(B10-4), (A1-7)+(B10-5), (A1-7)+(B11-1), (A1-7)+(B11-2), (A1-7)+(B11-2),
(A1-8)+(B1-1), (A1-8)+(B1-2), (A1-8)+(B1-3), (A1-8)+(B1-4), (A1-8)+(B1-5), (A1-8)+(B1-6), (A1-8)+(B2-1), (A1-8)+(B2-2), (A1-8)+(B2-3), (A1-8)+(B2-4), (A1-8)+(B2-5), (A1-8)+(B2-6), (A1-8)+(B2-7), (A1-8)+(B2-8), (A1-8)+(B2-9), (A1-8)+(B2-10), (A1-8)+(B2-11), (A1-8)+(B2-12), (A1-8)+(B2-13), (A1-8)+(B2-14), (A1-8)+(B2-15), (A1-8)+(B2-16), (A1-8)+(B2-17), (A1-8)+(B2-18), (A1-8)+(B2-19), (A1-8)+(B2-20), (A1-8)+(B2-21), (A1-8)+(B2-22), (A1-8)+(B2-23), (A1-8)+(B2-24), (A1-8)+(B2-25), (A1-8)+(B2-26), (A1-8)+(B2-27), (A1-8)+(B2-28), (A1-8)+(B2-29), (A1-8)+(B3-1), (A1-8)+(B3-2), (A1-8)+(B4-1), (A1-8)+(B4-2), (A1-8)+(B4-3), (A1-8)+(B4-4), (A1-8)+(B4-5), (A1-8)+(B4-6), (A1-8)+(B4-7), (A1-8)+(B4-8), (A1-8)+(B4-9), (A1-8)+(B4-10), (A1-8)+(B4-11), (A1-8)+(B5-1), (A1-8)+(B5-2), (A1-8)+(B5-3), (A1-8)+(B5-4), (A1-8)+(B5-5), (A1-8)+(B6-1), (A1-8)+(B6-2), (A1-8)+(B6-3), (A1-8)+(B6-4), (A1-8)+(B6-5), (A1-8)+(B6-6), (A1-8)+(B7-1), (A1-8)+(B7-2), (A1-8)+(B7-3), (A1-8)+(B7-4), (A1-8)+(B7-5), (A1-8)+(B7-6), (A1-8)+(B7-7)), (A1-8)+(B7-7), (A1-8)+(B7-8), (A1-8)+(B8-1), (A1-8)+(B8-2), (A1-8)+(B8-3), (A1-8)+(B8-4), (A1-8)+(B8-5), (A1-8)+(B8-6), (A1-8)+(B8-7), (A1-8)+(B9-1), (A1-8)+(B9-2), (A1-8)+(B10-1), (A1-8)+(B10-2), (A1-8)+(B10-3), (A1-8)+(B10-4), (A1-8)+(B10-5), (A1-8)+(B11-1), (A1-8)+(B11-2), (A1-8)+(B11-2),
(A1-9)+(B1-1), (A1-9)+(B1-2), (A1-9)+(B1-3), (A1-9)+(B1-4), (A1-9)+(B1-5), (A1-9)+(B1-6), (A1-9)+(B2-1), (A1-9)+(B2-2), (A1-9)+(B2-3), (A1-9)+(B2-4), (A1-9)+(B2-5), (A1-9)+(B2-6), (A1-9)+(B2-7), (A1-9)+(B2-8), (A1-9)+(B2-9), (A1-9)+(B2-10), (A1-9)+(B2-11), (A1-9)+(B2-12), (A1-9)+(B2-13), (A1-9)+(B2-14), (A1-9)+(B2-15), (A1-9)+(B2-16), (A1-9)+(B2-17), (A1-9)+(B2-18), (A1-9)+(B2-19), (A1-9)+(B2-20), (A1-9)+(B2-21), (A1-9)+(B2-22), (A1-9)+(B2-23), (A1-9)+(B2-24), (A1-9)+(B2-25), (A1-9)+(B2-26), (A1-9)+(B2-27), (A1-9)+(B2-28), (A1-9)+(B2-29), (A1-9)+(B3-1), (A1-9)+(B3-2), (A1-9)+(B4-1), (A1-9)+(B4-2), (A1-9)+(B4-3), (A1-9)+(B4-4), (A1-9)+(B4-5), (A1-9)+(B4-6), (A1-9)+(B4-7), (A1-9)+(B4-8), (A1-9)+(B4-9), (A1-9)+(B4-10), (A1-9)+(B4-11), (A1-9)+(B5-1), (A1-9)+(B5-2), (A1-9)+(B5-3), (A1-9)+(B5-4), (A1-9)+(B5-5), (A1-9)+(B6-1), (A1-9)+(B6-2), (A1-9)+(B6-3), (A1-9)+(B6-4), (A1-9)+(B6-5), (A1-9)+(B6-6), (A1-9)+(B7-1), (A1-9)+(B7-2), (A1-9)+(B7-3), (A1-9)+(B7-4), (A1-9)+(B7-5), (A1-9)+(B7-6), (A1-9)+(B7-7)), (A1-9)+(B7-7), (A1-9)+(B7-8), (A1-9)+(B8-1), (A1-9)+(B8-2), (A1-9)+(B8-3), (A1-9)+(B8-4), (A1-9)+(B8-5), (A1-9)+(B8-6), (A1-9)+(B8-7), (A1-9)+(B9-1), (A1-9)+(B9-2), (A1-9)+(B10-1), (A1-9)+(B10-2), (A1-9)+(B10-3), (A1-9)+(B10-4), (A1-9)+(B10-5), (A1-9)+(B11-1), (A1-9)+(B11-2), (A1-9)+(B11-2),
(A1-10)+(B1-1), (A1-10)+(B1-2), (A1-10)+(B1-3), (A1-10)+(B1-4), (A1-10)+(B1-5), (A1-10)+(B1-6), (A1-10)+(B2-1), (A1-10)+(B2-2), (A1-10)+(B2-3), (A1-10)+(B2-4), (A1-10)+(B2-5), (A1-10)+(B2-6), (A1-10)+(B2-7), (A1-10)+(B2-8), (A1-10)+(B2-9), (A1-10)+(B2-10), (A1-10)+(B2-11), (A1-10)+(B2-12), (A1-10)+(B2-13), (A1-10)+(B2-14), (A1-10)+(B2-15), (A1-10)+(B2-16), (A1-10)+(B2-17), (A1-10)+(B2-18), (A1-10)+(B2-19), (A1-10)+(B2-20), (A1-10)+(B2-21), (A1-10)+(B2-22), (A1-10)+(B2-23), (A1-10)+(B2-24), (A1-10)+(B2-25), (A1-10)+(B2-26), (A1-10)+(B2-27), (A1-10)+(B2-28), (A1-10)+(B2-29), (A1-10)+(B3-1), (A1-10)+(B3-2), (A1-10)+(B4-1), (A1-10)+(B4-2), (A1-10)+(B4-3), (A1-10)+(B4-4), (A1-10)+(B4-5), (A1-10)+(B4-6), (A1-10)+(B4-7), (A1-10)+(B4-8), (A1-10)+(B4-9), (A1-10)+(B4-10), (A1-10)+(B4-11), (A1-10)+(B5-1), (A1-10)+(B5-2), (A1-10)+(B5-3), (A1-10)+(B5-4), (A1-10)+(B5-5), (A1-10)+(B6-1), (A1-10)+(B6-2), (A1-10)+(B6-3), (A1-10)+(B6-4), (A1-10)+(B6-5), (A1-10)+(B6-6), (A1-10)+(B7-1), (A1-10)+(B7-2), (A1-10)+(B7-3), (A1-10)+(B7-4), (A1-10)+(B7-5), (A1-10)+(B7-6), (A1-10)+(B7-7)), (A1-10)+(B7-7), (A1-10)+(B7-8), (A1-10)+(B8-1), (A1-10)+(B8-2), (A1-10)+(B8-3), (A1-10)+(B8-4), (A1-10)+(B8-5), (A1-10)+(B8-6), (A1-10)+(B8-7), (A1-10)+(B9-1), (A1-10)+(B9-2), (A1-10)+(B10-1), (A1-10)+(B10-2), (A1-10)+(B10-3), (A1-10)+(B10-4), (A1-10)+(B10-5), (A1-10)+(B11-1), (A1-10)+(B11-2), (A1-10)+(B11-2),
(A1-11)+(B1-1), (A1-11)+(B1-2), (A1-11)+(B1-3), (A1-11)+(B1-4), (A1-11)+(B1-5), (A1-11)+(B1-6), (A1-11)+(B2-1), (A1-11)+(B2-2), (A1-11)+(B2-3), (A1-11)+(B2-4), (A1-11)+(B2-5), (A1-11)+(B2-6), (A1-11)+(B2-7), (A1-11)+(B2-8), (A1-11)+(B2-9), (A1-11)+(B2-10), (A1-11)+(B2-11), (A1-11)+(B2-12), (A1-11)+(B2-13), (A1-11)+(B2-14), (A1-11)+(B2-15), (A1-11)+(B2-16), (A1-11)+(B2-17), (A1-11)+(B2-18), (A1-11)+(B2-19), (A1-11)+(B2-20), (A1-11)+(B2-21), (A1-11)+(B2-22), (A1-11)+(B2-23), (A1-11)+(B2-24), (A1-11)+(B2-25), (A1-11)+(B2-26), (A1-11)+(B2-27), (A1-11)+(B2-28), (A1-11)+(B2-29), (A1-11)+(B3-1), (A1-11)+(B3-2), (A1-11)+(B4-1), (A1-11)+(B4-2), (A1-11)+(B4-3), (A1-11)+(B4-4), (A1-11)+(B4-5), (A1-11)+(B4-6), (A1-11)+(B4-7), (A1-11)+(B4-8), (A1-11)+(B4-9), (A1-11)+(B4-10), (A1-11)+(B4-11), (A1-11)+(B5-1), (A1-11)+(B5-2), (A1-11)+(B5-3), (A1-11)+(B5-4), (A1-11)+(B5-5), (A1-11)+(B6-1), (A1-11)+(B6-2), (A1-11)+(B6-3), (A1-11)+(B6-4), (A1-11)+(B6-5), (A1-11)+(B6-6), (A1-11)+(B7-1), (A1-11)+(B7-2), (A1-11)+(B7-3), (A1-11)+(B7-4), (A1-11)+(B7-5), (A1-11)+(B7-6), (A1-11)+(B7-7)), (A1-11)+(B7-7), (A1-11)+(B7-8), (A1-11)+(B8-1), (A1-11)+(B8-2), (A1-11)+(B8-3), (A1-11)+(B8-4), (A1-11)+(B8-5), (A1-11)+(B8-6), (A1-11)+(B8-7), (A1-11)+(B9-1), (A1-11)+(B9-2), (A1-11)+(B10-1), (A1-11)+(B10-2), (A1-11)+(B10-3), (A1-11)+(B10-4), (A1-11)+(B10-5), (A1-11)+(B11-1), (A1-11)+(B11-2), (A1-11)+(B11-2),
(A1-12)+(B1-1), (A1-12)+(B1-2), (A1-12)+(B1-3), (A1-12)+(B1-4), (A1-12)+(B1-5), (A1-12)+(B1-6), (A1-12)+(B2-1), (A1-12)+(B2-2), (A1-12)+(B2-3), (A1-12)+(B2-4), (A1-12)+(B2-5), (A1-12)+(B2-6), (A1-12)+(B2-7), (A1-12)+(B2-8), (A1-12)+(B2-9), (A1-12)+(B2-10), (A1-12)+(B2-11), (A1-12)+(B2-12), (A1-12)+(B2-13), (A1-12)+(B2-14), (A1-12)+(B2-15), (A1-12)+(B2-16), (A1-12)+(B2-17), (A1-12)+(B2-18), (A1-12)+(B2-19), (A1-12)+(B2-20), (A1-12)+(B2-21), (A1-12)+(B2-22), (A1-12)+(B2-23), (A1-12)+(B2-24), (A1-12)+(B2-25), (A1-12)+(B2-26), (A1-12)+(B2-27), (A1-12)+(B2-28), (A1-12)+(B2-29), (A1-12)+(B3-1), (A1-12)+(B3-2), (A1-12)+(B4-1), (A1-12)+(B4-2), (A1-12)+(B4-3), (A1-12)+(B4-4), (A1-12)+(B4-5), (A1-12)+(B4-6), (A1-12)+(B4-7), (A1-12)+(B4-8), (A1-12)+(B4-9), (A1-12)+(B4-10), (A1-12)+(B4-11), (A1-12)+(B5-1), (A1-12)+(B5-2), (A1-12)+(B5-3), (A1-12)+(B5-4), (A1-12)+(B5-5), (A1-12)+(B6-1), (A1-12)+(B6-2), (A1-12)+(B6-3), (A1-12)+(B6-4), (A1-12)+(B6-5), (A1-12)+(B6-6), (A1-12)+(B7-1), (A1-12)+(B7-2), (A1-12)+(B7-3), (A1-12)+(B7-4), (A1-12)+(B7-5), (A1-12)+(B7-6), (A1-12)+(B7-7)), (A1-12)+(B7-7), (A1-12)+(B7-8), (A1-12)+(B8-1), (A1-12)+(B8-2), (A1-12)+(B8-3), (A1-12)+(B8-4), (A1-12)+(B8-5), (A1-12)+(B8-6), (A1-12)+(B8-7), (A1-12)+(B9-1), (A1-12)+(B9-2), (A1-12)+(B10-1), (A1-12)+(B10-2), (A1-12)+(B10-3), (A1-12)+(B10-4), (A1-12)+(B10-5), (A1-12)+(B11-1), (A1-12)+(B11-2), (A1-12)+(B11-2),
