CN101835383A - 除草剂结合物 - Google Patents
除草剂结合物 Download PDFInfo
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- CN101835383A CN101835383A CN200880113301A CN200880113301A CN101835383A CN 101835383 A CN101835383 A CN 101835383A CN 200880113301 A CN200880113301 A CN 200880113301A CN 200880113301 A CN200880113301 A CN 200880113301A CN 101835383 A CN101835383 A CN 101835383A
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- CN
- China
- Prior art keywords
- alkyl
- ion
- methyl
- perhaps
- group
- Prior art date
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- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 134
- 239000004009 herbicide Substances 0.000 claims abstract description 184
- 150000001875 compounds Chemical class 0.000 claims abstract description 159
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 claims abstract description 86
- -1 Phosphonium ion Chemical class 0.000 claims abstract description 76
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 57
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 30
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 25
- 150000002367 halogens Chemical class 0.000 claims abstract description 22
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 19
- 244000025254 Cannabis sativa Species 0.000 claims abstract description 19
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000000460 chlorine Substances 0.000 claims abstract description 14
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 14
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 13
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims abstract description 12
- 150000001768 cations Chemical class 0.000 claims abstract description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 12
- RBSXHDIPCIWOMG-UHFFFAOYSA-N 1-(4,6-dimethoxypyrimidin-2-yl)-3-(2-ethylsulfonylimidazo[1,2-a]pyridin-3-yl)sulfonylurea Chemical compound CCS(=O)(=O)C=1N=C2C=CC=CN2C=1S(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 RBSXHDIPCIWOMG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 11
- UOUXAYAIONPXDH-UHFFFAOYSA-M flucarbazone-sodium Chemical compound [Na+].O=C1N(C)C(OC)=NN1C(=O)[N-]S(=O)(=O)C1=CC=CC=C1OC(F)(F)F UOUXAYAIONPXDH-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 11
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 10
- QZXATCCPQKOEIH-UHFFFAOYSA-N Florasulam Chemical compound N=1N2C(OC)=NC=C(F)C2=NC=1S(=O)(=O)NC1=C(F)C=CC=C1F QZXATCCPQKOEIH-UHFFFAOYSA-N 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- WZJZMXBKUWKXTQ-UHFFFAOYSA-N desmedipham Chemical compound CCOC(=O)NC1=CC=CC(OC(=O)NC=2C=CC=CC=2)=C1 WZJZMXBKUWKXTQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- GLBLPMUBLHYFCW-UHFFFAOYSA-N n-(5,7-dimethoxy-[1,2,4]triazolo[1,5-a]pyrimidin-2-yl)-2-methoxy-4-(trifluoromethyl)pyridine-3-sulfonamide Chemical compound N1=C2N=C(OC)C=C(OC)N2N=C1NS(=O)(=O)C1=C(OC)N=CC=C1C(F)(F)F GLBLPMUBLHYFCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- KVEQCVKVIFQSGC-UHFFFAOYSA-N tritosulfuron Chemical compound FC(F)(F)C1=NC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(F)(F)F)=N1 KVEQCVKVIFQSGC-UHFFFAOYSA-N 0.000 claims abstract description 10
- CTTHWASMBLQOFR-UHFFFAOYSA-N Amidosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)N(C)S(C)(=O)=O)=N1 CTTHWASMBLQOFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- UWVKRNOCDUPIDM-UHFFFAOYSA-N Ethoxysulfuron Chemical compound CCOC1=CC=CC=C1OS(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 UWVKRNOCDUPIDM-UHFFFAOYSA-N 0.000 claims abstract description 9
- JUJFQMPKBJPSFZ-UHFFFAOYSA-M Iodosulfuron-methyl-sodium Chemical compound [Na+].COC(=O)C1=CC=C(I)C=C1S(=O)(=O)[N-]C(=O)NC1=NC(C)=NC(OC)=N1 JUJFQMPKBJPSFZ-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000005619 Sulfosulfuron Substances 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005864 Sulphur Substances 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 9
- NIFKBBMCXCMCAO-UHFFFAOYSA-N methyl 2-[(4,6-dimethoxypyrimidin-2-yl)carbamoylsulfamoyl]-4-(methanesulfonamidomethyl)benzoate Chemical group COC(=O)C1=CC=C(CNS(C)(=O)=O)C=C1S(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 NIFKBBMCXCMCAO-UHFFFAOYSA-N 0.000 claims abstract description 9
- RSMUVYRMZCOLBH-UHFFFAOYSA-N metsulfuron methyl Chemical group COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(C)=NC(OC)=N1 RSMUVYRMZCOLBH-UHFFFAOYSA-N 0.000 claims abstract description 9
- DEDOPGXGGQYYMW-UHFFFAOYSA-N molinate Chemical compound CCSC(=O)N1CCCCCC1 DEDOPGXGGQYYMW-UHFFFAOYSA-N 0.000 claims abstract description 9
- AHTPATJNIAFOLR-UHFFFAOYSA-N thifensulfuron-methyl Chemical group S1C=CC(S(=O)(=O)NC(=O)NC=2N=C(OC)N=C(C)N=2)=C1C(=O)OC AHTPATJNIAFOLR-UHFFFAOYSA-N 0.000 claims abstract description 9
- VTNQPKFIQCLBDU-UHFFFAOYSA-N Acetochlor Chemical compound CCOCN(C(=O)CCl)C1=C(C)C=CC=C1CC VTNQPKFIQCLBDU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003666 Amidosulfuron Substances 0.000 claims abstract description 8
- 239000005503 Desmedipham Substances 0.000 claims abstract description 8
- 239000005529 Florasulam Substances 0.000 claims abstract description 8
- 239000005584 Metsulfuron-methyl Substances 0.000 claims abstract description 8
- WXZVAROIGSFCFJ-UHFFFAOYSA-N N,N-diethyl-2-(naphthalen-1-yloxy)propanamide Chemical compound C1=CC=C2C(OC(C)C(=O)N(CC)CC)=CC=CC2=C1 WXZVAROIGSFCFJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005607 Pyroxsulam Substances 0.000 claims abstract description 8
- 239000005623 Thifensulfuron-methyl Substances 0.000 claims abstract description 8
- 239000005629 Tritosulfuron Substances 0.000 claims abstract description 8
- WYEHFWKAOXOVJD-UHFFFAOYSA-N diflufenican Chemical compound FC1=CC(F)=CC=C1NC(=O)C1=CC=CN=C1OC1=CC=CC(C(F)(F)F)=C1 WYEHFWKAOXOVJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- JLYFCTQDENRSOL-VIFPVBQESA-N dimethenamid-P Chemical compound COC[C@H](C)N(C(=O)CCl)C=1C(C)=CSC=1C JLYFCTQDENRSOL-VIFPVBQESA-N 0.000 claims abstract description 8
- IANUJLZYFUDJIH-UHFFFAOYSA-N flufenacet Chemical compound C=1C=C(F)C=CC=1N(C(C)C)C(=O)COC1=NN=C(C(F)(F)F)S1 IANUJLZYFUDJIH-UHFFFAOYSA-N 0.000 claims abstract description 8
- STEPQTYSZVCJPV-UHFFFAOYSA-N metazachlor Chemical compound CC1=CC=CC(C)=C1N(C(=O)CCl)CN1N=CC=C1 STEPQTYSZVCJPV-UHFFFAOYSA-N 0.000 claims abstract description 8
- IDOWTHOLJBTAFI-UHFFFAOYSA-N phenmedipham Chemical compound COC(=O)NC1=CC=CC(OC(=O)NC=2C=C(C)C=CC=2)=C1 IDOWTHOLJBTAFI-UHFFFAOYSA-N 0.000 claims abstract description 8
- NQLVQOSNDJXLKG-UHFFFAOYSA-N prosulfocarb Chemical compound CCCN(CCC)C(=O)SCC1=CC=CC=C1 NQLVQOSNDJXLKG-UHFFFAOYSA-N 0.000 claims abstract description 8
- YMXOXAPKZDWXLY-QWRGUYRKSA-N tribenuron methyl Chemical group COC(=O)[C@H]1CCCC[C@@H]1S(=O)(=O)NC(=O)N(C)C1=NC(C)=NC(OC)=N1 YMXOXAPKZDWXLY-QWRGUYRKSA-N 0.000 claims abstract description 8