(A1-13)+(B1-1), (A1-13)+(B1-2), (A1-13)+(B1-3), (A1-13)+(B1-4), (A1-13)+(B1-5), (A1-13)+(B1-6), (A1-13)+(B2-1), (A1-13)+(B2-2), (A1-13)+(B2-3), (A1-13)+(B2-4), (A1-13)+(B2-5), (A1-13)+(B2-6), (A1-13)+(B2-7), (A1-13)+(B2-8), (A1-13)+(B2-9), (A1-13)+(B2-10), (A1-13)+(B2-11), (A1-13)+(B2-12), (A1-13)+(B2-13), (A1-13)+(B2-14), (A1-13)+(B2-15), (A1-13)+(B2-16), (A1-13)+(B2-17), (A1-13)+(B2-18), (A1-13)+(B2-19), (A1-13)+(B2-20), (A1-13)+(B2-21), (A1-13)+(B2-22), (A1-13)+(B2-23), (A1-13)+(B2-24), (A1-13)+(B2-25), (A1-13)+(B2-26), (A1-13)+(B2-27), (A1-13)+(B2-28), (A1-13)+(B2-29), (A1-13)+(B3-1), (A1-13)+(B3-2), (A1-13)+(B4-1), (A1-13)+(B4-2), (A1-13)+(B4-3), (A1-13)+(B4-4), (A1-13)+(B4-5), (A1-13)+(B4-6), (A1-13)+(B4-7), (A1-13)+(B4-8), (A1-13)+(B4-9), (A1-13)+(B4-10), (A1-13)+(B4-11), (A1-13)+(B5-1), (A1-13)+(B5-2), (A1-13)+(B5-3), (A1-13)+(B5-4), (A1-13)+(B5-5), (A1-13)+(B6-1), (A1-13)+(B6-2), (A1-13)+(B6-3), (A1-13)+(B6-4), (A1-13)+(B6-5), (A1-13)+(B6-6), (A1-13)+(B7-1), (A1-13)+(B7-2), (A1-13)+(B7-3), (A1-13)+(B7-4), (A1-13)+(B7-5), (A1-13)+(B7-6), (A1-13)+(B7-7)), (A1-13)+(B7-7), (A1-13)+(B7-8), (A1-13)+(B8-1), (A1-13)+(B8-2), (A1-13)+(B8-3), (A1-13)+(B8-4), (A1-13)+(B8-5), (A1-13)+(B8-6), (A1-13)+(B8-7), (A1-13)+(B9-1), (A1-13)+(B9-2), (A1-13)+(B10-1), (A1-13)+(B10-2), (A1-13)+(B10-3), (A1-13)+(B10-4), (A1-13)+(B10-5), (A1-13)+(B11-1), (A1-13)+(B11-2), (A1-13)+(B11-2),
(A1-14)+(B1-1), (A1-14)+(B1-2), (A1-14)+(B1-3), (A1-14)+(B1-4), (A1-14)+(B1-5), (A1-14)+(B1-6), (A1-14)+(B2-1), (A1-14)+(B2-2), (A1-14)+(B2-3), (A1-14)+(B2-4), (A1-14)+(B2-5), (A1-14)+(B2-6), (A1-14)+(B2-7), (A1-14)+(B2-8), (A1-14)+(B2-9), (A1-14)+(B2-10), (A1-14)+(B2-11), (A1-14)+(B2-12), (A1-14)+(B2-13), (A1-14)+(B2-14), (A1-14)+(B2-15), (A1-14)+(B2-16), (A1-14)+(B2-17), (A1-14)+(B2-18), (A1-14)+(B2-19), (A1-14)+(B2-20), (A1-14)+(B2-21), (A1-14)+(B2-22), (A1-14)+(B2-23), (A1-14)+(B2-24), (A1-14)+(B2-25), (A1-14)+(B2-26), (A1-14)+(B2-27), (A1-14)+(B2-28), (A1-14)+(B2-29), (A1-14)+(B3-1), (A1-14)+(B3-2), (A1-14)+(B4-1), (A1-14)+(B4-2), (A1-14)+(B4-3), (A1-14)+(B4-4), (A1-14)+(B4-5), (A1-14)+(B4-6), (A1-14)+(B4-7), (A1-14)+(B4-8), (A1-14)+(B4-9), (A1-14)+(B4-10), (A1-14)+(B4-11), (A1-14)+(B5-1), (A1-14)+(B5-2), (A1-14)+(B5-3), (A1-14)+(B5-4), (A1-14)+(B5-5), (A1-14)+(B6-1), (A1-14)+(B6-2), (A1-14)+(B6-3), (A1-14)+(B6-4), (A1-14)+(B6-5), (A1-14)+(B6-6), (A1-14)+(B7-1), (A1-14)+(B7-2), (A1-14)+(B7-3), (A1-14)+(B7-4), (A1-14)+(B7-5), (A1-14)+(B7-6), (A1-14)+(B7-7)), (A1-14)+(B7-7), (A1-14)+(B7-8), (A1-14)+(B8-1), (A1-14)+(B8-2), (A1-14)+(B8-3), (A1-14)+(B8-4), (A1-14)+(B8-5), (A1-14)+(B8-6), (A1-14)+(B8-7), (A1-14)+(B9-1), (A1-14)+(B9-2), (A1-14)+(B10-1), (A1-14)+(B10-2), (A1-14)+(B10-3), (A1-14)+(B10-4), (A1-14)+(B10-5), (A1-14)+(B11-1), (A1-14)+(B11-2), (A1-14)+(B11-2),
(A1-15)+(B1-1), (A1-15)+(B1-2), (A1-15)+(B1-3), (A1-15)+(B1-4), (A1-15)+(B1-5), (A1-15)+(B1-6), (A1-15)+(B2-1), (A1-15)+(B2-2), (A1-15)+(B2-3), (A1-15)+(B2-4), (A1-15)+(B2-5), (A1-15)+(B2-6), (A1-15)+(B2-7), (A1-15)+(B2-8), (A1-15)+(B2-9), (A1-15)+(B2-10), (A1-15)+(B2-11), (A1-15)+(B2-12), (A1-15)+(B2-13), (A1-15)+(B2-14), (A1-15)+(B2-15), (A1-15)+(B2-16), (A1-15)+(B2-17), (A1-15)+(B2-18), (A1-15)+(B2-19), (A1-15)+(B2-20), (A1-15)+(B2-21), (A1-15)+(B2-22), (A1-15)+(B2-23), (A1-15)+(B2-24), (A1-15)+(B2-25), (A1-15)+(B2-26), (A1-15)+(B2-27), (A1-15)+(B2-28), (A1-15)+(B2-29), (A1-15)+(B3-1), (A1-15)+(B3-2), (A1-15)+(B4-1), (A1-15)+(B4-2), (A1-15)+(B4-3), (A1-15)+(B4-4), (A1-15)+(B4-5), (A1-15)+(B4-6), (A1-15)+(B4-7), (A1-15)+(B4-8), (A1-15)+(B4-9), (A1-15)+(B4-10), (A1-15)+(B4-11), (A1-15)+(B5-1), (A1-15)+(B5-2), (A1-15)+(B5-3), (A1-15)+(B5-4), (A1-15)+(B5-5), (A1-15)+(B6-1), (A1-15)+(B6-2), (A1-15)+(B6-3), (A1-15)+(B6-4), (A1-15)+(B6-5), (A1-15)+(B6-6), (A1-15)+(B7-1), (A1-15)+(B7-2), (A1-15)+(B7-3), (A1-15)+(B7-4), (A1-15)+(B7-5), (A1-15)+(B7-6), (A1-15)+(B7-7)), (A1-15)+(B7-7), (A1-15)+(B7-8), (A1-15)+(B8-1), (A1-15)+(B8-2), (A1-15)+(B8-3), (A1-15)+(B8-4), (A1-15)+(B8-5), (A1-15)+(B8-6), (A1-15)+(B8-7), (A1-15)+(B9-1), (A1-15)+(B9-2), (A1-15)+(B10-1), (A1-15)+(B10-2), (A1-15)+(B10-3), (A1-15)+(B10-4), (A1-15)+(B10-5), (A1-15)+(B11-1), (A1-15)+(B11-2), (A1-15)+(B11-2),
(A1-16)+(B1-1), (A1-16)+(B1-2), (A1-16)+(B1-3), (A1-16)+(B1-4), (A1-16)+(B1-5), (A1-16)+(B1-6), (A1-16)+(B2-1), (A1-16)+(B2-2), (A1-16)+(B2-3), (A1-16)+(B2-4), (A1-16)+(B2-5), (A1-16)+(B2-6), (A1-16)+(B2-7), (A1-16)+(B2-8), (A1-16)+(B2-9), (A1-16)+(B2-10), (A1-16)+(B2-11), (A1-16)+(B2-12), (A1-16)+(B2-13), (A1-16)+(B2-14), (A1-16)+(B2-15), (A1-16)+(B2-16), (A1-16)+(B2-17), (A1-16)+(B2-18), (A1-16)+(B2-19), (A1-16)+(B2-20), (A1-16)+(B2-21), (A1-16)+(B2-22), (A1-16)+(B2-23), (A1-16)+(B2-24), (A1-16)+(B2-25), (A1-16)+(B2-26), (A1-16)+(B2-27), (A1-16)+(B2-28), (A1-16)+(B2-29), (A1-16)+(B3-1), (A1-16)+(B3-2), (A1-16)+(B4-1), (A1-16)+(B4-2), (A1-16)+(B4-3), (A1-16)+(B4-4), (A1-16)+(B4-5), (A1-16)+(B4-6), (A1-16)+(B4-7), (A1-16)+(B4-8), (A1-16)+(B4-9), (A1-16)+(B4-10), (A1-16)+(B4-11), (A1-16)+(B5-1), (A1-16)+(B5-2), (A1-16)+(B5-3), (A1-16)+(B5-4), (A1-16)+(B5-5), (A1-16)+(B6-1), (A1-16)+(B6-2), (A1-16)+(B6-3), (A1-16)+(B6-4), (A1-16)+(B6-5), (A1-16)+(B6-6), (A1-16)+(B7-1), (A1-16)+(B7-2), (A1-16)+(B7-3), (A1-16)+(B7-4), (A1-16)+(B7-5), (A1-16)+(B7-6), (A1-16)+(B7-7)), (A1-16)+(B7-7), (A1-16)+(B7-8), (A1-16)+(B8-1), (A1-16)+(B8-2), (A1-16)+(B8-3), (A1-16)+(B8-4), (A1-16)+(B8-5), (A1-16)+(B8-6), (A1-16)+(B8-7), (A1-16)+(B9-1), (A1-16)+(B9-2), (A1-16)+(B10-1), (A1-16)+(B10-2), (A1-16)+(B10-3), (A1-16)+(B10-4), (A1-16)+(B10-5), (A1-16)+(B11-1), (A1-16)+(B11-2), (A1-16)+(B11-2),
(A1-17)+(B1-1), (A1-17)+(B1-2), (A1-17)+(B1-3), (A1-17)+(B1-4), (A1-17)+(B1-5), (A1-17)+(B1-6), (A1-17)+(B2-1), (A1-17)+(B2-2), (A1-17)+(B2-3), (A1-17)+(B2-4), (A1-17)+(B2-5), (A1-17)+(B2-6), (A1-17)+(B2-7), (A1-17)+(B2-8), (A1-17)+(B2-9), (A1-17)+(B2-10), (A1-17)+(B2-11), (A1-17)+(B2-12), (A1-17)+(B2-13), (A1-17)+(B2-14), (A1-17)+(B2-15), (A1-17)+(B2-16), (A1-17)+(B2-17), (A1-17)+(B2-18), (A1-17)+(B2-19), (A1-17)+(B2-20), (A1-17)+(B2-21), (A1-17)+(B2-22), (A1-17)+(B2-23), (A1-17)+(B2-24), (A1-17)+(B2-25), (A1-17)+(B2-26), (A1-17)+(B2-27), (A1-17)+(B2-28), (A1-17)+(B2-29), (A1-17)+(B3-1), (A1-17)+(B3-2), (A1-17)+(B4-1), (A1-17)+(B4-2), (A1-17)+(B4-3), (A1-17)+(B4-4), (A1-17)+(B4-5), (A1-17)+(B4-6), (A1-17)+(B4-7), (A1-17)+(B4-8), (A1-17)+(B4-9), (A1-17)+(B4-10), (A1-17)+(B4-11), (A1-17)+(B5-1), (A1-17)+(B5-2), (A1-17)+(B5-3), (A1-17)+(B5-4), (A1-17)+(B5-5), (A1-17)+(B6-1), (A1-17)+(B6-2), (A1-17)+(B6-3), (A1-17)+(B6-4), (A1-17)+(B6-5), (A1-17)+(B6-6), (A1-17)+(B7-1), (A1-17)+(B7-2), (A1-17)+(B7-3), (A1-17)+(B7-4), (A1-17)+(B7-5), (A1-17)+(B7-6), (A1-17)+(B7-7)), (A1-17)+(B7-7), (A1-17)+(B7-8), (A1-17)+(B8-1), (A1-17)+(B8-2), (A1-17)+(B8-3), (A1-17)+(B8-4), (A1-17)+(B8-5), (A1-17)+(B8-6), (A1-17)+(B8-7), (A1-17)+(B9-1), (A1-17)+(B9-2), (A1-17)+(B10-1), (A1-17)+(B10-2), (A1-17)+(B10-3), (A1-17)+(B10-4), (A1-17)+(B10-5), (A1-17)+(B11-1), (A1-17)+(B11-2), (A1-17)+(B11-2),
(A1-18)+(B1-1), (A1-18)+(B1-2), (A1-18)+(B1-3), (A1-18)+(B1-4), (A1-18)+(B1-5), (A1-18)+(B1-6), (A1-18)+(B2-1), (A1-18)+(B2-2), (A1-18)+(B2-3), (A1-18)+(B2-4), (A1-18)+(B2-5), (A1-18)+(B2-6), (A1-18)+(B2-7), (A1-18)+(B2-8), (A1-18)+(B2-9), (A1-18)+(B2-10), (A1-18)+(B2-11), (A1-18)+(B2-12), (A1-18)+(B2-13), (A1-18)+(B2-14), (A1-18)+(B2-15), (A1-18)+(B2-16), (A1-18)+(B2-17), (A1-18)+(B2-18), (A1-18)+(B2-19), (A1-18)+(B2-20), (A1-18)+(B2-21), (A1-18)+(B2-22), (A1-18)+(B2-23), (A1-18)+(B2-24), (A1-18)+(B2-25), (A1-18)+(B2-26), (A1-18)+(B2-27), (A1-18)+(B2-28), (A1-18)+(B2-29), (A1-18)+(B3-1), (A1-18)+(B3-2), (A1-18)+(B4-1), (A1-18)+(B4-2), (A1-18)+(B4-3), (A1-18)+(B4-4), (A1-18)+(B4-5), (A1-18)+(B4-6), (A1-18)+(B4-7), (A1-18)+(B4-8), (A1-18)+(B4-9), (A1-18)+(B4-10), (A1-18)+(B4-11), (A1-18)+(B5-1), (A1-18)+(B5-2), (A1-18)+(B5-3), (A1-18)+(B5-4), (A1-18)+(B5-5), (A1-18)+(B6-1), (A1-18)+(B6-2), (A1-18)+(B6-3), (A1-18)+(B6-4), (A1-18)+(B6-5), (A1-18)+(B6-6), (A1-18)+(B7-1), (A1-18)+(B7-2), (A1-18)+(B7-3), (A1-18)+(B7-4), (A1-18)+(B7-5), (A1-18)+(B7-6), (A1-18)+(B7-7)), (A1-18)+(B7-7), (A1-18)+(B7-8), (A1-18)+(B8-1), (A1-18)+(B8-2), (A1-18)+(B8-3), (A1-18)+(B8-4), (A1-18)+(B8-5), (A1-18)+(B8-6), (A1-18)+(B8-7), (A1-18)+(B9-1), (A1-18)+(B9-2), (A1-18)+(B10-1), (A1-18)+(B10-2), (A1-18)+(B10-3), (A1-18)+(B10-4), (A1-18)+(B10-5), (A1-18)+(B11-1), (A1-18)+(B11-2), (A1-18)+(B11-2),
(A1-19)+(B1-1), (A1-19)+(B1-2), (A1-19)+(B1-3), (A1-19)+(B1-4), (A1-19)+(B1-5), (A1-19)+(B1-6), (A1-19)+(B2-1), (A1-19)+(B2-2), (A1-19)+(B2-3), (A1-19)+(B2-4), (A1-19)+(B2-5), (A1-19)+(B2-6), (A1-19)+(B2-7), (A1-19)+(B2-8), (A1-19)+(B2-9), (A1-19)+(B2-10), (A1-19)+(B2-11), (A1-19)+(B2-12), (A1-19)+(B2-13), (A1-19)+(B2-14), (A1-19)+(B2-15), (A1-19)+(B2-16), (A1-19)+(B2-17), (A1-19)+(B2-18), (A1-19)+(B2-19), (A1-19)+(B2-20), (A1-19)+(B2-21), (A1-19)+(B2-22), (A1-19)+(B2-23), (A1-19)+(B2-24), (A1-19)+(B2-25), (A1-19)+(B2-26), (A1-19)+(B2-27), (A1-19)+(B2-28), (A1-19)+(B2-29), (A1-19)+(B3-1), (A1-19)+(B3-2), (A1-19)+(B4-1), (A1-19)+(B4-2), (A1-19)+(B4-3), (A1-19)+(B4-4), (A1-19)+(B4-5), (A1-19)+(B4-6), (A1-19)+(B4-7), (A1-19)+(B4-8), (A1-19)+(B4-9), (A1-19)+(B4-10), (A1-19)+(B4-11), (A1-19)+(B5-1), (A1-19)+(B5-2), (A1-19)+(B5-3), (A1-19)+(B5-4), (A1-19)+(B5-5), (A1-19)+(B6-1), (A1-19)+(B6-2), (A1-19)+(B6-3), (A1-19)+(B6-4), (A1-19)+(B6-5), (A1-19)+(B6-6), (A1-19)+(B7-1), (A1-19)+(B7-2), (A1-19)+(B7-3), (A1-19)+(B7-4), (A1-19)+(B7-5), (A1-19)+(B7-6), (A1-19)+(B7-7)), (A1-19)+(B7-7), (A1-19)+(B7-8), (A1-19)+(B8-1), (A1-19)+(B8-2), (A1-19)+(B8-3), (A1-19)+(B8-4), (A1-19)+(B8-5), (A1-19)+(B8-6), (A1-19)+(B8-7), (A1-19)+(B9-1), (A1-19)+(B9-2), (A1-19)+(B10-1), (A1-19)+(B10-2), (A1-19)+(B10-3), (A1-19)+(B10-4), (A1-19)+(B10-5), (A1-19)+(B11-1), (A1-19)+(B11-2), (A1-19)+(B11-2),
(A1-20)+(B1-1), (A1-20)+(B1-2), (A1-20)+(B1-3), (A1-20)+(B1-4), (A1-20)+(B1-5), (A1-20)+(B1-6), (A1-20)+(B2-1), (A1-20)+(B2-2), (A1-20)+(B2-3), (A1-20)+(B2-4), (A1-20)+(B2-5), (A1-20)+(B2-6), (A1-20)+(B2-7), (A1-20)+(B2-8), (A1-20)+(B2-9), (A1-20)+(B2-10), (A1-20)+(B2-11), (A1-20)+(B2-12), (A1-20)+(B2-13), (A1-20)+(B2-14), (A1-20)+(B2-15), (A1-20)+(B2-16), (A1-20)+(B2-17), (A1-20)+(B2-18), (A1-20)+(B2-19), (A1-20)+(B2-20), (A1-20)+(B2-21), (A1-20)+(B2-22), (A1-20)+(B2-23), (A1-20)+(B2-24), (A1-20)+(B2-25), (A1-20)+(B2-26), (A1-20)+(B2-27), (A1-20)+(B2-28), (A1-20)+(B2-29), (A1-20)+(B3-1), (A1-20)+(B3-2), (A1-20)+(B4-1), (A1-20)+(B4-2), (A1-20)+(B4-3), (A1-20)+(B4-4), (A1-20)+(B4-5), (A1-20)+(B4-6), (A1-20)+(B4-7), (A1-20)+(B4-8), (A1-20)+(B4-9), (A1-20)+(B4-10), (A1-20)+(B4-11), (A1-20)+(B5-1), (A1-20)+(B5-2), (A1-20)+(B5-3), (A1-20)+(B5-4), (A1-20)+(B5-5), (A1-20)+(B6-1), (A1-20)+(B6-2), (A1-20)+(B6-3), (A1-20)+(B6-4), (A1-20)+(B6-5), (A1-20)+(B6-6), (A1-20)+(B7-1), (A1-20)+(B7-2), (A1-20)+(B7-3), (A1-20)+(B7-4), (A1-20)+(B7-5), (A1-20)+(B7-6), (A1-20)+(B7-7)), (A1-20)+(B7-7), (A1-20)+(B7-8), (A1-20)+(B8-1), (A1-20)+(B8-2), (A1-20)+(B8-3), (A1-20)+(B8-4), (A1-20)+(B8-5), (A1-20)+(B8-6), (A1-20)+(B8-7), (A1-20)+(B9-1), (A1-20)+(B9-2), (A1-20)+(B10-1), (A1-20)+(B10-2), (A1-20)+(B10-3), (A1-20)+(B10-4), (A1-20)+(B10-5), (A1-20)+(B11-1), (A1-20)+(B11-2), (A1-20)+(B11-2),
(A1-21)+(B1-1), (A1-21)+(B1-2), (A1-21)+(B1-3), (A1-21)+(B1-4), (A1-21)+(B1-5), (A1-21)+(B1-6), (A1-21)+(B2-1), (A1-21)+(B2-2), (A1-21)+(B2-3), (A1-21)+(B2-4), (A1-21)+(B2-5), (A1-21)+(B2-6), (A1-21)+(B2-7), (A1-21)+(B2-8), (A1-21)+(B2-9), (A1-21)+(B2-10), (A1-21)+(B2-11), (A1-21)+(B2-12), (A1-21)+(B2-13), (A1-21)+(B2-14), (A1-21)+(B2-15), (A1-21)+(B2-16), (A1-21)+(B2-17), (A1-21)+(B2-18), (A1-21)+(B2-19), (A1-21)+(B2-20), (A1-21)+(B2-21), (A1-21)+(B2-22), (A1-21)+(B2-23), (A1-21)+(B2-24), (A1-21)+(B2-25), (A1-21)+(B2-26), (A1-21)+(B2-27), (A1-21)+(B2-28), (A1-21)+(B2-29), (A1-21)+(B3-1), (A1-21)+(B3-2), (A1-21)+(B4-1), (A1-21)+(B4-2), (A1-21)+(B4-3), (A1-21)+(B4-4), (A1-21)+(B4-5), (A1-21)+(B4-6), (A1-21)+(B4-7), (A1-21)+(B4-8), (A1-21)+(B4-9), (A1-21)+(B4-10), (A1-21)+(B4-11), (A1-21)+(B5-1), (A1-21)+(B5-2), (A1-21)+(B5-3), (A1-21)+(B5-4), (A1-21)+(B5-5), (A1-21)+(B6-1), (A1-21)+(B6-2), (A1-21)+(B6-3), (A1-21)+(B6-4), (A1-21)+(B6-5), (A1-21)+(B6-6), (A1-21)+(B7-1), (A1-21)+(B7-2), (A1-21)+(B7-3), (A1-21)+(B7-4), (A1-21)+(B7-5), (A1-21)+(B7-6), (A1-21)+(B7-7)), (A1-21)+(B7-7), (A1-21)+(B7-8), (A1-21)+(B8-1), (A1-21)+(B8-2), (A1-21)+(B8-3), (A1-21)+(B8-4), (A1-21)+(B8-5), (A1-21)+(B8-6), (A1-21)+(B8-7), (A1-21)+(B9-1), (A1-21)+(B9-2), (A1-21)+(B10-1), (A1-21)+(B10-2), (A1-21)+(B10-3), (A1-21)+(B10-4), (A1-21)+(B10-5), (A1-21)+(B11-1), (A1-21)+(B11-2), (A1-21)+(B11-2),