- 239000005507 Diflufenican Substances 0.000 claims abstract description 7
- 239000005509 Dimethenamid-P Substances 0.000 claims abstract description 7
- 239000005531 Flufenacet Substances 0.000 claims abstract description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
- NAGRVUXEKKZNHT-UHFFFAOYSA-N Imazosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2N3C=CC=CC3=NC=2Cl)=N1 NAGRVUXEKKZNHT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005580 Metazachlor Substances 0.000 claims abstract description 7
- 239000005582 Metosulam Substances 0.000 claims abstract description 7
- VGHPMIFEKOFHHQ-UHFFFAOYSA-N Metosulam Chemical compound N1=C2N=C(OC)C=C(OC)N2N=C1S(=O)(=O)NC1=C(Cl)C=CC(C)=C1Cl VGHPMIFEKOFHHQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005585 Napropamide Substances 0.000 claims abstract description 7
- 239000005594 Phenmedipham Substances 0.000 claims abstract description 7
- 239000005603 Prosulfocarb Substances 0.000 claims abstract description 7
- HBCBJXOSTRIDAQ-UHFFFAOYSA-N [S].NC=O Chemical compound [S].NC=O HBCBJXOSTRIDAQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 7
- XIGAUIHYSDTJHW-UHFFFAOYSA-N mefenacet Chemical compound N=1C2=CC=CC=C2SC=1OCC(=O)N(C)C1=CC=CC=C1 XIGAUIHYSDTJHW-UHFFFAOYSA-N 0.000 claims abstract description 7
- JTHMVYBOQLDDIY-UHFFFAOYSA-N methyl 2-[(4-methyl-5-oxo-3-propoxy-1,2,4-triazole-1-carbonyl)sulfamoyl]benzoate Chemical compound O=C1N(C)C(OCCC)=NN1C(=O)NS(=O)(=O)C1=CC=CC=C1C(=O)OC JTHMVYBOQLDDIY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- JLYFCTQDENRSOL-UHFFFAOYSA-N 2-chloro-N-(2,4-dimethylthiophen-3-yl)-N-(1-methoxypropan-2-yl)acetamide Chemical compound COCC(C)N(C(=O)CCl)C=1C(C)=CSC=1C JLYFCTQDENRSOL-UHFFFAOYSA-N 0.000 claims abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005567 Imazosulfuron Substances 0.000 claims abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 6
- LTUNNEGNEKBSEH-UHFFFAOYSA-N Prosulfuron Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)CCC(F)(F)F)=N1 LTUNNEGNEKBSEH-UHFFFAOYSA-N 0.000 claims abstract description 6
- QHTQREMOGMZHJV-UHFFFAOYSA-N Thiobencarb Chemical compound CCN(CC)C(=O)SCC1=CC=C(Cl)C=C1 QHTQREMOGMZHJV-UHFFFAOYSA-N 0.000 claims abstract description 6
- AMRQXHFXNZFDCH-SECBINFHSA-N [(2r)-1-(ethylamino)-1-oxopropan-2-yl] n-phenylcarbamate Chemical compound CCNC(=O)[C@@H](C)OC(=O)NC1=CC=CC=C1 AMRQXHFXNZFDCH-SECBINFHSA-N 0.000 claims abstract description 6
- XCSGPAVHZFQHGE-UHFFFAOYSA-N alachlor Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl XCSGPAVHZFQHGE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- HKPHPIREJKHECO-UHFFFAOYSA-N butachlor Chemical compound CCCCOCN(C(=O)CCl)C1=C(CC)C=CC=C1CC HKPHPIREJKHECO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011575 calcium Substances 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 6
- NSWAMPCUPHPTTC-UHFFFAOYSA-N chlorimuron-ethyl Chemical group CCOC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(Cl)=CC(OC)=N1 NSWAMPCUPHPTTC-UHFFFAOYSA-N 0.000 claims abstract description 6
- BWUPSGJXXPATLU-UHFFFAOYSA-N dimepiperate Chemical compound C=1C=CC=CC=1C(C)(C)SC(=O)N1CCCCC1 BWUPSGJXXPATLU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- AIMMSOZBPYFASU-UHFFFAOYSA-N n-(4,6-dimethoxypyrimidin-2-yl)-n'-[3-(2,2,2-trifluoroethoxy)pyridin-1-ium-2-yl]sulfonylcarbamimidate Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)OCC(F)(F)F)=N1 AIMMSOZBPYFASU-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTCOGUMHFFWOJV-UHFFFAOYSA-N nicosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)C(=O)N(C)C)=N1 RTCOGUMHFFWOJV-UHFFFAOYSA-N 0.000 claims abstract description 6
- CSWIKHNSBZVWNQ-UHFFFAOYSA-N pethoxamide Chemical compound CCOCCN(C(=O)CCl)C(=C(C)C)C1=CC=CC=C1 CSWIKHNSBZVWNQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011591 potassium Substances 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 6
- PHNUZKMIPFFYSO-UHFFFAOYSA-N propyzamide Chemical compound C#CC(C)(C)NC(=O)C1=CC(Cl)=CC(Cl)=C1 PHNUZKMIPFFYSO-UHFFFAOYSA-N 0.000 claims abstract description 6
- MEFOUWRMVYJCQC-UHFFFAOYSA-N rimsulfuron Chemical compound CCS(=O)(=O)C1=CC=CN=C1S(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 MEFOUWRMVYJCQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- JKPSVOHVUGMYGH-UHFFFAOYSA-M sodium;(4,6-dimethoxypyrimidin-2-yl)-[[3-methoxycarbonyl-6-(trifluoromethyl)pyridin-2-yl]sulfonylcarbamoyl]azanide Chemical compound [Na+].COC(=O)C1=CC=C(C(F)(F)F)N=C1S(=O)(=O)NC(=O)[N-]C1=NC(OC)=CC(OC)=N1 JKPSVOHVUGMYGH-UHFFFAOYSA-M 0.000 claims abstract description 6
- KZNDFYDURHAESM-UHFFFAOYSA-N 2-chloro-n-(2-ethyl-6-methylphenyl)-n-(propan-2-yloxymethyl)acetamide Chemical compound CCC1=CC=CC(C)=C1N(COC(C)C)C(=O)CCl KZNDFYDURHAESM-UHFFFAOYSA-N 0.000 claims abstract description 5
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical compound CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005490 Carbetamide Substances 0.000 claims abstract description 5
- WMLPCIHUFDKWJU-UHFFFAOYSA-N Cinosulfuron Chemical compound COCCOC1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(OC)=NC(OC)=N1 WMLPCIHUFDKWJU-UHFFFAOYSA-N 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- DFCAFRGABIXSDS-UHFFFAOYSA-N Cycloate Chemical compound CCSC(=O)N(CC)C1CCCCC1 DFCAFRGABIXSDS-UHFFFAOYSA-N 0.000 claims abstract description 5
- QNXAVFXEJCPCJO-UHFFFAOYSA-N Diclosulam Chemical compound N=1N2C(OCC)=NC(F)=CC2=NC=1S(=O)(=O)NC1=C(Cl)C=CC=C1Cl QNXAVFXEJCPCJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- QAHFOPIILNICLA-UHFFFAOYSA-N Diphenamid Chemical compound C=1C=CC=CC=1C(C(=O)N(C)C)C1=CC=CC=C1 QAHFOPIILNICLA-UHFFFAOYSA-N 0.000 claims abstract description 5
- GUVLYNGULCJVDO-UHFFFAOYSA-N EPTC Chemical compound CCCN(CCC)C(=O)SCC GUVLYNGULCJVDO-UHFFFAOYSA-N 0.000 claims abstract description 5
- BXEHUCNTIZGSOJ-UHFFFAOYSA-N Esprocarb Chemical compound CC(C)C(C)N(CC)C(=O)SCC1=CC=CC=C1 BXEHUCNTIZGSOJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- HWATZEJQIXKWQS-UHFFFAOYSA-N Flazasulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)C(F)(F)F)=N1 HWATZEJQIXKWQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- RXCPQSJAVKGONC-UHFFFAOYSA-N Flumetsulam Chemical compound N1=C2N=C(C)C=CN2N=C1S(=O)(=O)NC1=C(F)C=CC=C1F RXCPQSJAVKGONC-UHFFFAOYSA-N 0.000 claims abstract description 5
- FMGZEUWROYGLAY-UHFFFAOYSA-N Halosulfuron-methyl Chemical group ClC1=NN(C)C(S(=O)(=O)NC(=O)NC=2N=C(OC)C=C(OC)N=2)=C1C(=O)OC FMGZEUWROYGLAY-UHFFFAOYSA-N 0.000 claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- FFQPZWRNXKPNPX-UHFFFAOYSA-N N-benzyl-2-[4-fluoro-3-(trifluoromethyl)phenoxy]butanamide Chemical compound C=1C=CC=CC=1CNC(=O)C(CC)OC1=CC=C(F)C(C(F)(F)F)=C1 FFQPZWRNXKPNPX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005586 Nicosulfuron Substances 0.000 claims abstract description 5
- SGEJQUSYQTVSIU-UHFFFAOYSA-N Pebulate Chemical compound CCCCN(CC)C(=O)SCCC SGEJQUSYQTVSIU-UHFFFAOYSA-N 0.000 claims abstract description 5
- WGVWLKXZBUVUAM-UHFFFAOYSA-N Pentanochlor Chemical compound CCCC(C)C(=O)NC1=CC=C(C)C(Cl)=C1 WGVWLKXZBUVUAM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005593 Pethoxamid Substances 0.000 claims abstract description 5
- 239000005602 Propyzamide Substances 0.000 claims abstract description 5
- 239000005604 Prosulfuron Substances 0.000 claims abstract description 5
- 239000005616 Rimsulfuron Substances 0.000 claims abstract description 5
- OKUGPJPKMAEJOE-UHFFFAOYSA-N S-propyl dipropylcarbamothioate Chemical compound CCCSC(=O)N(CCC)CCC OKUGPJPKMAEJOE-UHFFFAOYSA-N 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 5
- MWBPRDONLNQCFV-UHFFFAOYSA-N Tri-allate Chemical compound CC(C)N(C(C)C)C(=O)SCC(Cl)=C(Cl)Cl MWBPRDONLNQCFV-UHFFFAOYSA-N 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 5
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims abstract description 5
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims abstract description 5
- MAHPNPYYQAIOJN-UHFFFAOYSA-N azimsulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2N(N=CC=2C2=NN(C)N=N2)C)=N1 MAHPNPYYQAIOJN-UHFFFAOYSA-N 0.000 claims abstract description 5
- XMQFTWRPUQYINF-UHFFFAOYSA-N bensulfuron-methyl Chemical group COC(=O)C1=CC=CC=C1CS(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 XMQFTWRPUQYINF-UHFFFAOYSA-N 0.000 claims abstract description 5
- WZDDLAZXUYIVMU-UHFFFAOYSA-N bromobutide Chemical compound CC(C)(C)C(Br)C(=O)NC(C)(C)C1=CC=CC=C1 WZDDLAZXUYIVMU-UHFFFAOYSA-N 0.000 claims abstract description 5
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 claims abstract description 5
- CWJSHJJYOPWUGX-UHFFFAOYSA-N chlorpropham Chemical compound CC(C)OC(=O)NC1=CC=CC(Cl)=C1 CWJSHJJYOPWUGX-UHFFFAOYSA-N 0.000 claims abstract description 5
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及一种除草剂结合物,包括组分(A)和(B),其中(A)为一种或多种选自以下的除草剂:2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺和通式(I)的化合物其中阳离子(M+)为:(a)碱金属离子,优选锂、钠或钾,或者(b)碱土金属离子,优选钙或镁,或者(c)过渡金属离子,优选锰、铜、锌或铁,或者(d)铵离子,其中任选地一个、两个或三个或全部四个氢原子被选自以下的相同或不同基团所取代:(C1-C4)-烷基、羟基-(C1-C4)-烷基、(C3-C6)-环烷基、(C1-C4)-烷氧基-(C1-C4)-烷基、羟基-(C1-C4)-烷氧基-(C1-C4)-烷基、(C1-C6)-巯基烷基、苯基和苯甲基,其中上述基团任选地被选自以下的一个或多个相同或不同基团所取代:卤素如F、Cl、Br或I、硝基、氰基、叠氮基、(C1-C6)-烷基、(C1-C6)-卤代烷基、(C3-C6)-环烷基、(C1-C6)-烷氧基、(C1-C6)-卤代烷氧基和苯基,并且其中在每种情况下氮原子处的两个取代基一起任选地形成一个未取代的或取代的环,或者(e)鏻离子,或者(f)锍离子,优选三-((C1-C4)-烷基)锍,或者(g)氧鎓离子,优选三-((C1-C4)-烷基)氧鎓,或者(h)任选地为单环或稠环的和/或被(C1-C4)-烷基取代的饱和或不饱和/芳香族含氮杂环离子化合物,其在所述环系统中具有1-10个碳原子,和(B)一种或多种(磺)酰胺类除草剂,包括:氟丁酰草胺、溴丁酰草胺、二甲吩草胺、二甲吩草胺-P、双苯酰草胺、敌草胺、烯草胺、MT-5950、萘草胺、炔苯酰草胺、吡氟酰草胺、乙氧苯草胺、氟噻草胺、苯噻酰草胺、氯磺酰草胺、甲氯酰草胺、氟吡酰草胺、敌稗、N-苯基邻氨甲酰苯甲酸、乙草胺、甲草胺、丁草胺、二甲草胺、吡唑草胺、异丙甲草胺、S-异丙甲草胺、丙草胺、毒草胺、异丙草胺、噻吩草胺、磺草灵、甲萘威、双酰草胺、氯苯胺灵、甜菜安、甜菜宁、苯胺灵、丁草敌、环草敌、哌草丹、茵草敌、戊草丹、磺菌威、禾草敌、坪草丹、克草敌、苄草丹、稗草丹、禾草丹、野燕畏、灭草敌、酰嘧磺隆、四唑嘧磺隆、苄嘧磺隆、氯嘧磺隆、氯磺隆、醚磺隆、环丙嘧磺隆、胺苯磺隆、乙氧嘧磺隆、啶嘧磺隆、氟吡磺隆、氟啶嘧磺隆、甲酰氨磺隆、氯吡嘧磺隆、唑吡嘧磺隆、碘甲磺隆钠盐、甲磺胺磺隆、甲磺隆、单嘧磺隆、烟嘧磺隆、嘧苯胺磺隆、环氧嘧磺隆、氟嘧磺隆、氟磺隆、吡嘧磺隆、砜嘧磺隆、甲嘧磺隆、磺酰磺隆、噻吩磺隆、醚苯磺隆、苯磺隆、三氟啶磺隆、氟胺磺隆、三氟甲磺隆、HNPC-C9908(2-[[[[[4-甲氧基-6-(甲硫基)-2-嘧啶基]氨基]羰基]氨基]磺酰基]苯甲酸甲酯)、NC-330、NC-620、TH-547、monosulfuron-methyl、氟酮磺隆、丙苯磺隆、甲基噻烯卡巴腙、氯酯磺草胺、双氯磺草胺、双氟磺草胺、唑嘧磺草胺、磺草唑胺、五氟磺草胺和甲氧磺草胺。
Description
本发明涉及包括2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺和/或其盐,以及选自(磺)酰胺类化合物的除草活性化合物的除草剂结合物(Combination)。
本发明涉及用于防治不想要的植物的作物保护组合物的技术领域,例如通过播种前法(掺入或不掺入)、通过出苗前法或出苗后法在例如以下作物中防治不想要的植物:小麦(硬粒小麦和普通小麦)、玉米、大豆、甜菜、甘蔗、棉花、水稻、豆类(例如矮菜豆和蚕豆)、亚麻、大麦、燕麦、黑麦、小黑麦、油菜、马铃薯和黍类(高粱)、牧草和青草(greens)/草坪区域。
本发明具体涉及一种包括至少两种除草剂的除草剂结合物,以及涉及它用于防治不想要的植物的用途。
已知经取代的苯磺酰脲具有除草剂特性。它们是例如单取代或多取代的苯基衍生物(例如US 4127405、WO 9209608、BE 853374、WO9213845、EP 84020、WO 9406778、WO 02072560、US 4169719、US4629494、DE 4038430)。
此外,已知某些N-[(1,3,5-三嗪-2-基氨基羰基]芳基磺酰胺具有除草剂特性(参见DE 2715786)。根据WO 2006/114220,还已知在苯环处碘化的磺酰胺具有除草剂特性。但是,这些化合物的除草剂作用并非在各方面都令人满意,例如相容性、活性谱、对耐受性或抗性物种的防治、对花卉作物的作用或使用灵活性方面。
N-[(1,3,5-三嗪-2-基氨基羰基]芳基磺酰胺抗有害植物的除草剂活性已经处于一个较高水平;但是,其通常取决于施用率、各自的制剂形式、各自待防治的有害植物或者有害植物谱、气候条件和土壤条件等。另一个指标是除草剂的作用持续时间或者降解速度。如果合适的话,还要考虑到有害植物敏感性的变化,所述变化可能会在长期使用除草剂时发生或者是以地理限制性方式发生。对于不同的植物来说通过增加除草剂施用率来补偿活性的损失只能达到某一程度,这是因为例如这样会降低除草剂的选择性或者是因为即使提高施用率也得不到改进的作用。
本发明的一个目标是提供一种改良的作物保护组合物。
令人吃惊的是,现在已经发现通过结合使用2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺和/或其盐,以及选自(磺)酰胺类化合物的具有不同结构的除草剂实现了这一目标,它们在例如被用于在以下作物中防治不想要的植物时以一种特别有利的方式共同发挥作用,所述作物例如小麦(硬粒小麦和普通小麦)、玉米、大豆、甜菜、甘蔗、棉花、水稻、豆类(例如矮菜豆和蚕豆)、亚麻、大麦、燕麦、黑麦、小黑麦、油菜、马铃薯和黍类(高粱)、牧草地和青草/草坪区域。
(磺)酰胺类化合物是已知的用于防治不想要的植物的除草活性化合物;参见,例如EP 239414、US 4288244、DE 3303388、US 5457085、US 3120434、US 3480671、EP 206251、EP 205271、US 2556664、US3534098、EP 53011、US 04385927、EP 348737、DE 2822155、US 3894078、GB 869169、EP 447004、DE 1039779、HU 176582、US 3442945、DE2305495、DE 2648008、DE 2328340、DE 1014380、HU 53483、US 4802907、GB 1040541、US 2903478、US 3177061、US 2695225、DE 1567151、GB574995、DE 1031571、US 3175897、JP 1098331、US 2913327、WO8300329、JP 80127302、DE 1300947、DE 2135768、US 3175887、US3836524、JP 85067463、US 3582314、US 53330821、EP 131258、US4746353、US 4420325、US 4394506、US 4127405、US 4479821、US5009699、EP 136061、EP 324569、EP 184385、WO 2002030921、WO09215576、WO 09529899、US 4668277、EP 305939、WO 09641537、WO 09510507、EP 7677、CN 01080116、US 4789393、EP 971902、US5209771、EP 84020、EP 120814、EP 87780、WO 08804297、EP 477808、EP 30142、EP 44808、EP 202830、WO 09741112、EP 336587、DE 4038430、CN 01323789、EP 189069、WO 2005103044、WO 2003061388、EP 507171、WO 2001005788、US 5163995、EP 142152、US 5828924、WO 2002036595及上述公开本文中所引用的文献。
因此,本发明提供了一种除草剂结合物,包含选自(A)的除草剂和选自(B)的除草剂,其中
(A)为一种或多种选自以下的除草剂:2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺和通式(I)的化合物
其中
阳离子(M+)为:
(a)碱金属离子,优选锂、钠或钾,或者
(b)碱土金属离子,优选钙或镁,或者
(c)过渡金属离子,优选锰、铜、锌或铁,或者
(d)铵离子,其中任选地一个、两个、三个或全部四个氢原子被选自以下的相同或不同基团所取代:(C1-C4)-烷基、羟基-(C1-C4)-烷基、(C3-C6)-环烷基、(C1-C4)-烷氧基-(C1-C4)-烷基、羟基-(C1-C4)-烷氧基-(C1-C4)-烷基、(C1-C6)-巯基烷基、苯基和苯甲基,其中上述基团任选地被一个或多个选自以下的相同或不同基团所取代:卤素如F、Cl、Br或I、硝基、氰基、叠氮基、(C1-C6)-烷基、(C1-C6)-卤代烷基、(C3-C6)-环烷基、(C1-C6)-烷氧基、(C1-C6)-卤代烷氧基和苯基,并且其中在每种情况下氮原子上的两个取代基一起任选地形成一个未取代的或取代的环,或者
(e)鏻离子,或者
(f)锍离子,优选三-((C1-C4)-烷基)锍,或者
(g)氧鎓离子,优选三-((C1-C4)-烷基)氧鎓,或者
(h)任选地为单环或稠环的和/或被(C1-C4)-烷基取代的饱和或不饱和/芳香族含氮杂环离子化合物,其在环系统中具有1-10个碳原子,
和
(B)为一种或多种选自(磺)酰胺类的除草剂,包括:
烷基酰胺类亚组(亚组1),由以下物质组成:
氟丁酰草胺(beflubutamid)[CAS RN 113614-08-7](=B1-1);溴丁酰草胺(bromobutide)[CAS RN 74712-19-9](=B1-2);二甲吩草胺(dimethenamid)[CAS RN 87674-68-8](=B1-3);二甲吩草胺-P(dimethenamid-P)[CAS RN 163515-14-8](=B1-4);双苯酰草胺(diphenamid)[CAS RN 957-51-7](=B1-5);敌草胺(napropamide)[CASRN 15299-99-7](=B1-6);烯草胺(pethoxamid)[CAS RN 106700-29-2](=B1-7);MT-5950,即N-[3-氯-4-(1-甲基乙基)-苯基]-2-甲基戊酰胺[CAS RN106827-21-8](=B1-8);
苯甲酰胺类亚组(亚组2),由以下物质组成:
萘草胺(naptalam)[CAS RN 132-66-1](=B2-1);炔苯酰草胺(propyzamide)[CAS RN 23950-58-5](=B2-2);