(A1-22)+(B1-1), (A1-22)+(B1-2), (A1-22)+(B1-3), (A1-22)+(B1-4), (A1-22)+(B1-5), (A1-22)+(B1-6), (A1-22)+(B2-1), (A1-22)+(B2-2), (A1-22)+(B2-3), (A1-22)+(B2-4), (A1-22)+(B2-5), (A1-22)+(B2-6), (A1-22)+(B2-7), (A1-22)+(B2-8), (A1-22)+(B2-9), (A1-22)+(B2-10), (A1-22)+(B2-11), (A1-22)+(B2-12), (A1-22)+(B2-13), (A1-22)+(B2-14), (A1-22)+(B2-15), (A1-22)+(B2-16), (A1-22)+(B2-17), (A1-22)+(B2-18), (A1-22)+(B2-19), (A1-22)+(B2-20), (A1-22)+(B2-21), (A1-22)+(B2-22), (A1-22)+(B2-23), (A1-22)+(B2-24), (A1-22)+(B2-25), (A1-22)+(B2-26), (A1-22)+(B2-27), (A1-22)+(B2-28), (A1-22)+(B2-29), (A1-22)+(B3-1), (A1-22)+(B3-2), (A1-22)+(B4-1), (A1-22)+(B4-2), (A1-22)+(B4-3), (A1-22)+(B4-4), (A1-22)+(B4-5), (A1-22)+(B4-6), (A1-22)+(B4-7), (A1-22)+(B4-8), (A1-22)+(B4-9), (A1-22)+(B4-10), (A1-22)+(B4-11), (A1-22)+(B5-1), (A1-22)+(B5-2), (A1-22)+(B5-3), (A1-22)+(B5-4), (A1-22)+(B5-5), (A1-22)+(B6-1), (A1-22)+(B6-2), (A1-22)+(B6-3), (A1-22)+(B6-4), (A1-22)+(B6-5), (A1-22)+(B6-6), (A1-22)+(B7-1), (A1-22)+(B7-2), (A1-22)+(B7-3), (A1-22)+(B7-4), (A1-22)+(B7-5), (A1-22)+(B7-6), (A1-22)+(B7-7)), (A1-22)+(B7-7), (A1-22)+(B7-8), (A1-22)+(B8-1), (A1-22)+(B8-2), (A1-22)+(B8-3), (A1-22)+(B8-4), (A1-22)+(B8-5), (A1-22)+(B8-6), (A1-22)+(B8-7), (A1-22)+(B9-1), (A1-22)+(B9-2), (A1-22)+(B10-1), (A1-22)+(B10-2), (A1-22)+(B10-3), (A1-22)+(B10-4), (A1-22)+(B10-5), (A1-22)+(B11-1), (A1-22)+(B11-2), (A1-22)+(B11-2),
(A1-23)+(B1-1), (A1-23)+(B1-2), (A1-23)+(B1-3), (A1-23)+(B1-4), (A1-23)+(B1-5), (A1-23)+(B1-6), (A1-23)+(B2-1), (A1-23)+(B2-2), (A1-23)+(B2-3), (A1-23)+(B2-4), (A1-23)+(B2-5), (A1-23)+(B2-6), (A1-23)+(B2-7), (A1-23)+(B2-8), (A1-23)+(B2-9), (A1-23)+(B2-10), (A1-23)+(B2-11), (A1-23)+(B2-12), (A1-23)+(B2-13), (A1-23)+(B2-14), (A1-23)+(B2-15), (A1-23)+(B2-16), (A1-23)+(B2-17), (A1-23)+(B2-18), (A1-23)+(B2-19), (A1-23)+(B2-20), (A1-23)+(B2-21), (A1-23)+(B2-22), (A1-23)+(B2-23), (A1-23)+(B2-24), (A1-23)+(B2-25), (A1-23)+(B2-26), (A1-23)+(B2-27), (A1-23)+(B2-28), (A1-23)+(B2-29), (A1-23)+(B3-1), (A1-23)+(B3-2), (A1-23)+(B4-1), (A1-23)+(B4-2), (A1-23)+(B4-3), (A1-23)+(B4-4), (A1-23)+(B4-5), (A1-23)+(B4-6), (A1-23)+(B4-7), (A1-23)+(B4-8), (A1-23)+(B4-9), (A1-23)+(B4-10), (A1-23)+(B4-11), (A1-23)+(B5-1), (A1-23)+(B5-2), (A1-23)+(B5-3), (A1-23)+(B5-4), (A1-23)+(B5-5), (A1-23)+(B6-1), (A1-23)+(B6-2), (A1-23)+(B6-3), (A1-23)+(B6-4), (A1-23)+(B6-5), (A1-23)+(B6-6), (A1-23)+(B7-1), (A1-23)+(B7-2), (A1-23)+(B7-3), (A1-23)+(B7-4), (A1-23)+(B7-5), (A1-23)+(B7-6), (A1-23)+(B7-7)), (A1-23)+(B7-7), (A1-23)+(B7-8), (A1-23)+(B8-1), (A1-23)+(B8-2), (A1-23)+(B8-3), (A1-23)+(B8-4), (A1-23)+(B8-5), (A1-23)+(B8-6), (A1-23)+(B8-7), (A1-23)+(B9-1), (A1-23)+(B9-2), (A1-23)+(B10-1), (A1-23)+(B10-2), (A1-23)+(B10-3), (A1-23)+(B10-4), (A1-23)+(B10-5), (A1-23)+(B11-1), (A1-23)+(B11-2), (A1-23)+(B11-2),
(A1-24)+(B1-1), (A1-24)+(B1-2), (A1-24)+(B1-3), (A1-24)+(B1-4), (A1-24)+(B1-5), (A1-24)+(B1-6), (A1-24)+(B2-1), (A1-24)+(B2-2), (A1-24)+(B2-3), (A1-24)+(B2-4), (A1-24)+(B2-5), (A1-24)+(B2-6), (A1-24)+(B2-7), (A1-24)+(B2-8), (A1-24)+(B2-9), (A1-24)+(B2-10), (A1-24)+(B2-11), (A1-24)+(B2-12), (A1-24)+(B2-13), (A1-24)+(B2-14), (A1-24)+(B2-15), (A1-24)+(B2-16), (A1-24)+(B2-17), (A1-24)+(B2-18), (A1-24)+(B2-19), (A1-24)+(B2-20), (A1-24)+(B2-21), (A1-24)+(B2-22), (A1-24)+(B2-23), (A1-24)+(B2-24), (A1-24)+(B2-25), (A1-24)+(B2-26), (A1-24)+(B2-27), (A1-24)+(B2-28), (A1-24)+(B2-29), (A1-24)+(B3-1), (A1-24)+(B3-2), (A1-24)+(B4-1), (A1-24)+(B4-2), (A1-24)+(B4-3), (A1-24)+(B4-4), (A1-24)+(B4-5), (A1-24)+(B4-6), (A1-24)+(B4-7), (A1-24)+(B4-8), (A1-24)+(B4-9), (A1-24)+(B4-10), (A1-24)+(B4-11), (A1-24)+(B5-1), (A1-24)+(B5-2), (A1-24)+(B5-3), (A1-24)+(B5-4), (A1-24)+(B5-5), (A1-24)+(B6-1), (A1-24)+(B6-2), (A1-24)+(B6-3), (A1-24)+(B6-4), (A1-24)+(B6-5), (A1-24)+(B6-6), (A1-24)+(B7-1), (A1-24)+(B7-2), (A1-24)+(B7-3), (A1-24)+(B7-4), (A1-24)+(B7-5), (A1-24)+(B7-6), (A1-24)+(B7-7)), (A1-24)+(B7-7), (A1-24)+(B7-8), (A1-24)+(B8-1), (A1-24)+(B8-2), (A1-24)+(B8-3), (A1-24)+(B8-4), (A1-24)+(B8-5), (A1-24)+(B8-6), (A1-24)+(B8-7), (A1-24)+(B9-1), (A1-24)+(B9-2), (A1-24)+(B10-1), (A1-24)+(B10-2), (A1-24)+(B10-3), (A1-24)+(B10-4), (A1-24)+(B10-5), (A1-24)+(B11-1), (A1-24)+(B11-2), (A1-24)+(B11-2),
(A1-25)+(B1-1), (A1-25)+(B1-2), (A1-25)+(B1-3), (A1-25)+(B1-4), (A1-25)+(B1-5), (A1-25)+(B1-6), (A1-25)+(B2-1), (A1-25)+(B2-2), (A1-25)+(B2-3), (A1-25)+(B2-4), (A1-25)+(B2-5), (A1-25)+(B2-6), (A1-25)+(B2-7), (A1-25)+(B2-8), (A1-25)+(B2-9), (A1-25)+(B2-10), (A1-25)+(B2-11), (A1-25)+(B2-12), (A1-25)+(B2-13), (A1-25)+(B2-14), (A1-25)+(B2-15), (A1-25)+(B2-16), (A1-25)+(B2-17), (A1-25)+(B2-18), (A1-25)+(B2-19), (A1-25)+(B2-20), (A1-25)+(B2-21), (A1-25)+(B2-22), (A1-25)+(B2-23), (A1-25)+(B2-24), (A1-25)+(B2-25), (A1-25)+(B2-26), (A1-25)+(B2-27), (A1-25)+(B2-28), (A1-25)+(B2-29), (A1-25)+(B3-1), (A1-25)+(B3-2), (A1-25)+(B4-1), (A1-25)+(B4-2), (A1-25)+(B4-3), (A1-25)+(B4-4), (A1-25)+(B4-5), (A1-25)+(B4-6), (A1-25)+(B4-7), (A1-25)+(B4-8), (A1-25)+(B4-9), (A1-25)+(B4-10), (A1-25)+(B4-11), (A1-25)+(B5-1), (A1-25)+(B5-2), (A1-25)+(B5-3), (A1-25)+(B5-4), (A1-25)+(B5-5), (A1-25)+(B6-1), (A1-25)+(B6-2), (A1-25)+(B6-3), (A1-25)+(B6-4), (A1-25)+(B6-5), (A1-25)+(B6-6), (A1-25)+(B7-1), (A1-25)+(B7-2), (A1-25)+(B7-3), (A1-25)+(B7-4), (A1-25)+(B7-5), (A1-25)+(B7-6), (A1-25)+(B7-7)), (A1-25)+(B7-7), (A1-25)+(B7-8), (A1-25)+(B8-1), (A1-25)+(B8-2), (A1-25)+(B8-3), (A1-25)+(B8-4), (A1-25)+(B8-5), (A1-25)+(B8-6), (A1-25)+(B8-7), (A1-25)+(B9-1), (A1-25)+(B9-2), (A1-25)+(B10-1), (A1-25)+(B10-2), (A1-25)+(B10-3), (A1-25)+(B10-4), (A1-25)+(B10-5), (A1-25)+(B11-1), (A1-25)+(B11-2), (A1-25)+(B11-2),
(A1-26)+(B1-1), (A1-26)+(B1-2), (A1-26)+(B1-3), (A1-26)+(B1-4), (A1-26)+(B1-5), (A1-26)+(B1-6), (A1-26)+(B2-1), (A1-26)+(B2-2), (A1-26)+(B2-3), (A1-26)+(B2-4), (A1-26)+(B2-5), (A1-26)+(B2-6), (A1-26)+(B2-7), (A1-26)+(B2-8), (A1-26)+(B2-9), (A1-26)+(B2-10), (A1-26)+(B2-11), (A1-26)+(B2-12), (A1-26)+(B2-13), (A1-26)+(B2-14), (A1-26)+(B2-15), (A1-26)+(B2-16), (A1-26)+(B2-17), (A1-26)+(B2-18), (A1-26)+(B2-19), (A1-26)+(B2-20), (A1-26)+(B2-21), (A1-26)+(B2-22), (A1-26)+(B2-23), (A1-26)+(B2-24), (A1-26)+(B2-25), (A1-26)+(B2-26), (A1-26)+(B2-27), (A1-26)+(B2-28), (A1-26)+(B2-29), (A1-26)+(B3-1), (A1-26)+(B3-2), (A1-26)+(B4-1), (A1-26)+(B4-2), (A1-26)+(B4-3), (A1-26)+(B4-4), (A1-26)+(B4-5), (A1-26)+(B4-6), (A1-26)+(B4-7), (A1-26)+(B4-8), (A1-26)+(B4-9), (A1-26)+(B4-10), (A1-26)+(B4-11), (A1-26)+(B5-1), (A1-26)+(B5-2), (A1-26)+(B5-3), (A1-26)+(B5-4), (A1-26)+(B5-5), (A1-26)+(B6-1), (A1-26)+(B6-2), (A1-26)+(B6-3), (A1-26)+(B6-4), (A1-26)+(B6-5), (A1-26)+(B6-6), (A1-26)+(B7-1), (A1-26)+(B7-2), (A1-26)+(B7-3), (A1-26)+(B7-4), (A1-26)+(B7-5), (A1-26)+(B7-6), (A1-26)+(B7-7)), (A1-26)+(B7-7), (A1-26)+(B7-8), (A1-26)+(B8-1), (A1-26)+(B8-2), (A1-26)+(B8-3), (A1-26)+(B8-4), (A1-26)+(B8-5), (A1-26)+(B8-6), (A1-26)+(B8-7), (A1-26)+(B9-1), (A1-26)+(B9-2), (A1-26)+(B10-1), (A1-26)+(B10-2), (A1-26)+(B10-3), (A1-26)+(B10-4), (A1-26)+(B10-5), (A1-26)+(B11-1), (A1-26)+(B11-2), (A1-26)+(B11-2),