苯胺(anilide)类亚组(亚组3),由以下物质组成:
吡氟酰草胺(diflufenican)[CAS RN 83164-33-4](=B3-1);乙氧苯草胺(etobenzanid)[CAS RN 79540-50-4](=B3-2);氟噻草胺(flufenacet)[CAS RN 142459-58-3](=B3-3);苯噻酰草胺(mefenacet)[CAS RN73250-68-7](=B3-4);氯磺酰草胺(mefluidide)[CAS RN 53780-34-0](=B3-5);甲氯酰草胺(pentanochlor)[CAS RN 2307-68-8](=B3-6);氟吡酰草胺(picolinafen)[CAS RN 137641-05-5](=B3-7);敌稗(propanil)[CAS RN 709-98-8](=B3-8);N-苯基邻氨甲酰苯甲酸[CAS RN 4727-29-1](=B3-9);
氯乙酰苯胺(chloracetanilide)类亚组(亚组4),由以下物质组成:
乙草胺(acetochlor)[CAS RN 34256-82-1](=B4-1);甲草胺(alachlor)[CAS RN 15972-60-8](=B4-2);丁草胺(butachlor)[CAS RN 23184-66-9](=B4-3);二甲草胺(dimethachlor)[CAS RN 50563-36-5](=B4-4);吡唑草胺(metazachlor)[CAS RN 67129-08-2](=B4-5);异丙甲草胺(metolachlor)[CAS RN 51218-45-2](=B4-6);S-异丙甲草胺(S-metolachlor)[CAS RN 87392-12-9,(S)-异构体,[CAS RN 178961-20-1,(R)-异构体(=B4-7);丙草胺(pretilachlor)[CAS RN 51218-49-6](=B4-8);毒草胺(propachlor)[CAS RN 1918-16-7](=B4-9);异丙草胺(propisochlor)[CAS RN 86763-47-5](2-氯-6’-乙基-N-异丙氧基甲基乙酰邻甲苯胺)(=B4-10);噻吩草胺(thenylchlor)[CAS RN 96491-05-3](=B4-11);
氨基甲酸酯类亚组(亚组5),由以下物质组成:
磺草灵(asulam)[CAS RN 3337-71-1](=B5-1);甲萘威(carbaryl)[CAS RN 63-25-2](=B5-2);双酰草胺(carbetamide)[CAS RN 16118-49-3](=B5-3);氯苯胺灵(chlorpropham)[CAS RN 101-21-3](=B5-4);甜菜安(desmedipham)[CAS RN 13684-56-5](=B5-5);甜菜宁(phenmedipham)[CAS RN 13684-63-4](=B5-6);苯胺灵(propham)[CAS RN 122-42-9](=B5-7);
硫代氨基甲酸酯类亚组(亚组6),由以下物质组成:
丁草敌(butylate)[CAS RN 2008-41-5](=B6-1);环草敌(cycloate)[CAS RN 1134-23-2](=B6-2);哌草丹(dimepiperate)[CAS RN61432-55-1](=B6-3);茵草敌(EPTC)[CAS RN 759-94-4](=B6-4);戊草丹(esprocarb)[CAS RN 85758-20-2](=B6-5);磺菌威(methasulfocarb)[CAS RN 66952-49-6](=B6-6);禾草敌(molinate)[CAS RN 2212-67-1](=B6-7);坪草丹(orbencarb)[CAS RN 34622-58-7](=B6-8);克草敌(pebulate)[CAS 8N 1114-71-2](=B6-9);苄草丹(prosulfocarb)[CASRN 52888-80-9](=B6-10);稗草丹(pyributicarb)[CAS RN 88678-67-5](=B6-11);禾草丹(thiobencarb)[CAS RN 28249-77-6](=B6-12);野燕畏(tri-allate)[CAS RN 2303-17-5](=B6-13);灭草敌(vernolate)[CASRN 1929-77-7](=B6-14);
磺酰脲类亚组(亚组7),由以下物质组成:
酰嘧磺隆(amidosulfuron)[CAS RN 120923-37-7](=B7-1);四唑嘧磺隆(azimsulfuron)[CAS RN 120162-55-2](=B7-2);苄嘧磺隆(bensulfuron-methyl)[CAS RN 83055-99-6](=B7-3);氯嘧磺隆(chlorimuron-ethyl)[CAS RN 90982-32-4](=B7-4);氯磺隆(chlorsulfuron)[CAS RN 64902-72-3](=B7-5);醚磺隆(cinosulfuron)[CAS RN 94593-91-6](=B7-6);环丙嘧磺隆(cyclosulfamuron)[CAS RN136849-15-5](=B7-7);胺苯磺隆(ethametsulfuron-methyl)[CAS RN97780-06-8](=B7-8);乙氧嘧磺隆(ethoxysulfuron)[CAS RN 126801-58-9](=B7-9);啶嘧磺隆(flazasulfuron)[CAS RN 104040-78-0](=B7-10);氟吡磺隆(flucetosulfuron)[CAS RN 412928-75-7](=B7-11);氟啶嘧磺隆(flupyrsulfuron-methyl-sodium)[CAS RN 144740-54-5][(=B7-12);甲酰氨磺隆(foramsulfuron)[CAS RN 173159-57-4](=B7-13);氯吡嘧磺隆(halosulfuron-methyl)[[CAS RN 100784-20-1(=B7-14);唑吡嘧磺隆(imazosulfuron)[CAS RN 122548-33-8](=B7-15);碘甲磺隆钠盐(iodosulfuron-methyl-sodium)[CAS RN 144550-36-7](=B7-16);甲磺胺磺隆(mesosulfuron-methyl)[CAS RN 208465-21-8](=B7-17);甲磺隆(metsulfuron-methyl)[CAS RN 74223-64-6](=B7-18);单嘧磺隆(monosulfuron)[CAS RN 155860-63-2](=B7-19);烟嘧磺隆(nicosulfuron)[CAS RN 111991-09-4](=B7-20);嘧苯胺磺隆(orthosulfamuron)[CAS RN 213464-77-8](=B7-21);环氧嘧磺隆(oxasulfuron)[CAS RN 144651-06-9](=B7-22);氟嘧磺隆(primisulfuron-methyl)[CAS RN 86209-51-0](=B7-23);氟磺隆(prosulfuron)[CAS RN 94125-34-5](=B7-24);吡嘧磺隆(pyrazosulfuron-ethyl)[CAS RN 93697-74-6](=B7-25);砜嘧磺隆(rimsulfuron)[CAS RN 122931-48-0](=B7-26);甲嘧磺隆(sulfometuron-methyl)[CAS RN 74222-97-2](=B7-27);磺酰磺隆(sulfosulfuron)[CAS RN 141776-32-1](=B7-28);噻吩磺隆(thifensulfuron-methyl)[CAS RN 79277-27-3](=B7-29);醚苯磺隆(triasulfuron)[CAS RN 82097-50-5](=B7-30);苯磺隆(tribenuron-methyl)[CAS RN 101200-48-0](=B7-31);三氟啶磺隆(trifloxysulfuron)[CAS RN 145099-21-4](三氟啶磺隆钠)(=B7-32);氟胺磺隆(triflusulfuron-methyl)[CAS RN 126535-15-7](=B7-33);三氟甲磺隆(tritosulfuron)[CAS RN 142469-14-5](=B7-34);HNPC-C9908[CAS RN 441050-97-1](2-[[[[[4-甲氧基-6-(甲硫基)-2-嘧啶基]氨基]羰基]氨基]磺酰基]甲基苯甲酸酯)(=B7-35);NC-330[CAS RN 104770-29-8](=B7-36);NC-620[CAS RN 868680-84-6](=B7-37);TH-547[CAS RN570415-88-2](=B7-38);monosulfuron-methyl[CAS RN 175076-90-1](=B7-39);
磺酰基氨基羰基三唑啉酮(triazolinone)类亚组(亚组8),由以下物质组成:
氟酮磺隆(flucarbazone-sodium)[CAS RN 181274-17-9](=B8-1);丙苯磺隆(propoxycarbazone-sodium)[CAS RN 181274-15-7](=B8-2);甲基噻烯卡巴腙(thiencarbazone-methyl)[CAS RN 317815-83-1](=B8-3);
三唑并嘧啶类亚组(亚组9),由以下物质组成:
氯酯磺草胺(cloransulam-methyl)[147150-35-4](=B9-1);双氯磺草胺(diclosulam)[CAS RN 145701-21-9][(=B9-2);双氟磺草胺(florasulam)[CAS RN 145701-23-1](=B9-3);唑嘧磺草胺(flumetsulam)[CAS RN 98967-40-9](=B9-4);磺草唑胺(metosulam)[CAS RN139528-85-1](=B9-5);五氟磺草胺(penoxsulam)[CAS RN 219714-96-2](=B9-6);甲氧磺草胺(pyroxsulam)[CAS RN 422556-08-9](=B9-7)。
B组中所述名称(通用名)后方括号中的“CAS RN”是指“化学文摘服务社注册号(Chemical Abstract Service Registry Number)”,它是一种通用的参考号,能够将所命名的物质清楚地加以分类,因为“CAS RN”还特别区分了异构体,包括立体异构体。
优选的除草剂(A)为2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺和其中阳离子(M+)如下的式(I)化合物:
(a)碱金属离子,优选锂、钠或钾,或者
(b)碱土金属离子,优选钙或镁,或者
(c)过渡金属离子,优选锰、铜、锌或铁,或者
(d)铵离子,其中任选地一个、两个、三个或全部四个氢原子被选自以下的相同或不同基团所取代:(C1-C4)-烷基、羟基-(C1-C4)-烷基、(C3-C4)-环烷基、(C1-C2)-烷氧基-(C1-C2)-烷基、羟基-(C1-C2)-烷氧基-(C1-C2)-烷基、(C1-C2)-巯基烷基、苯基和苯甲基,其中上述基团任选地被选自以下的一个或多个相同或不同基团所取代:卤素如F、Cl、Br或I、硝基、氰基、叠氮基、(C1-C2)-烷基、(C1-C2)-卤代烷基、(C3-C4)-环烷基、(C1-C2)-烷氧基、(C1-C2)-卤代烷氧基和苯基,并且其中在每种情况下氮原子上的两个取代基一起任选地形成一个未取代的或取代的环,或者
(e)季鏻离子,优选四-((C1-C4)-烷基)鏻和四苯基鏻,其中所述(C1-C4)-烷基基团和苯基基团任选地被选自以下的相同或不同基团所单取代或多取代:卤素如F、Cl、Br或I、(C1-C2)-烷基,(C1-C2)-卤代烷基、(C3-C4)-环烷基、(C1-C2)-烷氧基、(C1-C2)-卤代烷氧基,或者
(f)叔锍离子,优选三-((C1-C4)-烷基)锍或三苯基锍,其中所述(C1-C4)-烷基基团和苯基基团任选地被选自以下的相同或不同基团所单取代或多取代:卤素例如F、Cl、Br或I、(C1-C2)-烷基,(C1-C2)-卤代烷基、(C3-C4)-环烷基、(C1-C2)-烷氧基、(C1-C2)-卤代烷氧基,或者
(g)叔氧鎓离子,优选三-((C1-C4)-烷基)氧鎓,其中所述(C1-C4)-烷基基团和苯基基团任选地被选自以下的相同或不同基团所单取代或多取代:卤素例如F、Cl、Br或I、(C1-C2)-烷基,(C1-C2)-卤代烷基、(C3-C4)-环烷基、(C1-C2)-烷氧基、(C1-C2)-卤代烷氧基,或者
(h)以下杂环化合物的阳离子,例如吡啶、喹啉、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、2,4-二甲基吡啶、2,5-二甲基吡啶、2,6-二甲基吡啶、5-乙基-2-甲基吡啶、哌啶、吡咯烷、吗啉、硫吗啉(thiomorpholine)、吡咯、咪唑、1,5-二氮杂双环[4.3.0]壬-5-烯(DBN)、1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)。
即使没有明确提及,在基团定义中所提到的烃基团(如烷基、烯基或炔基)以及与杂原子结合的烃基团如烷氧基、烷硫基、卤代烷基或烷氨基都可为直链或支链的。
用作除草剂(A)的优选化合物的实例为2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺(A-0)和下表A中列出的式(I)的化合物(即化合物(A-1至A-35))。
表A:通式(I)的化合物,
其中M+表示所述化合物的相应的盐
化合物 | M+ |
A-1 | 锂 |
化合物 | M+ |
A-2 | 钠 |
A-3 | 钾 |
A-4 | 镁 |
A-5 | 钙 |
A-6 | 铵 |
A-7 | 甲基铵 |
A-8 | 二甲基铵 |
A-9 | 四甲基铵 |
A-10 | 乙基铵 |
化合物 | M+ |
A-11 | 二乙基铵 |
A-12 | 四乙基铵 |
A-13 | 丙基铵 |
A-14 | 四丙基铵 |
A-15 | 异丙基铵 |
A-16 | 二异丙基铵 |
A-17 | 丁基铵 |
A-18 | 四丁基铵 |
A-19 | (2-羟基乙-1-基)铵 |
A-20 | 双-N,N-(2-羟基乙-1-基)铵 |
A-21 | 三-N,N,N-(2-羟基乙-1-基)铵 |
A-22 | 1-苯基乙基铵 |
A-23 | 2-苯基乙基铵 |
A-24 | 三甲基锍 |
A-25 | 三甲基氧鎓 |
A-26 | 吡啶鎓 |
A-27 | 2-甲基吡啶鎓 |
A-28 | 4-甲基吡啶鎓 |
A-29 | 2,4-二甲基吡啶鎓 |
A-30 | 2,6-二甲基吡啶鎓 |
化合物 | M+ |
A-31 | 哌啶鎓 |
化合物 | M+ |
A-32 | 咪唑鎓 |
A-33 | 吗啉鎓 |
A-34 | 1,5-二氮杂双环[4.3.0]壬-7-烯鎓 |
A-35 | 1,8-二氮杂双环[5.4.0]十一碳-7-烯鎓 |
特别优选的除草剂(A)为2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺和其中阳离子(M+)如下的式(I)化合物,