(A1-27)+(B1-1), (A1-27)+(B1-2), (A1-27)+(B1-3), (A1-27)+(B1-4), (A1-27)+(B1-5), (A1-27)+(B1-6), (A1-27)+(B2-1), (A1-27)+(B2-2), (A1-27)+(B2-3), (A1-27)+(B2-4), (A1-27)+(B2-5), (A1-27)+(B2-6), (A1-27)+(B2-7), (A1-27)+(B2-8), (A1-27)+(B2-9), (A1-27)+(B2-10), (A1-27)+(B2-11), (A1-27)+(B2-12), (A1-27)+(B2-13), (A1-27)+(B2-14), (A1-27)+(B2-15), (A1-27)+(B2-16), (A1-27)+(B2-17), (A1-27)+(B2-18), (A1-27)+(B2-19), (A1-27)+(B2-20), (A1-27)+(B2-21), (A1-27)+(B2-22), (A1-27)+(B2-23), (A1-27)+(B2-24), (A1-27)+(B2-25), (A1-27)+(B2-26), (A1-27)+(B2-27), (A1-27)+(B2-28), (A1-27)+(B2-29), (A1-27)+(B3-1), (A1-27)+(B3-2), (A1-27)+(B4-1), (A1-27)+(B4-2), (A1-27)+(B4-3), (A1-27)+(B4-4), (A1-27)+(B4-5), (A1-27)+(B4-6), (A1-27)+(B4-7), (A1-27)+(B4-8), (A1-27)+(B4-9), (A1-27)+(B4-10), (A1-27)+(B4-11), (A1-27)+(B5-1), (A1-27)+(B5-2), (A1-27)+(B5-3), (A1-27)+(B5-4), (A1-27)+(B5-5), (A1-27)+(B6-1), (A1-27)+(B6-2), (A1-27)+(B6-3), (A1-27)+(B6-4), (A1-27)+(B6-5), (A1-27)+(B6-6), (A1-27)+(B7-1), (A1-27)+(B7-2), (A1-27)+(B7-3), (A1-27)+(B7-4), (A1-27)+(B7-5), (A1-27)+(B7-6), (A1-27)+(B7-7)), (A1-27)+(B7-7), (A1-27)+(B7-8), (A1-27)+(B8-1), (A1-27)+(B8-2), (A1-27)+(B8-3), (A1-27)+(B8-4), (A1-27)+(B8-5), (A1-27)+(B8-6), (A1-27)+(B8-7), (A1-27)+(B9-1), (A1-27)+(B9-2), (A1-27)+(B10-1), (A1-27)+(B10-2), (A1-27)+(B10-3), (A1-27)+(B10-4), (A1-27)+(B10-5), (A1-27)+(B11-1), (A1-27)+(B11-2), (A1-27)+(B11-2),
(A1-28)+(B1-1), (A1-28)+(B1-2), (A1-28)+(B1-3), (A1-28)+(B1-4), (A1-28)+(B1-5), (A1-28)+(B1-6), (A1-28)+(B2-1), (A1-28)+(B2-2), (A1-28)+(B2-3), (A1-28)+(B2-4), (A1-28)+(B2-5), (A1-28)+(B2-6), (A1-28)+(B2-7), (A1-28)+(B2-8), (A1-28)+(B2-9), (A1-28)+(B2-10), (A1-28)+(B2-11), (A1-28)+(B2-12), (A1-28)+(B2-13), (A1-28)+(B2-14), (A1-28)+(B2-15), (A1-28)+(B2-16), (A1-28)+(B2-17), (A1-28)+(B2-18), (A1-28)+(B2-19), (A1-28)+(B2-20), (A1-28)+(B2-21), (A1-28)+(B2-22), (A1-28)+(B2-23), (A1-28)+(B2-24), (A1-28)+(B2-25), (A1-28)+(B2-26), (A1-28)+(B2-27), (A1-28)+(B2-28), (A1-28)+(B2-29), (A1-28)+(B3-1), (A1-28)+(B3-2), (A1-28)+(B4-1), (A1-28)+(B4-2), (A1-28)+(B4-3), (A1-28)+(B4-4), (A1-28)+(B4-5), (A1-28)+(B4-6), (A1-28)+(B4-7), (A1-28)+(B4-8), (A1-28)+(B4-9), (A1-28)+(B4-10), (A1-28)+(B4-11), (A1-28)+(B5-1), (A1-28)+(B5-2), (A1-28)+(B5-3), (A1-28)+(B5-4), (A1-28)+(B5-5), (A1-28)+(B6-1), (A1-28)+(B6-2), (A1-28)+(B6-3), (A1-28)+(B6-4), (A1-28)+(B6-5), (A1-28)+(B6-6), (A1-28)+(B7-1), (A1-28)+(B7-2), (A1-28)+(B7-3), (A1-28)+(B7-4), (A1-28)+(B7-5), (A1-28)+(B7-6), (A1-28)+(B7-7)), (A1-28)+(B7-7), (A1-28)+(B7-8), (A1-28)+(B8-1), (A1-28)+(B8-2), (A1-28)+(B8-3), (A1-28)+(B8-4), (A1-28)+(B8-5), (A1-28)+(B8-6), (A1-28)+(B8-7), (A1-28)+(B9-1), (A1-28)+(B9-2), (A1-28)+(B10-1), (A1-28)+(B10-2), (A1-28)+(B10-3), (A1-28)+(B10-4), (A1-28)+(B10-5), (A1-28)+(B11-1), (A1-28)+(B11-2), (A1-28)+(B11-2),
(A1-29)+(B1-1), (A1-29)+(B1-2), (A1-29)+(B1-3), (A1-29)+(B1-4), (A1-29)+(B1-5), (A1-29)+(B1-6), (A1-29)+(B2-1), (A1-29)+(B2-2), (A1-29)+(B2-3), (A1-29)+(B2-4), (A1-29)+(B2-5), (A1-29)+(B2-6), (A1-29)+(B2-7), (A1-29)+(B2-8), (A1-29)+(B2-9), (A1-29)+(B2-10), (A1-29)+(B2-11), (A1-29)+(B2-12), (A1-29)+(B2-13), (A1-29)+(B2-14), (A1-29)+(B2-15), (A1-29)+(B2-16), (A1-29)+(B2-17), (A1-29)+(B2-18), (A1-29)+(B2-19), (A1-29)+(B2-20), (A1-29)+(B2-21), (A1-29)+(B2-22), (A1-29)+(B2-23), (A1-29)+(B2-24), (A1-29)+(B2-25), (A1-29)+(B2-26), (A1-29)+(B2-27), (A1-29)+(B2-28), (A1-29)+(B2-29), (A1-29)+(B3-1), (A1-29)+(B3-2), (A1-29)+(B4-1), (A1-29)+(B4-2), (A1-29)+(B4-3), (A1-29)+(B4-4), (A1-29)+(B4-5), (A1-29)+(B4-6), (A1-29)+(B4-7), (A1-29)+(B4-8), (A1-29)+(B4-9), (A1-29)+(B4-10), (A1-29)+(B4-11), (A1-29)+(B5-1), (A1-29)+(B5-2), (A1-29)+(B5-3), (A1-29)+(B5-4), (A1-29)+(B5-5), (A1-29)+(B6-1), (A1-29)+(B6-2), (A1-29)+(B6-3), (A1-29)+(B6-4), (A1-29)+(B6-5), (A1-29)+(B6-6), (A1-29)+(B7-1), (A1-29)+(B7-2), (A1-29)+(B7-3), (A1-29)+(B7-4), (A1-29)+(B7-5), (A1-29)+(B7-6), (A1-29)+(B7-7)), (A1-29)+(B7-7), (A1-29)+(B7-8), (A1-29)+(B8-1), (A1-29)+(B8-2), (A1-29)+(B8-3), (A1-29)+(B8-4), (A1-29)+(B8-5), (A1-29)+(B8-6), (A1-29)+(B8-7), (A1-29)+(B9-1), (A1-29)+(B9-2), (A1-29)+(B10-1), (A1-29)+(B10-2), (A1-29)+(B10-3), (A1-29)+(B10-4), (A1-29)+(B10-5), (A1-29)+(B11-1), (A1-29)+(B11-2), (A1-29)+(B11-2),
(A1-30)+(B1-1), (A1-30)+(B1-2), (A1-30)+(B1-3), (A1-30)+(B1-4), (A1-30)+(B1-5), (A1-30)+(B1-6), (A1-30)+(B2-1), (A1-30)+(B2-2), (A1-30)+(B2-3), (A1-30)+(B2-4), (A1-30)+(B2-5), (A1-30)+(B2-6), (A1-30)+(B2-7), (A1-30)+(B2-8), (A1-30)+(B2-9), (A1-30)+(B2-10), (A1-30)+(B2-11), (A1-30)+(B2-12), (A1-30)+(B2-13), (A1-30)+(B2-14), (A1-30)+(B2-15), (A1-30)+(B2-16), (A1-30)+(B2-17), (A1-30)+(B2-18), (A1-30)+(B2-19), (A1-30)+(B2-20), (A1-30)+(B2-21), (A1-30)+(B2-22), (A1-30)+(B2-23), (A1-30)+(B2-24), (A1-30)+(B2-25), (A1-30)+(B2-26), (A1-30)+(B2-27), (A1-30)+(B2-28), (A1-30)+(B2-29), (A1-30)+(B3-1), (A1-30)+(B3-2), (A1-30)+(B4-1), (A1-30)+(B4-2), (A1-30)+(B4-3), (A1-30)+(B4-4), (A1-30)+(B4-5), (A1-30)+(B4-6), (A1-30)+(B4-7), (A1-30)+(B4-8), (A1-30)+(B4-9), (A1-30)+(B4-10), (A1-30)+(B4-11), (A1-30)+(B5-1), (A1-30)+(B5-2), (A1-30)+(B5-3), (A1-30)+(B5-4), (A1-30)+(B5-5), (A1-30)+(B6-1), (A1-30)+(B6-2), (A1-30)+(B6-3), (A1-30)+(B6-4), (A1-30)+(B6-5), (A1-30)+(B6-6), (A1-30)+(B7-1), (A1-30)+(B7-2), (A1-30)+(B7-3), (A1-30)+(B7-4), (A1-30)+(B7-5), (A1-30)+(B7-6), (A1-30)+(B7-7)), (A1-30)+(B7-7), (A1-30)+(B7-8), (A1-30)+(B8-1), (A1-30)+(B8-2), (A1-30)+(B8-3), (A1-30)+(B8-4), (A1-30)+(B8-5), (A1-30)+(B8-6), (A1-30)+(B8-7), (A1-30)+(B9-1), (A1-30)+(B9-2), (A1-30)+(B10-1), (A1-30)+(B10-2), (A1-30)+(B10-3), (A1-30)+(B10-4), (A1-30)+(B10-5), (A1-30)+(B11-1), (A1-30)+(B11-2), (A1-30)+(B11-2),
(A1-31)+(B1-1), (A1-31)+(B1-2), (A1-31)+(B1-3), (A1-31)+(B1-4), (A1-31)+(B1-5), (A1-31)+(B1-6), (A1-31)+(B2-1), (A1-31)+(B2-2), (A1-31)+(B2-3), (A1-31)+(B2-4), (A1-31)+(B2-5), (A1-31)+(B2-6), (A1-31)+(B2-7), (A1-31)+(B2-8), (A1-31)+(B2-9), (A1-31)+(B2-10), (A1-31)+(B2-11), (A1-31)+(B2-12), (A1-31)+(B2-13), (A1-31)+(B2-14), (A1-31)+(B2-15), (A1-31)+(B2-16), (A1-31)+(B2-17), (A1-31)+(B2-18), (A1-31)+(B2-19), (A1-31)+(B2-20), (A1-31)+(B2-21), (A1-31)+(B2-22), (A1-31)+(B2-23), (A1-31)+(B2-24), (A1-31)+(B2-25), (A1-31)+(B2-26), (A1-31)+(B2-27), (A1-31)+(B2-28), (A1-31)+(B2-29), (A1-31)+(B3-1), (A1-31)+(B3-2), (A1-31)+(B4-1), (A1-31)+(B4-2), (A1-31)+(B4-3), (A1-31)+(B4-4), (A1-31)+(B4-5), (A1-31)+(B4-6), (A1-31)+(B4-7), (A1-31)+(B4-8), (A1-31)+(B4-9), (A1-31)+(B4-10), (A1-31)+(B4-11), (A1-31)+(B5-1), (A1-31)+(B5-2), (A1-31)+(B5-3), (A1-31)+(B5-4), (A1-31)+(B5-5), (A1-31)+(B6-1), (A1-31)+(B6-2), (A1-31)+(B6-3), (A1-31)+(B6-4), (A1-31)+(B6-5), (A1-31)+(B6-6), (A1-31)+(B7-1), (A1-31)+(B7-2), (A1-31)+(B7-3), (A1-31)+(B7-4), (A1-31)+(B7-5), (A1-31)+(B7-6), (A1-31)+(B7-7)), (A1-31)+(B7-7), (A1-31)+(B7-8), (A1-31)+(B8-1), (A1-31)+(B8-2), (A1-31)+(B8-3), (A1-31)+(B8-4), (A1-31)+(B8-5), (A1-31)+(B8-6), (A1-31)+(B8-7), (A1-31)+(B9-1), (A1-31)+(B9-2), (A1-31)+(B10-1), (A1-31)+(B10-2), (A1-31)+(B10-3), (A1-31)+(B10-4), (A1-31)+(B10-5), (A1-31)+(B11-1), (A1-31)+(B11-2), (A1-31)+(B11-2),
(A1-32)+(B1-1), (A1-32)+(B1-2), (A1-32)+(B1-3), (A1-32)+(B1-4), (A1-32)+(B1-5), (A1-32)+(B1-6), (A1-32)+(B2-1), (A1-32)+(B2-2), (A1-32)+(B2-3), (A1-32)+(B2-4), (A1-32)+(B2-5), (A1-32)+(B2-6), (A1-32)+(B2-7), (A1-32)+(B2-8), (A1-32)+(B2-9), (A1-32)+(B2-10), (A1-32)+(B2-11), (A1-32)+(B2-12), (A1-32)+(B2-13), (A1-32)+(B2-14), (A1-32)+(B2-15), (A1-32)+(B2-16), (A1-32)+(B2-17), (A1-32)+(B2-18), (A1-32)+(B2-19), (A1-32)+(B2-20), (A1-32)+(B2-21), (A1-32)+(B2-22), (A1-32)+(B2-23), (A1-32)+(B2-24), (A1-32)+(B2-25), (A1-32)+(B2-26), (A1-32)+(B2-27), (A1-32)+(B2-28), (A1-32)+(B2-29), (A1-32)+(B3-1), (A1-32)+(B3-2), (A1-32)+(B4-1), (A1-32)+(B4-2), (A1-32)+(B4-3), (A1-32)+(B4-4), (A1-32)+(B4-5), (A1-32)+(B4-6), (A1-32)+(B4-7), (A1-32)+(B4-8), (A1-32)+(B4-9), (A1-32)+(B4-10), (A1-32)+(B4-11), (A1-32)+(B5-1), (A1-32)+(B5-2), (A1-32)+(B5-3), (A1-32)+(B5-4), (A1-32)+(B5-5), (A1-32)+(B6-1), (A1-32)+(B6-2), (A1-32)+(B6-3), (A1-32)+(B6-4), (A1-32)+(B6-5), (A1-32)+(B6-6), (A1-32)+(B7-1), (A1-32)+(B7-2), (A1-32)+(B7-3), (A1-32)+(B7-4), (A1-32)+(B7-5), (A1-32)+(B7-6), (A1-32)+(B7-7)), (A1-32)+(B7-7), (A1-32)+(B7-8), (A1-32)+(B8-1), (A1-32)+(B8-2), (A1-32)+(B8-3), (A1-32)+(B8-4), (A1-32)+(B8-5), (A1-32)+(B8-6), (A1-32)+(B8-7), (A1-32)+(B9-1), (A1-32)+(B9-2), (A1-32)+(B10-1), (A1-32)+(B10-2), (A1-32)+(B10-3), (A1-32)+(B10-4), (A1-32)+(B10-5), (A1-32)+(B11-1), (A1-32)+(B11-2), (A1-32)+(B11-2),
(A1-33)+(B1-1), (A1-33)+(B1-2), (A1-33)+(B1-3), (A1-33)+(B1-4), (A1-33)+(B1-5), (A1-33)+(B1-6), (A1-33)+(B2-1), (A1-33)+(B2-2), (A1-33)+(B2-3), (A1-33)+(B2-4), (A1-33)+(B2-5), (A1-33)+(B2-6), (A1-33)+(B2-7), (A1-33)+(B2-8), (A1-33)+(B2-9), (A1-33)+(B2-10), (A1-33)+(B2-11), (A1-33)+(B2-12), (A1-33)+(B2-13), (A1-33)+(B2-14), (A1-33)+(B2-15), (A1-33)+(B2-16), (A1-33)+(B2-17), (A1-33)+(B2-18), (A1-33)+(B2-19), (A1-33)+(B2-20), (A1-33)+(B2-21), (A1-33)+(B2-22), (A1-33)+(B2-23), (A1-33)+(B2-24), (A1-33)+(B2-25), (A1-33)+(B2-26), (A1-33)+(B2-27), (A1-33)+(B2-28), (A1-33)+(B2-29), (A1-33)+(B3-1), (A1-33)+(B3-2), (A1-33)+(B4-1), (A1-33)+(B4-2), (A1-33)+(B4-3), (A1-33)+(B4-4), (A1-33)+(B4-5), (A1-33)+(B4-6), (A1-33)+(B4-7), (A1-33)+(B4-8), (A1-33)+(B4-9), (A1-33)+(B4-10), (A1-33)+(B4-11), (A1-33)+(B5-1), (A1-33)+(B5-2), (A1-33)+(B5-3), (A1-33)+(B5-4), (A1-33)+(B5-5), (A1-33)+(B6-1), (A1-33)+(B6-2), (A1-33)+(B6-3), (A1-33)+(B6-4), (A1-33)+(B6-5), (A1-33)+(B6-6), (A1-33)+(B7-1), (A1-33)+(B7-2), (A1-33)+(B7-3), (A1-33)+(B7-4), (A1-33)+(B7-5), (A1-33)+(B7-6), (A1-33)+(B7-7)), (A1-33)+(B7-7), (A1-33)+(B7-8), (A1-33)+(B8-1), (A1-33)+(B8-2), (A1-33)+(B8-3), (A1-33)+(B8-4), (A1-33)+(B8-5), (A1-33)+(B8-6), (A1-33)+(B8-7), (A1-33)+(B9-1), (A1-33)+(B9-2), (A1-33)+(B10-1), (A1-33)+(B10-2), (A1-33)+(B10-3), (A1-33)+(B10-4), (A1-33)+(B10-5), (A1-33)+(B11-1), (A1-33)+(B11-2), (A1-33)+(B11-2),
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(A1-61)+(B1-1), (A1-61)+(B1-2), (A1-61)+(B1-3), (A1-61)+(B1-4), (A1-61)+(B1-5), (A1-61)+(B1-6), (A1-61)+(B2-1), (A1-61)+(B2-2), (A1-61)+(B2-3), (A1-61)+(B2-4), (A1-61)+(B2-5), (A1-61)+(B2-6), (A1-61)+(B2-7), (A1-61)+(B2-8), (A1-61)+(B2-9), (A1-61)+(B2-10), (A1-61)+(B2-11), (A1-61)+(B2-12), (A1-61)+(B2-13), (A1-61)+(B2-14), (A1-61)+(B2-15), (A1-61)+(B2-16), (A1-61)+(B2-17), (A1-61)+(B2-18), (A1-61)+(B2-19), (A1-61)+(B2-20), (A1-61)+(B2-21), (A1-61)+(B2-22), (A1-61)+(B2-23), (A1-61)+(B2-24), (A1-61)+(B2-25), (A1-61)+(B2-26), (A1-61)+(B2-27), (A1-61)+(B2-28), (A1-61)+(B2-29), (A1-61)+(B3-1), (A1-61)+(B3-2), (A1-61)+(B4-1), (A1-61)+(B4-2), (A1-61)+(B4-3), (A1-61)+(B4-4), (A1-61)+(B4-5), (A1-61)+(B4-6), (A1-61)+(B4-7), (A1-61)+(B4-8), (A1-61)+(B4-9), (A1-61)+(B4-10), (A1-61)+(B4-11), (A1-61)+(B5-1), (A1-61)+(B5-2), (A1-61)+(B5-3), (A1-61)+(B5-4), (A1-61)+(B5-5), (A1-61)+(B6-1), (A1-61)+(B6-2), (A1-61)+(B6-3), (A1-61)+(B6-4), (A1-61)+(B6-5), (A1-61)+(B6-6), (A1-61)+(B7-1), (A1-61)+(B7-2), (A1-61)+(B7-3), (A1-61)+(B7-4), (A1-61)+(B7-5), (A1-61)+(B7-6), (A1-61)+(B7-7)), (A1-61)+(B7-7), (A1-61)+(B7-8), (A1-61)+(B8-1), (A1-61)+(B8-2), (A1-61)+(B8-3), (A1-61)+(B8-4), (A1-61)+(B8-5), (A1-61)+(B8-6), (A1-61)+(B8-7), (A1-61)+(B9-1), (A1-61)+(B9-2), (A1-61)+(B10-1), (A1-61)+(B10-2), (A1-61)+(B10-3), (A1-61)+(B10-4), (A1-61)+(B10-5), (A1-61)+(B11-1), (A1-61)+(B11-2), (A1-61)+(B11-2),
(A2-1)+(B1-1), (A2-1)+(B1-2), (A2-1)+(B1-3), (A2-1)+(B1-4), (A2-1)+(B1-5), (A2-1)+(B1-6), (A2-1)+(B2-1), (A2-1)+(B2-2), (A2-1)+(B2-3), (A2-1)+(B2-4), (A2-1)+(B2-5), (A2-1)+(B2-6), (A2-1)+(B2-7), (A2-1)+(B2-8), (A2-1)+(B2-9), (A2-1)+(B2-10), (A2-1)+(B2-11), (A2-1)+(B2-12), (A2-1)+(B2-13), (A2-1)+(B2-14), (A2-1)+(B2-15), (A2-1)+(B2-16), (A2-1)+(B2-17), (A2-1)+(B2-18), (A2-1)+(B2-19), (A2-1)+(B2-20), (A2-1)+(B2-21), (A2-1)+(B2-22), (A2-1)+(B2-23), (A2-1)+(B2-24), (A2-1)+(B2-25), (A2-1)+(B2-26), (A2-1)+(B2-27), (A2-1)+(B2-28), (A2-1)+(B2-29), (A2-1)+(B3-1), (A2-1)+(B3-2), (A2-1)+(B4-1), (A2-1)+(B4-2), (A2-1)+(B4-3), (A2-1)+(B4-4), (A2-1)+(B4-5), (A2-1)+(B4-6), (A2-1)+(B4-7), (A2-1)+(B4-8), (A2-1)+(B4-9), (A2-1)+(B4-10), (A2-1)+(B4-11), (A2-1)+(B5-1), (A2-1)+(B5-2), (A2-1)+(B5-3), (A2-1)+(B5-4), (A2-1)+(B5-5), (A2-1)+(B6-1), (A2-1)+(B6-2), (A2-1)+(B6-3), (A2-1)+(B6-4), (A2-1)+(B6-5), (A2-1)+(B6-6), (A2-1)+(B7-1), (A2-1)+(B7-2), (A2-1)+(B7-3), (A2-1)+(B7-4), (A2-1)+(B7-5), (A2-1)+(B7-6), (A2-1)+(B7-7)), (A2-1)+(B7-7), (A2-1)+(B7-8), (A2-1)+(B8-1), (A2-1)+(B8-2), (A2-1)+(B8-3), (A2-1)+(B8-4), (A2-1)+(B8-5), (A2-1)+(B8-6), (A2-1)+(B8-7), (A2-1)+(B9-1), (A2-1)+(B9-2), (A2-1)+(B10-1), (A2-1)+(B10-2), (A2-1)+(B10-3), (A2-1)+(B10-4), (A2-1)+(B10-5), (A2-1)+(B11-1), (A2-1)+(B11-2), (A2-1)+(B11-2),
(A2-2)+(B1-1), (A2-2)+(B1-2), (A2-2)+(B1-3), (A2-2)+(B1-4), (A2-2)+(B1-5), (A2-2)+(B1-6), (A2-2)+(B2-1), (A2-2)+(B2-2), (A2-2)+(B2-3), (A2-2)+(B2-4), (A2-2)+(B2-5), (A2-2)+(B2-6), (A2-2)+(B2-7), (A2-2)+(B2-8), (A2-2)+(B2-9), (A2-2)+(B2-10), (A2-2)+(B2-11), (A2-2)+(B2-12), (A2-2)+(B2-13), (A2-2)+(B2-14), (A2-2)+(B2-15), (A2-2)+(B2-16), (A2-2)+(B2-17), (A2-2)+(B2-18), (A2-2)+(B2-19), (A2-2)+(B2-20), (A2-2)+(B2-21), (A2-2)+(B2-22), (A2-2)+(B2-23), (A2-2)+(B2-24), (A2-2)+(B2-25), (A2-2)+(B2-26), (A2-2)+(B2-27), (A2-2)+(B2-28), (A2-2)+(B2-29), (A2-2)+(B3-1), (A2-2)+(B3-2), (A2-2)+(B4-1), (A2-2)+(B4-2), (A2-2)+(B4-3), (A2-2)+(B4-4), (A2-2)+(B4-5), (A2-2)+(B4-6), (A2-2)+(B4-7), (A2-2)+(B4-8), (A2-2)+(B4-9), (A2-2)+(B4-10), (A2-2)+(B4-11), (A2-2)+(B5-1), (A2-2)+(B5-2), (A2-2)+(B5-3), (A2-2)+(B5-4), (A2-2)+(B5-5), (A2-2)+(B6-1), (A2-2)+(B6-2), (A2-2)+(B6-3), (A2-2)+(B6-4), (A2-2)+(B6-5), (A2-2)+(B6-6), (A2-2)+(B7-1), (A2-2)+(B7-2), (A2-2)+(B7-3), (A2-2)+(B7-4), (A2-2)+(B7-5), (A2-2)+(B7-6), (A2-2)+(B7-7)), (A2-2)+(B7-7), (A2-2)+(B7-8), (A2-2)+(B8-1), (A2-2)+(B8-2), (A2-2)+(B8-3), (A2-2)+(B8-4), (A2-2)+(B8-5), (A2-2)+(B8-6), (A2-2)+(B8-7), (A2-2)+(B9-1), (A2-2)+(B9-2), (A2-2)+(B10-1), (A2-2)+(B10-2), (A2-2)+(B10-3), (A2-2)+(B10-4), (A2-2)+(B10-5), (A2-2)+(B11-1), (A2-2)+(B11-2), (A2-2)+(B11-2),