钠离子、钾离子、锂离子、镁离子、钙离子、NH4 +离子、(2-羟基乙-1-基)铵离子、双-N,N-(2-羟基乙-1-基)铵离子、三-N,N,N-(2-羟基乙-1-基)铵离子、甲基铵离子、二甲基铵离子、三甲基铵离子、四甲基铵离子、乙基铵离子、二乙基铵离子、三乙基铵离子、四乙基铵离子、异丙基铵离子、二异丙基铵离子、四丙基铵离子、四丁基铵离子、2-(2-羟基乙-1-氧基)乙-1-基铵离子、二(2-羟基乙-1-基)铵离子、三甲基苯甲基铵离子、三-((C1-C4)-烷基)锍离子或三-((C1-C4)-烷基)氧鎓离子、苯甲基铵离子、1-苯基乙基铵离子、2-苯基乙基铵离子、二异丙基乙基铵离子、吡啶鎓离子、哌啶鎓离子、咪唑鎓离子、吗啉鎓离子、1,8-二氮杂双环[5.4.0]十一碳-7-烯鎓离子。
特别优选的除草剂(A)为2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺和其中阳离子(M+)为钠离子、钾离子、镁离子、钙离子或NH4 +离子的式(I)化合物。
同样特别优选的除草剂(A)为2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺和其中阳离子(M+)为钠离子、钾离子或NH4 +离子的式(I)化合物。
优选作为除草剂(B)的化合物有:
二甲吩草胺(=B1-3);二甲吩草胺-P(=B1-4);敌草胺(=B1-6);烯草胺(=B1-7);炔苯酰草胺(=B2-2);吡氟酰草胺(=B3-1);氟噻草胺(=B3-3);苯噻酰草胺(=B3-4);氟吡酰草胺(=B3-7);敌稗(=B3-8);乙草胺(=B4-1);甲草胺(=B4-2);丁草胺(=B4-3);吡唑草胺(=B4-5);异丙甲草胺(=B4-6);S-异丙甲草胺(=B4-7);丙草胺(=B4-8);噻吩草胺(=B4-11);磺草灵(=B5-1);双酰草胺(=B5-3);甜菜安(=B5-5);甜菜宁(=B5-6);戊草丹(=B6-5);禾草敌(=B6-7);苄草丹(=B6-10);禾草丹(=B6-12);酰嘧磺隆(=B7-1);氯嘧磺隆(=B7-4);环丙嘧磺隆(=B7-7);乙氧嘧磺隆(=B7-9);氟啶嘧磺隆(=B7-12);甲酰氨磺隆(=B7-13);碘甲磺隆钠盐(=B7-16);甲磺胺磺隆(=B7-17);甲磺隆(=B7-18);烟嘧磺隆(=B7-20);嘧苯胺磺隆(=B7-21);氟磺隆(=B7-24);吡嘧磺隆(=B7-25);砜嘧磺隆(=B7-26);磺酰磺隆(=B7-28);噻吩磺隆(=B7-29);苯磺隆(=B7-31);三氟啶磺隆(钠)(=B7-32);三氟甲磺隆(=B7-34);氟酮磺隆(=B8-1);丙苯磺隆(=B8-2);甲基噻烯卡巴腙(=B8-3);双氟磺草胺(=B9-3);磺草唑胺(=B9-5);五氟磺草胺(=B9-6);甲氧磺草胺(=B9-7)。
特别优选用作除草剂(B)的化合物有:
二甲吩草胺-P(=B1-4);敌草胺(=B1-6);吡氟酰草胺(=B3-1);氟噻草胺(=B3-3);苯噻酰草胺(=B3-4);乙草胺(=B4-1);吡唑草胺(=B4-5);S-异丙甲草胺(=B4-7);磺草灵(=B5-1);甜菜安(=B5-5);甜菜宁(=B5-6);禾草敌(=B6-7);苄草丹(=B6-10);酰嘧磺隆(=B7-1);乙氧嘧磺隆(=B7-9);甲酰氨磺隆(=B7-13);碘甲磺隆钠盐(=B7-16);甲磺胺磺隆(=B7-17);甲磺隆(=B7-18);磺酰磺隆(=B7-28);噻吩磺隆(=B7-29);苯磺隆(=B7-31);三氟甲磺隆(=B7-34);氟酮磺隆(=B8-1);丙苯磺隆(=B8-2);甲基噻烯卡巴腙(=B8-3);双氟磺草胺(=B9-3);磺草唑胺(=B9-5);甲氧磺草胺(=B9-7)。
根据取代基的类型和连接方式,除草剂(A)和(B)可以立体异构体的形式存在。通式(I)包括由其具体空间形式限定的所有可能的立体异构体,如对映异构体、非对映异构体、Z和E异构体。
例如,如果存在一个或多个烯基,则可能存在非对映异构体(Z和E异构体)。例如,如果存在一个或多个不对称取代的碳原子,则可能存在对映异构体和非对映异构体。可以使用常规分离方法由制备的混合物获得立体异构体,例如利用色谱分离方法。还可通过立体选择反应和采用旋光性原料和/或助剂来制备立体异构体。因此,本发明还涉及除草剂(A)和/或除草剂(B)的所有立体异构体,但不再以其具体立体形式示出这些除草剂,并且本发明还涉及它们的混合物。
此外,本发明的除草剂结合物还可包括其他组分,例如不同类型的农业化学活性化合物和/或作物保护中常用的制剂助剂和/或添加剂,或者本发明的除草剂结合物可与这些组分一起使用。
2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺的盐的制备,特别是通式(I)的化合物的制备在现有技术中是已知的;还可参照2007年10月24日提交的Bayer CropScience AG的欧洲专利申请EP07020807.9,标题为“Salts of 2-iodo-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)carbamoyl]benzenesulfonamide,processes for theirpreparation and their use as herbicides and plant growth regulators”。
在一个优选的实施方案中,本发明的除草剂结合物包括有效量的除草剂(A)和(B),并且/或者具有协同作用。在例如当将除草剂(A)和(B)以共同制剂(coformulation)或以桶混(tank mix)形式一起施用时可以观察到协同作用;但是,当将所述活性化合物在不同时间(分开)施用时,也可以观察到协同作用。还可以分成多个部分的形式施用(序贯施用)所述除草剂或除草剂结合物,例如出苗前使用,然后进行出苗后使用;或者出苗后早期施用,然后进行出苗后中或晚期施用。优选将所研究的结合物的除草剂(A)和(B)联合施用或几乎同时施用。
协同效应使得单个除草剂的施用率降低,在相同施用率下达到更高的效力,防治尚未被防治(空白)的物种,防治对单一除草剂或对多种除草剂耐受或具有抗性的物种,延长施用期和/或降低所需的单次施用的次数,并且因此使得对于用户来说杂草防治系统更加经济和环保。
例如,本发明的除草剂(A)+(B)的结合物使得可以这样一种方式协同地增强其活性,所述方式即——远远的并且以出乎意料的方式——超过单独使用除草剂(A)和(B)所能达到的活性。
所述通式(I)包括所有立体异构体及其混合物,特别是外消旋混合物,以及——如果存在对映异构体——具有生物活性的各个对映异构体。
(A)组的除草剂抑制乙酰乳酸合酶(ALS)并且因此抑制植物中的蛋白质生物合成。除草剂(A)的施用率可以在一个宽范围内变化,例如0.001g至1,500g AS/ha(下文中AS/ha是指“每公顷的活性物质”=基于100%的纯净活性化合物计)。以0.001g至1,500g AS/ha的施用率施用时,除草剂(A)(优选化合物A-0至A-35)——以出苗前法和出苗后法使用时——可防治的有害植物谱相对较广,例如一年生和多年生的单子叶和双子叶杂草以及不想要的作物。对于本发明的结合物,施用率通常更低,例如在0.001g至1000g AS/ha的范围内,优选0.1g至500g AS/ha,特别优选0.5g至250g AS/ha。
组(B)的除草剂对例如脂肪酸生物合成、细胞分裂、光合体系II和乙酰乳酸合酶均具有影响,并且它们既适于在出苗前施用也适于在出苗后施用。除草剂(B)的施用率可以在一个宽范围内变化,例如在0.001g和15000g AS/ha之间(下文中,AS/ha意指“每公顷的活性物质”=以100%的纯活性化合物计)。在0.01g至10000g AS/ha的施用率下、通过出苗前和出苗后方法使用时,除草剂(B)——优选化合物B(1-1)至B(9-7)——能防治相对较宽谱的有害植物,例如一年生和多年生的单子叶或双子叶杂草,以及不想要的作物植物。对于本发明结合物而言,施用率通常更低,例如在0.05g至15000g AS/ha的范围内,优选0.1g至10000gAS/ha,特别优选0.5g至8000g AS/ha。
优选含有一种或多种除草剂(A)和一种或多种除草剂(B)的除草剂结合物。更优选以下方案的含有除草剂(A)和一种或多种除草剂(B)的结合物:
(A-0)+(B1-1)、(A-0)+(B1-2)、(A-0)+(B9-7)、(A-1)+(B1-1)、(A-1)+(B1-2)、(A-1)+(B9-7)、(A-35)+(B1-1)、(A-35)+(B1-2)、(A-35)+(B9-7)。
本文中,本发明的结合物同样还包括一种或多种不同于除草剂(A)和(B)但也可作为选择性除草剂发挥作用的其他农业化学活性化合物。
对于三种或三种以上活性化合物的结合物,下文中所具体示出的用于本发明双组分结合物的情况也同样适用,只要它们包含本发明所述的双组分结合物。
可以通过例如参照所述单个化合物的施用率找出化合物(A)和(B)的合适比例范围。在本发明的结合物中,通常可以降低所述施用率。下面列出了本发明结合物的优选(A)∶(B)混合比例:
(A)∶(B)=50000∶1至1∶100000,优选500∶1至1∶16000,特别优选250∶1至1∶8000。
特别值得注意的是使用含有下列化合物(A)+(B)的除草剂组合物:
(A-0)+(B1-1),(A-0)+(B1-2),(A-0)+(B1-3),(A-0)+(B1-),(A-0)+(B1-5),
(A-0)+(B1-6),(A-0)+(B1-7),(A-0)+(B1-8),(A-0)+(B2-1),(A-0)+(B2-2),
(A-0)+(B3-1),(A-0)+(B3-2),(A-0)+(B3-3),(A-0)+(B3-4),(A-0)+(B3-5),
(A-0)+(B3-6),(A-0)+(B-3-7),(A-0)+(B3-8),(A-0)+(B3-9),(A-0)+(B4-1),
(A-0)+(B4-2),(A-0)+(B4-3),(A-0)+(B4-4),(A-0)+(B4-5),(A-0)+(B4-6),
(A-0)+(B4-7),(A-0)+(B4-8),(A-0)+(B4-9),(A-0)+(B4-10),(A-0)+(B4-11),
(A-0)+(B5-1),(A-0)+(B5-2),(A-0)+(B5-3),(A-0)+(B5-4),(A-0)+(B5-5),
(A-0)+(B5-6),(A-0)+(B5-7),(A-0)+(B6-1),(A-0)+(B6-2),(A-0)+(B6-3),
(A-0)+(B6-4),(A-0)+(B6-5),(A-0)+(B6-6),(A-0)+(B6-7),(A-0)+(B6-8),
(A-0)+(B6-9),(A-0)+(B6-10),(A-0)+(B6-11),(A-0)+(B6-12),(A-0)+(B6-13),
(A-0)+(B6-14),(A-0)+(B7-1),(A-0)+(B7-2),(A-0)+(B7-3),(A-0)+(B7-4),
(A-0)+(B7-5),(A-0)+(B7-6),(A-0)+(B7-7),(A-0)+(B7-8),(A-0)+(B7-9),
(A-0)+(B7-10),(A-0)+(B7-11),(A-0)+(B7-12),(A-0)+(B7-13),
(A-0)+(B7-14),(A-0)+(B7-15),(A-0)+(B7-16),(A-0)+(B7-17),
(A-0)+(B7-18),(A-0)+(B7-19),(A-0)+(B7-20),(A-0)+(B7-21),
(A-0)+(B7-22),(A-0)+(B7-23),(A-0)+(B7-24),(A-0)+(B7-25),
(A-0)+(B7-26),(A-0)+(B7-27),(A-0)+(B7-28),(A-0)+(B7-29),
(A-0)+(B7-30),(A-0)+(B-31),(A-0)+(B7-32),(A-0)+(B7-33),
(A-0)+(B7-34),(A-0)+(B7-35),(A-0)+(B7-36),(A-0)+(B7-37),
(A-0)+(B7-38),(A-0)+(B7-39),(A-0)+(B8-1),(A-0)+(B8-2),(A-0)+(B8-3),
(A-0)+(B9-1),(A-0)+(B9-2),(A-0)+(B9-3),(A-0)+(B9-4),(A-0)+(B9-5),
(A-0)+(B9-6),(A-0)+(B9-7).
(A-1)+(B1-1),(A-1)+(B1-2),(A-1)+(B1-3),(A-1)+(B1-4),(A-1)+(B1-5),
(A-1)+(B1-6),(A-1)+(B1-7),(A-1)+(B1-8),(A-1)+(B2-1),(A-1)+(B2-2),
(A-1)+(B3-1),(A-1)+(B3-2),(A-1)+(B3-3),(A-1)+(B3-4),(A-1)+(B3-5),
(A-1)+(B3-6),(A-1)+(B-3-7),(A-1)+(B3-8),(A-1)+(B3-9),(A-1)+(B4-1),
(A-1)+(B4-2),(A-1)+(B4-3),(A-1)+(B4-4),(A-1)+(B4-5),(A-1)+(B4-6),
(A-1)+(B4-7),(A-1)+(B4-8),(A-1)+(B4-9),(A-1)+(B4-10),(A-1)+(B4-11),
(A-1)+(B5-1),(A-1)+(B5-2),(A-1)+(B5-3),(A-1)+(B5-4),(A-1)+(B5-5),
(A-1)+(B5-6),(A-1)+(B5-7),(A-1)+(B6-1),(A-1)+(B6-2),(A-1)+(B6-3),
(A-1)+(B6-4),(A-1)+(B6-5),(A-1)+(B6-6),(A-1)+(B6-7),(A-1)+(B6-8),
(A-1)+(B6-9),(A-1)+(B6-10),(A-1)+(B6-11),(A-1)+(B6-12),(A-1)+(B6-13),
(A-1)+(B6-14),(A-1)+(B7-1),(A-1)+(B7-2),(A-1)+(B7-3),(A-1)+(B7-4),
(A-1)+(B7-5),(A-1)+(B7-6),(A-1)+(B7-7),(A-1)+(B7-8),(A-1)+(B7-9),
(A-1)+(B7-10),(A-1)+(B7-11),(A-1)+(B7-12),(A-1)+(B7-13),
(A-1)+(B7-14),(A-1)+(B7-15),(A-1)+(B7-16),(A-1)+(B7-17),
(A-1)+(B7-18),(A-1)+(B7-19),(A-1)+(B7-20),(A-1)+(B7-21),
(A-1)+(B7-22),(A-1)+(B7-23),(A-1)+(B7-24),(A-1)+(B7-25),
(A-1)+(B7-26),(A-1)+(B7-27),(A-1)+(B7-28),(A-1)+(B7-29),
(A-1)+(B7-30),(A-1)+(B-31),(A-1)+(B7-32),(A-1)+(B7-33),
(A-1)+(B7-34),(A-1)+(B7-35),(A-1)+(B7-36),(A-1)+(B7-37),
(A-1)+(B7-38),(A-1)+(B7-39),(A-1)+(B8-1),(A-1)+(B8-2),(A-1)+(B8-3),
(A-1)+(B9-1),(A-1)+(B9-2),(A-1)+(B9-3),(A-1)+(B9-4),(A-1)+(B9-5),
(A-1)+(B9-6),(A-1)+(B9-7).