(A2-3)+(B1-1), (A2-3)+(B1-2), (A2-3)+(B1-3), (A2-3)+(B1-4), (A2-3)+(B1-5), (A2-3)+(B1-6), (A2-3)+(B2-1), (A2-3)+(B2-2), (A2-3)+(B2-3), (A2-3)+(B2-4), (A2-3)+(B2-5), (A2-3)+(B2-6), (A2-3)+(B2-7), (A2-3)+(B2-8), (A2-3)+(B2-9), (A2-3)+(B2-10), (A2-3)+(B2-11), (A2-3)+(B2-12), (A2-3)+(B2-13), (A2-3)+(B2-14), (A2-3)+(B2-15), (A2-3)+(B2-16), (A2-3)+(B2-17), (A2-3)+(B2-18), (A2-3)+(B2-19), (A2-3)+(B2-20), (A2-3)+(B2-21), (A2-3)+(B2-22), (A2-3)+(B2-23), (A2-3)+(B2-24), (A2-3)+(B2-25), (A2-3)+(B2-26), (A2-3)+(B2-27), (A2-3)+(B2-28), (A2-3)+(B2-29), (A2-3)+(B3-1), (A2-3)+(B3-2), (A2-3)+(B4-1), (A2-3)+(B4-2), (A2-3)+(B4-3), (A2-3)+(B4-4), (A2-3)+(B4-5), (A2-3)+(B4-6), (A2-3)+(B4-7), (A2-3)+(B4-8), (A2-3)+(B4-9), (A2-3)+(B4-10), (A2-3)+(B4-11), (A2-3)+(B5-1), (A2-3)+(B5-2), (A2-3)+(B5-3), (A2-3)+(B5-4), (A2-3)+(B5-5), (A2-3)+(B6-1), (A2-3)+(B6-2), (A2-3)+(B6-3), (A2-3)+(B6-4), (A2-3)+(B6-5), (A2-3)+(B6-6), (A2-3)+(B7-1), (A2-3)+(B7-2), (A2-3)+(B7-3), (A2-3)+(B7-4), (A2-3)+(B7-5), (A2-3)+(B7-6), (A2-3)+(B7-7)), (A2-3)+(B7-7), (A2-3)+(B7-8), (A2-3)+(B8-1), (A2-3)+(B8-2), (A2-3)+(B8-3), (A2-3)+(B8-4), (A2-3)+(B8-5), (A2-3)+(B8-6), (A2-3)+(B8-7), (A2-3)+(B9-1), (A2-3)+(B9-2), (A2-3)+(B10-1), (A2-3)+(B10-2), (A2-3)+(B10-3), (A2-3)+(B10-4), (A2-3)+(B10-5), (A2-3)+(B11-1), (A2-3)+(B11-2), (A2-3)+(B11-2),
(A2-4)+(B1-1), (A2-4)+(B1-2), (A2-4)+(B1-3), (A2-4)+(B1-4), (A2-4)+(B1-5), (A2-4)+(B1-6), (A2-4)+(B2-1), (A2-4)+(B2-2), (A2-4)+(B2-3), (A2-4)+(B2-4), (A2-4)+(B2-5), (A2-4)+(B2-6), (A2-4)+(B2-7), (A2-4)+(B2-8), (A2-4)+(B2-9), (A2-4)+(B2-10), (A2-4)+(B2-11), (A2-4)+(B2-12), (A2-4)+(B2-13), (A2-4)+(B2-14), (A2-4)+(B2-15), (A2-4)+(B2-16), (A2-4)+(B2-17), (A2-4)+(B2-18), (A2-4)+(B2-19), (A2-4)+(B2-20), (A2-4)+(B2-21), (A2-4)+(B2-22), (A2-4)+(B2-23), (A2-4)+(B2-24), (A2-4)+(B2-25), (A2-4)+(B2-26), (A2-4)+(B2-27), (A2-4)+(B2-28), (A2-4)+(B2-29), (A2-4)+(B3-1), (A2-4)+(B3-2), (A2-4)+(B4-1), (A2-4)+(B4-2), (A2-4)+(B4-3), (A2-4)+(B4-4), (A2-4)+(B4-5), (A2-4)+(B4-6), (A2-4)+(B4-7), (A2-4)+(B4-8), (A2-4)+(B4-9), (A2-4)+(B4-10), (A2-4)+(B4-11), (A2-4)+(B5-1), (A2-4)+(B5-2), (A2-4)+(B5-3), (A2-4)+(B5-4), (A2-4)+(B5-5), (A2-4)+(B6-1), (A2-4)+(B6-2), (A2-4)+(B6-3), (A2-4)+(B6-4), (A2-4)+(B6-5), (A2-4)+(B6-6), (A2-4)+(B7-1), (A2-4)+(B7-2), (A2-4)+(B7-3), (A2-4)+(B7-4), (A2-4)+(B7-5), (A2-4)+(B7-6), (A2-4)+(B7-7)), (A2-4)+(B7-7), (A2-4)+(B7-8), (A2-4)+(B8-1), (A2-4)+(B8-2), (A2-4)+(B8-3), (A2-4)+(B8-4), (A2-4)+(B8-5), (A2-4)+(B8-6), (A2-4)+(B8-7), (A2-4)+(B9-1), (A2-4)+(B9-2), (A2-4)+(B10-1), (A2-4)+(B10-2), (A2-4)+(B10-3), (A2-4)+(B10-4), (A2-4)+(B10-5), (A2-4)+(B11-1), (A2-4)+(B11-2), (A2-4)+(B11-2).
In the inventive herbicidal compositions, the application rate of the herbicides of the general formula (I) (component A) is typically 1 to 500 g of active ingredient (a.i.) per hectare, preferably 2 to 300 g of a.i./ha, more preferably 3 to 200 g of a.i./ha. The application rate of the herbicides of component B is typically 1 to 5000 g of active ingredient per hectare, preferably 2 to 3000 g of a.i./ha, more preferably 3 to 2000 g of a.i./ha. The application rate of the safeners of component C is typically 1 to 500 g of active ingredient per hectare, preferably 2 to 400 g of a.i./ha, more preferably 3 to 300 g of a.i./ha.
On application of the inventive herbicidal compositions, a very broad spectrum of harmful plants is controlled pre-emergence and post-emergence, for example annual and perennial mono- or dicotyledonous weeds and unwanted crop plants. The inventive herbicidal compositions are particularly suitable for use in crops such as cereals, corn, rice, soya, oilseed rape, sugar beet, cotton, sugar cane, and also for use in perennial crops, plantations and on non-crop land. They are likewise highly suitable for use in transgenic crops of corn, cereals, sugar beet, rice, cotton and Glycine max. (e.g. RR soya or LL soya) and crossbreeds thereof), Phaseolus, Pisum, Vicia and Arachis, or vegetable crops from various botanical groups such as potato, leek, cabbage, carrot, tomato, onion, and also perennial and plantation crops such as pome fruit and stone fruit, soft fruit, wine, Hevea, bananas, sugar cane, coffee, tea, citrus, nut plantations, lawn, palm crops and forest crops. For the use of the inventive herbicide-safener combinations (A)+(B), these crops are likewise preferred, particular preference being given to use in cereals (e.g. wheat, barley, rye, oats), rice, corn, millet/sorghum, sugar beet, sugar cane, sunflower, oilseed rape and cotton. The herbicide-safener combinations (A)+(B) can also be used in tolerant and non-tolerant mutant crops and tolerant and non-tolerant transgenic crops, preferably of corn, rice, cereals, oilseed rape, cotton, sugar beet and soya, for example those resistant to imidazolinone herbicides, atrazine, glufosinate, glyphosate, 2,4 D, dicamba and herbicides from the group of the inhibitors of hydroxyphenylpyruvate dioxygenase, such as sulcotrione, mesotrione, tembotrione, tefuryltrione, benzobicyclon, bicyclopyrone and ketospiradox.
A herbicidally effective amount in the context of the invention means an amount of one or more herbicides capable of adversely affecting plant growth. An antidotically effective amount in the context of the invention means an amount of one or more safeners capable of reducing the phytotoxic effect of crop protection active ingredients (for example of herbicides) on crop plants.
According to their properties, the safeners (C) present in the inventive herbicidal compositions can also be used for pretreatment of the seed of the crop plant (for example for dressing of the seed) or introduced into the seed furrows prior to sowing or employed together with the herbicide prior to or after emergence of the plants. Pre-emergence treatment includes both the treatment of the area under cultivation (including any water present in the area under cultivation, for example in the case of applications to rice) prior to sowing and the treatment of the areas under cultivation in which seeds have been sown but which are not yet covered by growing plants. Preference is given to application together with the herbicide. For this purpose, it is possible to use tank-mixes or ready-made formulations.