(A-2)+(B1-1),(A-2)+(B1-2),(A-2)+(B1-3),(A-2)+(B1-4),(A-2)+(B1-5),
(A-2)+(B1-6),(A-2)+(B1-7),(A-2)+(B1-8),(A-2)+(B2-1),(A-2)+(B2-2),
(A-2)+(B3-1),(A-2)+(B3-2),(A-2)+(B3-3),(A-2)+(B3-4),(A-2)+(B3-5),
(A-2)+(B3-6),(A-2)+(B-3-7),(A-2)+(B3-8),(A-2)+(B3-9),(A-2)+(B4-1),
(A-2)+(B4-2),(A-2)+(B4-3),(A-2)+(B4-4),(A-2)+(B4-5),(A-2)+(B4-6),
(A-2)+(B4-7),(A-2)+(B4-8),(A-2)+(B4-9),(A-2)+(B4-10),(A-2)+(B4-11),
(A-2)+(B5-1),(A-2)+(B5-2),(A-2)+(B5-3),(A-2)+(B5-4),(A-2)+(B5-5),
(A-2)+(B5-6),(A-2)+(B5-7),(A-2)+(B6-1),(A-2)+(B6-2),(A-2)+(B6-3),
(A-2)+(B6-4),(A-2)+(B6-5),(A-2)+(B6-6),(A-2)+(B6-7),(A-2)+(B6-8),
(A-2)+(B6-9),(A-2)+(B6-10),(A-2)+(B6-11),(A-2)+(B6-12),(A-2)+(B6-13),
(A-2)+(B6-14),(A-2)+(B7-1),(A-2)+(B7-2),(A-2)+(B7-3),(A-2)+(B7-4),
(A-2)+(B7-5),(A-2)+(B7-6),(A-2)+(B7-7),(A-2)+(B7-8),(A-2)+(B7-9),
(A-2)+(B7-10),(A-2)+(B7-11),(A-2)+(B7-12),(A-2)+(B7-13),
(A-2)+(B7-14),(A-2)+(B7-15),(A-2)+(B7-16),(A-2)+(B7-17),
(A-2)+(B7-18),(A-2)+(B7-19),(A-2)+(B7-20),(A-2)+(B7-21),
(A-2)+(B7-22),(A-2)+(B7-23),(A-2)+(B7-24),(A-2)+(B7-25),
(A-2)+(B7-26),(A-2)+(B7-27),(A-2)+(B7-28),(A-2)+(B7-29),
(A-2)+(B7-30),(A-2)+(B-31),(A-2)+(B7-32),(A-2)+(B7-33),
(A-2)+(B7-34),(A-2)+(B7-35),(A-2)+(B7-36),(A-2)+(B7-37),
(A-2)+(B7-38),(A-2)+(B7-39)(A-2)+(B8-1),(A-2)+(B8-2),(A-2)+(B8-3),
(A-2)+(B9-1),(A-2)+(B9-2),(A-2)+(B9-3),(A-2)+(B9-4),(A-2)+(B9-5),
(A-2)+(B9-6),(A-2)+(B9-7).
(A-3)+(B1-1),(A-3)+(B1-2),(A-3)+(B1-3),(A-3)+(B1-4),(A-3)+(B1-5),
(A-3)+(B1-6),(A-3)+(B1-7),(A-3)+(B1-8),(A-3)+(B2-1),(A-3)+(B2-2),
(A-3)+(B3-1),(A-3)+(B3-2),(A-3)+(B3-3),(A-3)+(B3-4),(A-3)+(B3-5),
(A-3)+(B3-6),(A-3)+(B-3-7),(A-3)+(B3-8),(A-3)+(B3-9),(A-3)+(B4-1),
(A-3)+(B4-2),(A-3)+(B4-3),(A-3)+(B4-4),(A-3)+(B4-5),(A-3)+(B4-6),
(A-3)+(B4-7),(A-3)+(B4-8),(A-3)+(B4-9),(A-3)+(B4-10),(A-3)+(B4-11),
(A-3)+(B5-1),(A-3)+(B5-2),(A-3)+(B5-3),(A-3)+(B5-4),(A-3)+(B5-5),
(A-3)+(B5-6),(A-3)+(B5-7),(A-3)+(B6-1),(A-3)+(B6-2),(A-3)+(B6-3),
(A-3)+(B6-4),(A-3)+(B6-5),(A-3)+(B6-6),(A-3)+(B6-7),(A-3)+(B6-8),
(A-3)+(B6-9),(A-3)+(B6-10),(A-3)+(B6-11),(A-3)+(B6-12),(A-3)+(B6-13),
(A-3)+(B6-14),(A-3)+(B7-1),(A-3)+(B7-2),(A-3)+(B7-3),(A-3)+(B7-4),
(A-3)+(B7-5),(A-3)+(B7-6),(A-3)+(B7-7),(A-3)+(B7-8),(A-3)+(B7-9),
(A-3)+(B7-10),(A-3)+(B7-11),(A-3)+(B7-12),(A-3)+(B7-13),
(A-3)+(B7-14),(A-3)+(B7-15),(A-3)+(B7-16),(A-3)+(B7-17),
(A-3)+(B7-18),(A-3)+(B7-19),(A-3)+(B7-20),(A-3)+(B7-21),
(A-3)+(B7-22),(A-3)+(B7-23),(A-3)+(B7-24),(A-3)+(B7-25),
(A-3)+(B7-26),(A-3)+(B7-27),(A-3)+(B7-28),(A-3)+(B7-29),
(A-3)+(B7-30),(A-3)+(B-31),(A-3)+(B7-32),(A-3)+(B7-33),
(A-3)+(B7-34),(A-3)+(B7-35),(A-3)+(B7-36),(A-3)+(B7-37),
(A-3)+(B7-38),(A-3)+(B7-39),(A-3)+(B8-1),(A-3)+(B8-2),(A-3)+(B8-3),
(A-3)+(B9-1),(A-3)+(B9-2),(A-3)+(B9-3),(A-3)+(B9-4),(A-3)+(B9-5),
(A-3)+(B9-6),(A-3)+(B9-7).
(A-4)+(B1-1),(A-4)+(B1-2),(A-4)+(B1-3),(A-4)+(B1-4),(A-4)+(B1-5),
(A-4)+(B1-6),(A-4)+(B1-7),(A-4)+(B1-8),(A-4)+(B2-1),(A-4)+(B2-2),
(A-4)+(B3-1),(A-4)+(B3-2),(A-4)+(B3-3),(A-4)+(B3-4),(A-4)+(B3-5),
(A-4)+(B3-6),(A-4)+(B-3-7),(A-4)+(B3-8),(A-4)+(B3-9),(A-4)+(B4-1),
(A-4)+(B4-2),(A-4)+(B4-3),(A-4)+(B4-4),(A-4)+(B4-5),(A-4)+(B4-6),
(A-4)+(B4-7),(A-4)+(B4-8),(A-4)+(B4-9),(A-4)+(B4-10),(A-4)+(B4-11),
(A-4)+(B5-1),(A-4)+(B5-2),(A-4)+(B5-3),(A-4)+(B5-4),(A-4)+(B5-5),
(A-4)+(B5-6),(A-4)+(B5-7),(A-4)+(B6-1),(A-4)+(B6-2),(A-4)+(B6-3),
(A-4)+(B6-4),(A-4)+(B6-5),(A-4)+(B6-6),(A-4)+(B6-7),(A-4)+(B6-8),
(A-4)+(B6-9),(A-4)+(B6-10),(A-4)+(B6-11),(A-4)+(B6-12),(A-4)+(B6-13),
(A-4)+(B6-14),(A-4)+(B7-1),(A-4)+(B7-2),(A-4)+(B7-3),(A-4)+(B7-4),
(A-4)+(B7-5),(A-4)+(B7-6),(A-4)+(B7-7),(A-4)+(B7-8),(A-4)+(B7-9),
(A-4)+(B7-10),(A-4)+(B7-11),(A-4)+(B7-12),(A-4)+(B7-13),
(A-4)+(B7-14),(A-4)+(B7-15),(A-4)+(B7-16),(A-4)+(B7-17),
(A-4)+(B7-18),(A-4)+(B7-19),(A-4)+(B7-20),(A-4)+(B7-21),
(A-4)+(B7-22),(A-4)+(B7-23),(A-4)+(B7-24),(A-4)+(B7-25),
(A-4)+(B7-26),(A-4)+(B7-27),(A-4)+(B7-28),(A-4)+(B7-29),
(A-4)+(B7-30),(A-4)+(B-31),(A-4)+(B7-32),(A-4)+(B7-33),
(A-4)+(B7-34),(A-4)+(B7-35),(A-4)+(B7-36),(A-4)+(B7-37),
(A-4)+(B7-38),(A-4)+(B7-39),(A-4)+(B8-1),(A-4)+(B8-2),(A-4)+(B8-3),
(A-4)+(B9-1),(A-4)+(B9-2),(A-4)+(B9-3),(A-4)+(B9-4),(A-4)+(B9-5),
(A-4)+(B9-6),(A-4)+(B9-7).