In a preferred embodiment, the seed (for example grains, seeds or vegetative propagation organs such as tubers or budded parts of shoots) or seedlings are pretreated with the safeners (C), optionally in combination with other active agrochemical ingredients. For pretreatment of the seed, the active ingredients can be applied to the seed, for example by dressing, or the active ingredients and the seed can be added to water or other solvents, and the active ingredients can be taken up, for example, by adsorption or diffusion in a dipping process or by swelling or pre-germination. For pretreatment of seedlings, the young plants can be contacted with the safeners, optionally in combination with other active agrochemical ingredients, for example by spraying, dipping or watering, and then transplanted and optionally aftertreated with the herbicides (A) and (B).
The seed or seedlings can be treated with the safeners (C) alone or together with other active agrochemical ingredients—such as fungicides, insecticides or plant fortifiers, fertilizers or swelling and germination accelerators. After the pretreatment application, the safeners may subsequently be applied once again before, after or together with one or more herbicides of the formula (I) (A) and herbicides (B), possibly also in combination with other known herbicides. The pretreatment of the seed or seedlings can achieve improved long-term efficacy of the safeners.
The present invention thus further provides a method of controlling unwanted plants in plant crops, which is characterized in that components (A), (B) and optionally (C) of the inventive herbicidal compositions are deployed, for example separately or together, on the plants (for example harmful plants such as mono- or dicotyledonous weeds or unwanted crop plants), the seed (for example grains, seeds or vegetative propagation organs such as tubers or budded parts of shoots) or the area on which the plants grow (for example the area under cultivation). One or more safeners (C) may be applied before, after or simultaneously with the herbicide(s) of the general formula (I) (A) and the herbicides (B) to the plants, the seed or the area on which the plants grow (for example the area under cultivation). In a preferred embodiment, the safeners (C) are used for seed treatment.
Unwanted plants are understood to mean all plants which grow at sites where they are unwanted. These may, for example, be harmful plants (for example monocotyledonous or dicotyledonous weeds or unwanted crop plants), including, for example, those which are resistant to certain active herbicidal compounds, such as glyphosate, atrazine, glufosinate or imidazolinone herbicides. Monocotyledonous weeds are classified, for example, in the genera Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera, Phalaris. Dicotyledonous weeds are classified, for example, in the genera Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum, Euphorbia, Kochia, Biden, Stellaria.
The invention also provides for the use of the inventive herbicidal compositions for controlling unwanted vegetation, preferably in plant crops.
The inventive herbicidal compositions can be prepared by known methods, for example as mixed formulations of the individual components, optionally with further active ingredients, additives and/or customary formulation auxiliaries, and these are then applied in a customary manner after dilution with water, or as tank mixes by joint dilution of the separately formulated or partly separately formulated individual components with water. Likewise possible is the application at different times (split application) of the separately formulated or partly separately formulated individual components. It is also possible to apply the individual components or the herbicidal compositions in a plurality of portions (sequential application), for example by pre-emergence applications followed by post-emergence applications or by early post-emergence applications followed by medium or late post-emergence applications. Preference is given to the joint or immediately successive application of the active ingredients in the respective combination.
The inventive herbicidal compositions can also be used for control of harmful plants in crops of genetically modified plants which are known or are yet to be developed.
In general, transgenic plants are characterized by particular advantageous properties, for example by resistances to certain pesticides, in particular certain herbicides, resistances to plant diseases or pathogens of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses. Other particular properties relate, for example, to the harvested material with regard to quantity, quality, storability, composition and specific constituents. For instance, there are known transgenic plants with an elevated starch content or altered starch quality, or those with a different fatty acid composition in the harvested material. Other particular properties may be tolerance or resistance to abiotic stressors, for example heat, low temperatures, drought, salinity and ultraviolet radiation.
Preference is given to the use of the inventive herbicidal compositions in economically important transgenic crops of useful plants and ornamentals, for example of cereals such as wheat, barley, rye, oats, millet/sorghum, rice, cassava and corn, or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, peas and other vegetables.
Conventional ways of producing novel plants which have modified properties in comparison to existing plants consist, for example, in traditional breeding methods and the generation of mutants. Alternatively, novel plants with modified properties can be generated with the aid of recombinant methods (see, for example, EP-A-0221044, EP-A-0131624). For example, there have been descriptions in several cases of:
Numerous molecular biology techniques which can be used to produce novel transgenic plants with modified properties are known in principle; see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, or Christou, “Trends in Plant Science” 1 (1996) 423-431).
For such recombinant manipulations, nucleic acid molecules which allow mutagenesis or sequence alteration by recombination of DNA sequences can be introduced into plasmids. With the aid of standard methods, it is possible, for example, to undertake base exchanges, remove parts of sequences or add natural or synthetic sequences. For the connection of the DNA fragments to one another, it is possible to add adapters or linkers to the fragments; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y.; or Winnacker “Gene und Klone”, VCH Weinheim, 2nd edition, 1996.
For example, the generation of plant cells with a reduced activity of a gene product can be achieved by expressing at least one corresponding antisense RNA, a sense RNA for achieving a cosuppression effect, or by expressing at least one suitably constructed ribozyme which specifically cleaves transcripts of the abovementioned gene product.
To this end, it is firstly possible to use DNA molecules which encompass the entire coding sequence of a gene product inclusive of any flanking sequences which may be present, and also DNA molecules which only encompass portions of the coding sequence, in which case it is necessary for these portions to be long enough to have an antisense effect in the cells. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical to them.
When expressing nucleic acid molecules in plants, the protein synthesized may be localized in any desired compartment of the plant cell. However, to achieve localization in a particular compartment, it is possible, for example, to join the coding region to DNA sequences which ensure localization in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). The nucleic acid molecules can also be expressed in the organelles of the plant cells.
The transgenic plant cells can be regenerated by known techniques to give rise to entire plants. In principle, the transgenic plants may be plants of any desired plant species, i.e. not only monocotyledonous but also dicotyledonous plants.
Thus, transgenic plants can be obtained whose properties are altered by overexpression, suppression or inhibition of homologous (=natural) genes or gene sequences or expression of heterologous (=foreign) genes or gene sequences.
Preferably the inventive compositions can be used in transgenic crops which are resistant to growth regulators such as, for example, dicamba, or to herbicides which inhibit essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), or to herbicides from the group of the sulfonylureas, the glyphosates, glufosinates or benzoylisoxazoles and analogous active ingredients.
On employment of the inventive compositions in transgenic crops, not only do the effects toward harmful plants observed in other crops occur, but often also effects which are specific to application in the particular transgenic crop, for example an altered or specifically widened spectrum of weeds which can be controlled, altered application rates which can be used for the application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and influencing of growth and yield of the transgenic crop plants.
The invention therefore also provides for the use of the inventive compositions for control of harmful plants in transgenic crop plants.
Preference is given to the use of the inventive compositions in economically important transgenic crops of useful plants and ornamentals, for example of cereals (e.g. wheat, barley, rye, oats), millet/sorghum, rice, cassava and corn, or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, peas and other vegetable crops.
The invention therefore also provides for the use of the inventive compositions for control of harmful plants in transgenic crop plants or crop plants having tolerance through selective breeding.
The herbicides (A), (B) and the safeners (C) can be converted together or separately to customary formulations, for example for application by spraying, watering, sprinkling and seed dressing, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active ingredient-impregnated natural and synthetic substances, microencapsulations in polymeric substances. The formulations may comprise the customary auxiliaries and additives.
These formulations are produced in a known manner, for example by mixing the active ingredients with extenders, i.e. liquid solvents, pressurized liquefied gases and/or solid carriers, optionally with use of surfactants, i.e. emulsifiers and/or dispersants and/or foam formers.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Useful liquid solvents essentially include: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example mineral oil fractions, mineral and vegetable oils, alcohols such as butanol or glycol and the ethers and esters thereof, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulfoxide, and water.
Useful solid carriers include: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; useful solid carriers for granules include: for example crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours, and granules of organic material, such as sawdust, coconut shells, corn cobs and tobacco stalks; useful emulsifiers and/or foam formers include: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolyzates; useful dispersants include: for example lignosulfite waste liquors and methylcellulose.
In the formulations, it is possible to use tackifiers such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Further additives may be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian blue, and organic colorants such as alizarin colorants, azo colorants and metal phthalocyanine colorants, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations contain generally between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90% by weight.
As such or in their formulations, the herbicides (A), (B) and the safeners (C) can also be used as a mixture with other active agrochemical ingredients for controlling unwanted vegetation, for example for controlling weeds or for controlling unwanted crop plants, finished formulations or tank mixes, for example, being possible.
Also possible are mixtures with other known active ingredients such as fungicides, insecticides, acaricides, nematicides, bird antifeedants, plant nutrients and soil structure improvers, and likewise with additives and formulation auxiliaries customary in crop protection.
The herbicides (A), (B) and the safeners (C) can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. Application is typically accomplished, for example, by watering, sprinkling, spraying, broadcasting.
The active ingredients can be deployed on the plants, plant parts, seed or area under cultivation (farmland), preferably on the seed or the green plants and plant parts, and optionally additionally on the farmland. One means of application is the co-deployment of the active ingredients in the form of tank-mixes, by mixing the optimally formulated concentrated formulations of the individual active ingredients together in the tank with water and deploying the spray liquor obtained.
A co-formulation of the inventive combination of active ingredients (A), (B) and (C) has the advantage of easier applicability, because the amounts of the components can already be set in the optimal ratio with respect to one another. Moreover, the auxiliaries in the formulation can be optimized to one another.
For application, the formulations in commercial form are, if appropriate, diluted in a customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules with water. Dust-type formulations, granules for soil application or granules for scattering and sprayable solutions are not normally diluted further with other inert substances prior to application.
BIOLOGICAL EXAMPLES
All trials whose results are shown were conducted in a greenhouse by the methodology specified below. The effect of the inventive herbicidal compositions was examined on the following harmful plants 14 and 21 days after application:
Echinochloa crus-galli (ECHCG), Eleusine indica (ELEIN), Setaria viridis (SETVI), Amaranthus retroflexus (AMARE), Chenopodium album (CHEAL), Kochia scoparia (KCHSC), Solanum nigrum (SOLNI), Avena fatua (AVEFA), Bromus sterilis (BROST), Lolium multiflorum (LOLMU), Phalaris minor (PHAMI), Poa annua (POAAN), Galium aparine (GALAP), Matricaria inodora (MATIN) and Polygonum convolvulus (POLCO).
The harmful plant seeds were sown in pots (diameter 8 cm) with sandy loam soil and germinated under optimal conditions. The inventive herbicidal compositions or the active ingredients alone were applied post-emergence to the planted pots with a spray volume of 300 L/ha. The trial was conducted in a greenhouse under optimum growth conditions. The herbicidal effects were assessed visually by comparison of untreated and treated plants. The percentages mean: 0%=no effects, 100%=the plants die off completely). The percentages are used to calculate interactions between individual treatments and combination treatments according to S. R. Colby, Weeds 15, pages 20 to 22 (1967).
The abbreviations mean:
Assessment:
The results are shown in the tables below.
Number | Date | Country | Kind |
---|---|---|---|
13190182 | Oct 2013 | EP | regional |
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/EP2014/072645 | 10/22/2014 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
---|---|---|---|
WO2015/059187 | 4/30/2015 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
4902340 | Hubele | Feb 1990 | A |
6251827 | Ziemer et al. | Jun 2001 | B1 |
6914035 | Ziemer et al. | Jul 2005 | B2 |
8404618 | Plant et al. | Mar 2013 | B2 |
8551918 | Polge | Oct 2013 | B2 |
20140080705 | Koehn et al. | Mar 2014 | A1 |
Number | Date | Country |
---|---|---|
2004000767 | Apr 2004 | CH |
00049071 | Apr 1982 | EP |
9847356 | Oct 1998 | WO |
02060255 | Aug 2002 | WO |
03022050 | Mar 2003 | WO |
2004014138 | Feb 2004 | WO |
2005055716 | Jun 2005 | WO |
2005104848 | Nov 2005 | WO |
2012126932 | Sep 2012 | WO |
Entry |
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Number | Date | Country | |
---|---|---|---|
20160242419 A1 | Aug 2016 | US |