(A-5)+(B1-1),(A-5)+(B1-2),(A-5)+(B1-3),(A-5)+(B1-4),(A-5)+(B1-5),
(A-5)+(B1-6),(A-5)+(B1-7),(A-5)+(B1-8),(A-5)+(B2-1),(A-5)+(B2-2),
(A-5)+(B3-1),(A-5)+(B3-2),(A-5)+(B3-3),(A-5)+(B3-4),(A-5)+(B3-5),
(A-5)+(B3-6),(A-5)+(B-3-7),(A-5)+(B3-8),(A-5)+(B3-9),(A-5)+(B4-1),
(A-5)+(B4-2),(A-5)+(B4-3),(A-5)+(B4-4),(A-5)+(B4-5),(A-5)+(B4-6),
(A-5)+(B4-7),(A-5)+(B4-8),(A-5)+(B4-9),(A-5)+(B4-10),(A-5)+(B4-11),
(A-5)+(B5-1),(A-5)+(B5-2),(A-5)+(B5-3),(A-5)+(B5-4),(A-5)+(B5-5),
(A-5)+(B5-6),(A-5)+(B5-7),(A-5)+(B6-1),(A-5)+(B6-2),(A-5)+(B6-3),
(A-5)+(B6-4),(A-5)+(B6-5),(A-5)+(B6-6),(A-5)+(B6-7),(A-5)+(B6-8),
(A-5)+(B6-9),(A-5)+(B6-10),(A-5)+(B6-11),(A-5)+(B6-12),(A-5)+(B6-13),
(A-5)+(B6-14),(A-5)+(B7-1),(A-5)+(B7-2),(A-5)+(B7-3),(A-5)+(B7-4),
(A-5)+(B7-5),(A-5)+(B7-6),(A-5)+(B7-7),(A-5)+(B7-8),(A-5)+(B7-9),
(A-5)+(B7-10),(A-5)+(B7-11),(A-5)+(B7-12),(A-5)+(B7-13),
(A-5)+(B7-14),(A-5)+(B7-15),(A-5)+(B7-16),(A-5)+(B7-17),
(A-5)+(B7-18),(A-5)+(B7-19),(A-5)+(B7-20),(A-5)+(B7-21),
(A-5)+(B7-22),(A-5)+(B7-23),(A-5)+(B7-24),(A-5)+(B7-25),
(A-5)+(B7-26),(A-5)+(B7-27),(A-5)+(B7-28),(A-5)+(B7-29),
(A-5)+(B7-30),(A-5)+(B-31),(A-5)+(B7-32),(A-5)+(B7-33),
(A-5)+(B7-34),(A-5)+(B7-35),(A-5)+(B7-36),(A-5)+(B7-37),
(A-5)+(B7-38),(A-5)+(B7-39),(A-5)+(B8-1),(A-5)+(B8-2),(A-5)+(B8-3),
(A-5)+(B9-1),(A-5)+(B9-2),(A-5)+(B9-3),(A-5)+(B9-4),(A-5)+(B9-5),
(A-5)+(B9-6),(A-5)+(B9-7).
(A-6)+(B1-1),(A-6)+(B1-2),(A-6)+(B1-3),(A-6)+(B1-4),(A-6)+(B1-5),
(A-6)+(B1-6),(A-6)+(B1-7),(A-6)+(B1-8),(A-6)+(B2-1),(A-6)+(B2-2),
(A-6)+(B3-1),(A-6)+(B3-2),(A-6)+(B3-3),(A-6)+(B3-4),(A-6)+(B3-5),
(A-6)+(B3-6),(A-6)+(B-3-7),(A-6)+(B3-8),(A-6)+(B3-9),(A-6)+(B4-1),
(A-6)+(B4-2),(A-6)+(B4-3),(A-6)+(B4-4),(A-6)+(B4-5),(A-6)+(B4-6),
(A-6)+(B4-7),(A-6)+(B4-8),(A-6)+(B4-9),(A-6)+(B4-10),(A-6)+(B4-11),
(A-6)+(B5-1),(A-6)+(B5-2),(A-6)+(B5-3),(A-6)+(B5-4),(A-6)+(B5-5),
(A-6)+(B5-6),(A-6)+(B5-7),(A-6)+(B6-1),(A-6)+(B6-2),(A-6)+(B6-3),
(A-6)+(B6-4),(A-6)+(B6-5),(A-6)+(B6-6),(A-6)+(B6-7),(A-6)+(B6-8),
(A-6)+(B6-9),(A-6)+(B6-10),(A-6)+(B6-11),(A-6)+(B6-12),(A-6)+(B6-13),
(A-6)+(B6-14),(A-6)+(B7-1),(A-6)+(B7-2),(A-6)+(B7-3),(A-6)+(B7-4),
(A-6)+(B7-5),(A-6)+(B7-6),(A-6)+(B7-7),(A-6)+(B7-8),(A-6)+(B7-9),
(A-6)+(B7-10),(A-6)+(B7-11),(A-6)+(B7-12),(A-6)+(B7-13),
(A-6)+(B7-14),(A-6)+(B7-15),(A-6)+(B7-16),(A-6)+(B7-17),
(A-6)+(B7-18),(A-6)+(B7-19),(A-6)+(B7-20),(A-6)+(B7-21),
(A-6)+(B7-22),(A-6)+(B7-23),(A-6)+(B7-24),(A-6)+(B7-25),
(A-6)+(B7-26),(A-6)+(B7-27),(A-6)+(B7-28),(A-6)+(B7-29),
(A-6)+(B7-30),(A-6)+(B-31),(A-6)+(B7-32),(A-6)+(B7-33),
(A-6)+(B7-34),(A-6)+(B7-35),(A-6)+(B7-36),(A-6)+(B7-37),
(A-6)+(B7-38),(A-6)+(B7-39),(A-6)+(B8-1),(A-6)+(B8-2),(A-6)+(B8-3),
(A-6)+(B9-1),(A-6)+(B9-2),(A-6)+(B9-3),(A-6)+(B9-4),(A-6)+(B9-5),
(A-6)+(B9-6),(A-6)+(B9-7).
(A-7)+(B1-1),(A-7)+(B1-2),(A-7)+(B1-3),(A-7)+(B1-4),(A-7)+(B1-5),
(A-7)+(B1-6),(A-7)+(B1-7),(A-7)+(B1-8),(A-7)+(B2-1),(A-7)+(B2-2),
(A-7)+(B3-1),(A-7)+(B3-2),(A-7)+(B3-3),(A-7)+(B3-4),(A-7)+(B3-5),
(A-7)+(B3-6),(A-7)+(B-3-7),(A-7)+(B3-8),(A-7)+(B3-9),(A-7)+(B4-1),
(A-7)+(B4-2),(A-7)+(B4-3),(A-7)+(B4-4),(A-7)+(B4-5),(A-7)+(B4-6),
(A-7)+(B4-7),(A-7)+(B4-8),(A-7)+(B4-9),(A-7)+(B4-10),(A-7)+(B4-11),
(A-7)+(B5-1),(A-7)+(B5-2),(A-7)+(B5-3),(A-7)+(B5-4),(A-7)+(B5-5),
(A-7)+(B5-6),(A-7)+(B5-7),(A-7)+(B6-1),(A-7)+(B6-2),(A-7)+(B6-3),
(A-7)+(B6-4),(A-7)+(B6-5),(A-7)+(B6-6),(A-7)+(B6-7),(A-7)+(B6-8),
(A-7)+(B6-9),(A-7)+(B6-10),(A-7)+(B6-11),(A-7)+(B6-12),(A-7)+(B6-13),
(A-7)+(B6-14),(A-7)+(B7-1),(A-7)+(B7-2),(A-7)+(B7-3),(A-7)+(B7-4),
(A-7)+(B7-5),(A-7)+(B7-6),(A-7)+(B7-7),(A-7)+(B7-8),(A-7)+(B7-9),
(A-7)+(B7-10),(A-7)+(B7-11),(A-7)+(B7-12),(A-7)+(B7-13),
(A-7)+(B7-14),(A-7)+(B7-15),(A-7)+(B7-16),(A-7)+(B7-17),
(A-7)+(B7-18),(A-7)+(B7-19),(A-7)+(B7-20),(A-7)+(B7-21),
(A-7)+(B7-22),(A-7)+(B7-23),(A-7)+(B7-24),(A-7)+(B7-25),
(A-7)+(B7-26),(A-7)+(B7-27),(A-7)+(B7-28),(A-7)+(B7-29),
(A-7)+(B7-30),(A-7)+(B-31),(A-7)+(B7-32),(A-7)+(B7-33),
(A-7)+(B7-34),(A-7)+(B7-35),(A-7)+(B7-36),(A-7)+(B7-37),
(A-7)+(B7-38),(A-7)+(B7-39),(A-7)+(B8-1),(A-7)+(B8-2),(A-7)+(B8-3),
(A-7)+(B9-1),(A-7)+(B9-2),(A-7)+(B9-3),(A-7)+(B9-4),(A-7)+(B9-5),
(A-7)+(B9-6),(A-7)+(B9-7).
(A-8)+(B1-1),(A-8)+(B1-2),(A-8)+(B1-3),(A-8)+(B1-4),(A-8)+(B1-5),
(A-8)+(B1-6),(A-8)+(B1-7),(A-8)+(B1-8),(A-8)+(B2-1),(A-8)+(B2-2),
(A-8)+(B3-1),(A-8)+(B3-2),(A-8)+(B3-3),(A-8)+(B3-4),(A-8)+(B3-5),
(A-8)+(B3-6),(A-8)+(B-3-7),(A-8)+(B3-8),(A-8)+(B3-9),(A-8)+(B4-1),
(A-8)+(B4-2),(A-8)+(B4-3),(A-8)+(B4-4),(A-8)+(B4-5),(A-8)+(B4-6),
(A-8)+(B4-7),(A-8)+(B4-8),(A-8)+(B4-9),(A-8)+(B4-10),(A-8)+(B4-11),
(A-8)+(B5-1),(A-8)+(B5-2),(A-8)+(B5-3),(A-8)+(B5-4),(A-8)+(B5-5),
(A-8)+(B5-6),(A-8)+(B5-7),(A-8)+(B6-1),(A-8)+(B6-2),(A-8)+(B6-3),
(A-8)+(B6-4),(A-8)+(B6-5),(A-8)+(B6-6),(A-8)+(B6-7),(A-8)+(B6-8),
(A-8)+(B6-9),(A-8)+(B6-10),(A-8)+(B6-11),(A-8)+(B6-12),(A-8)+(B6-13),
(A-8)+(B6-14),(A-8)+(B7-1),(A-8)+(B7-2),(A-8)+(B7-3),(A-8)+(B7-4),
(A-8)+(B7-5),(A-8)+(B7-6),(A-8)+(B7-7),(A-8)+(B7-8),(A-8)+(B7-9),
(A-8)+(B7-10),(A-8)+(B7-11),(A-8)+(B7-12),(A-8)+(B7-13),
(A-8)+(B7-14),(A-8)+(B7-15),(A-8)+(B7-16),(A-8)+(B7-17),
(A-8)+(B7-18),(A-8)+(B7-19),(A-8)+(B7-20),(A-8)+(B7-21),
(A-8)+(B7-22),(A-8)+(B7-23),(A-8)+(B7-24),(A-8)+(B7-25),
(A-8)+(B7-26),(A-8)+(B7-27),(A-8)+(B7-28),(A-8)+(B7-29),
(A-8)+(B7-30),(A-8)+(B-31),(A-8)+(B7-32),(A-8)+(B7-33),
(A-8)+(B7-34),(A-8)+(B7-35),(A-8)+(B7-36),(A-8)+(B7-37),
(A-8)+(B7-38),(A-8)+(B7-39),(A-8)+(B8-1),(A-8)+(B8-2),(A-8)+(B8-3),
(A-8)+(B9-1),(A-8)+(B9-2),(A-8)+(B9-3),(A-8)+(B9-4),(A-8)+(B9-5),
(A-8)+(B9-6),(A-8)+(B9-7).
(A-9)+(B1-1),(A-9)+(B1-2),(A-9)+(B1-3),(A-9)+(B1-4),(A-9)+(B1-5),
(A-9)+(B1-6),(A-9)+(B1-7),(A-9)+(B1-8),(A-9)+(B2-1),(A-9)+(B2-2),
(A-9)+(B3-1),(A-9)+(B3-2),(A-9)+(B3-3),(A-9)+(B3-4),(A-9)+(B3-5),
(A-9)+(B3-6),(A-9)+(B-3-7),(A-9)+(B3-8),(A-9)+(B3-9),(A-9)+(B4-1),
(A-9)+(B4-2),(A-9)+(B4-3),(A-9)+(B4-4),(A-9)+(B4-5),(A-9)+(B4-6),
(A-9)+(B4-7),(A-9)+(B4-8),(A-9)+(B4-9),(A-9)+(B4-10),(A-9)+(B4-11),
(A-9)+(B5-1),(A-9)+(B5-2),(A-9)+(B5-3),(A-9)+(B5-4),(A-9)+(B5-5),
(A-9)+(B5-6),(A-9)+(B5-7),(A-9)+(B6-1),(A-9)+(B6-2),(A-9)+(B6-3),
(A-9)+(B6-4),(A-9)+(B6-5),(A-9)+(B6-6),(A-9)+(B6-7),(A-9)+(B6-8),
(A-9)+(B6-9),(A-9)+(B6-10),(A-9)+(B6-11),(A-9)+(B6-12),(A-9)+(B6-13),
(A-9)+(B6-14),(A-9)+(B7-1),(A-9)+(B7-2),(A-9)+(B7-3),(A-9)+(B7-4),
(A-9)+(B7-5),(A-9)+(B7-6),(A-9)+(B7-7),(A-9)+(B7-8),(A-9)+(B7-9),
(A-9)+(B7-10),(A-9)+(B7-11),(A-9)+(B7-12),(A-9)+(B7-13),
(A-9)+(B7-14),(A-9)+(B7-15),(A-9)+(B7-16),(A-9)+(B7-17),
(A-9)+(B7-18),(A-9)+(B7-19),(A-9)+(B7-20),(A-9)+(B7-21),
(A-9)+(B7-22),(A-9)+(B7-23),(A-9)+(B7-24),(A-9)+(B7-25),
(A-9)+(B7-26),(A-9)+(B7-27),(A-9)+(B7-28),(A-9)+(B7-29),
(A-9)+(B7-30),(A-9)+(B-31),(A-9)+(B7-32),(A-9)+(B7-33),
(A-9)+(B7-34),(A-9)+(B7-35),(A-9)+(B7-36),(A-9)+(B7-37),
(A-9)+(B7-38),(A-9)+(B7-39),(A-9)+(B8-1),(A-9)+(B8-2),(A-9)+(B8-3),
(A-9)+(B9-1),(A-9)+(B9-2),(A-9)+(B9-3),(A-9)+(B9-4),(A-9)+(B9-5),
(A-9)+(B9-6),(A-9)+(B9-7).
(A-10)+(B1-1),(A-10)+(B1-2),(A-10)+(B1-3),(A-10)+(B1-4),(A-10)+(B1-5),
(A-10)+(B1-6),(A-10)+(B1-7),(A-10)+(B1-8),(A-10)+(B2-1),(A-10)+(B2-2),
(A-10)+(B3-1),(A-10)+(B3-2),(A-10)+(B3-3),(A-10)+(B3-4),(A-10)+(B3-5),
(A-10)+(B3-6),(A-10)+(B-3-7),(A-10)+(B3-8),(A-10)+(B3-9),(A-10)+(B4-1),
(A-10)+(B4-2),(A-10)+(B4-3),(A-10)+(B4-4),(A-10)+(B4-5),(A-10)+(B4-6),
(A-10)+(B4-7),(A-10)+(B4-8),(A-10)+(B4-9),(A-10)+(B4-10),(A-10)+(B4-11),
(A-10)+(B5-1),(A-10)+(B5-2),(A-10)+(B5-3),(A-10)+(B5-4),(A-10)+(B5-5),
(A-10)+(B5-6),(A-10)+(B5-7),(A-10)+(B6-1),(A-10)+(B6-2),(A-10)+(B6-3),
(A-10)+(B6-4),(A-10)+(B6-5),(A-10)+(B6-6),(A-10)+(B6-7),(A-10)+(B6-8),
(A-10)+(B6-9),(A-10)+(B6-10),(A-10)+(B6-11),(A-10)+(B6-12),
(A-10)+(B6-13),(A-10)+(B6-14),(A-10)+(B7-1),(A-10)+(B7-2),(A-10)+(B7-3),
(A-10)+(B7-4),(A-10)+(B7-5),(A-10)+(B7-6),(A-10)+(B7-7),(A-10)+(B7-8),
(A-10)+(B7-9),(A-10)+(B7-10),(A-10)+(B7-11),(A-10)+(B7-12),
(A-10)+(B7-13),(A-10)+(B7-14),(A-10)+(B7-15),(A-10)+(B7-16),
(A-10)+(B7-17),(A-10)+(B7-18),(A-10)+(B7-19),(A-10)+(B7-20),
(A-10)+(B7-21),(A-10)+(B7-22),(A-10)+(B7-23),(A-10)+(B7-24),
(A-10)+(B7-25),(A-10)+(B7-26),(A-10)+(B7-27),(A-10)+(B7-28),
(A-10)+(B7-29),(A-10)+(B7-30),(A-10)+(B-31),(A-10)+(B7-32),
(A-10)+(B7-33),(A-10)+(B7-34),(A-10)+(B7-35),(A-10)+(B7-36),
(A-10)+(B7-37),(A-10)+(B7-38),(A-10)+(B7-39),(A-10)+(B8-1),
(A-10)+(B8-2),(A-10)+(B8-3),(A-10)+(B9-1),(A-10)+(B9-2),(A-10)+(B9-3),
(A-10)+(B9-4),(A-10)+(B9-5),(A-10)+(B9-6),(A-10)+(B9-7).
(A-11)+(B1-1),(A-11)+(B1-2),(A-11)+(B1-3),(A-11)+(B1-4),(A-11)+(B1-5),
(A-11)+(B1-6),(A-11)+(B1-7),(A-11)+(B1-8),(A-11)+(B2-1),(A-11)+(B2-2),
(A-11)+(B3-1),(A-11)+(B3-2),(A-11)+(B3-3),(A-11)+(B3-4),(A-11)+(B3-5),
(A-11)+(B3-6),(A-11)+(B-3-7),(A-11)+(B3-8),(A-11)+(B3-9),(A-11)+(B4-1),
(A-11)+(B4-2),(A-11)+(B4-3),(A-11)+(B4-4),(A-11)+(B4-5),(A-11)+(B4-6),
(A-11)+(B4-7),(A-11)+(B4-8),(A-11)+(B4-9),(A-11)+(B4-10),(A-11)+(B4-11),
(A-11)+(B5-1),(A-11)+(B5-2),(A-11)+(B5-3),(A-11)+(B5-4),(A-11)+(B5-5),
(A-11)+(B5-6),(A-11)+(B5-7),(A-11)+(B6-1),(A-11)+(B6-2),(A-11)+(B6-3),
(A-11)+(B6-4),(A-11)+(B6-5),(A-11)+(B6-6),(A-11)+(B6-7),(A-11)+(B6-8),
(A-11)+(B6-9),(A-11)+(B6-10),(A-11)+(B6-11),(A-11)+(B6-12),
(A-11)+(B6-13),(A-11)+(B6-14),(A-11)+(B7-1),(A-11)+(B7-2),(A-11)+(B7-3),
(A-11)+(B7-4),(A-11)+(B7-5),(A-11)+(B7-6),(A-11)+(B7-7),(A-11)+(B7-8),
(A-11)+(B7-9),(A-11)+(B7-10),(A-11)+(B7-11),(A-11)+(B7-12),
(A-11)+(B7-13),(A-11)+(B7-14),(A-11)+(B7-15),(A-11)+(B7-16),
(A-11)+(B7-17),(A-11)+(B7-18),(A-11)+(B7-19),(A-11)+(B7-20),
(A-11)+(B7-21),(A-11)+(B7-22),(A-11)+(B7-23),(A-11)+(B7-24),
(A-11)+(B7-25),(A-11)+(B7-26),(A-11)+(B7-27),(A-11)+(B7-28),
(A-11)+(B7-29),(A-11)+(B7-30),(A-11)+(B-31),(A-11)+(B7-32),
(A-11)+(B7-33),(A-11)+(B7-34),(A-11)+(B7-35),(A-11)+(B7-36),
(A-11)+(B7-37),(A-11)+(B7-38),(A-11)+(B7-39),(A-11)+(B8-1),
(A-11)+(B8-2),(A-11)+(B8-3),(A-11)+(B9-1),(A-11)+(B9-2),(A-11)+(B9-3),
(A-11)+(B9-4),(A-11)+(B9-5),(A-11)+(B9-6),(A-11)+(B9-7).
(A-12)+(B1-1),(A-12)+(B1-2),(A-12)+(B1-3),(A-12)+(B1-4),(A-12)+(B1-5),
(A-12)+(B1-6),(A-12)+(B1-7),(A-12)+(B1-8),(A-12)+(B2-1),(A-12)+(B2-2),
(A-12)+(B3-1),(A-12)+(B3-2),(A-12)+(B3-3),(A-12)+(B3-4),(A-12)+(B3-5),
(A-12)+(B3-6),(A-12)+(B-3-7),(A-12)+(B3-8),(A-12)+(B3-9),(A-12)+(B4-1),
(A-12)+(B4-2),(A-12)+(B4-3),(A-12)+(B4-4),(A-12)+(B4-5),(A-12)+(B4-6),
(A-12)+(B4-7),(A-12)+(B4-8),(A-12)+(B4-9),(A-12)+(B4-10),(A-12)+(B4-11),
(A-12)+(B5-1),(A-12)+(B5-2),(A-12)+(B5-3),(A-12)+(B5-4),(A-12)+(B5-5),
(A-12)+(B5-6),(A-12)+(B5-7),(A-12)+(B6-1),(A-12)+(B6-2),(A-12)+(B6-3),
(A-12)+(B6-4),(A-12)+(B6-5),(A-12)+(B6-6),(A-12)+(B6-7),(A-12)+(B6-8),
(A-12)+(B6-9),(A-12)+(B6-10),(A-12)+(B6-11),(A-12)+(B6-12),
(A-12)+(B6-13),(A-12)+(B6-14),(A-12)+(B7-1),(A-12)+(B7-2),(A-12)+(B7-3),
(A-12)+(B7-4),(A-12)+(B7-5),(A-12)+(B7-6),(A-12)+(B7-7),(A-12)+(B7-8),
(A-12)+(B7-9),(A-12)+(B7-10),(A-12)+(B7-11),(A-12)+(B7-12),
(A-12)+(B7-13),(A-12)+(B7-14),(A-12)+(B7-15),(A-12)+(B7-16),
(A-12)+(B7-17),(A-12)+(B7-18),(A-12)+(B7-19),(A-12)+(B7-20),
(A-12)+(B7-21),(A-12)+(B7-22),(A-12)+(B7-23),(A-12)+(B7-24),
(A-12)+(B7-25),(A-12)+(B7-26),(A-12)+(B7-27),(A-12)+(B7-28),
(A-12)+(B7-29),(A-12)+(B7-30),(A-12)+(B-31),(A-12)+(B7-32),
(A-12)+(B7-33),(A-12)+(B7-34),(A-12)+(B7-35),(A-12)+(B7-36),
(A-12)+(B7-37),(A-12)+(B7-38),(A-12)+(B7-39),(A-12)+(B8-1),
(A-12)+(B8-2),(A-12)+(B8-3),(A-12)+(B9-1),(A-12)+(B9-2),
(A-12)+(B9-3),(A-12)+(B9-4),(A-12)+(B9-5),(A-12)+(B9-6),
(A-12)+(B9-7).
(A-13)+(B1-1),(A-13)+(B1-2),(A-13)+(B1-3),(A-13)+(B1-4),(A-13)+(B1-5),
(A-13)+(B1-6),(A-13)+(B1-7),(A-13)+(B1-8),(A-13)+(B2-1),(A-13)+(B2-2),
(A-13)+(B3-1),(A-13)+(B3-2),(A-13)+(B3-3),(A-13)+(B3-4),(A-13)+(B3-5),
(A-13)+(B3-6),(A-13)+(B-3-7),(A-13)+(B3-8),(A-13)+(B3-9),(A-13)+(B4-1),
(A-13)+(B4-2),(A-13)+(B4-3),(A-13)+(B4-4),(A-13)+(B4-5),(A-13)+(B4-6),
(A-13)+(B4-7),(A-13)+(B4-8),(A-13)+(B4-9),(A-13)+(B4-10),(A-13)+(B4-11),
(A-13)+(B5-1),(A-13)+(B5-2),(A-13)+(B5-3),(A-13)+(B5-4),(A-13)+(B5-5),
(A-13)+(B5-6),(A-13)+(B5-7),(A-13)+(B6-1),(A-13)+(B6-2),(A-13)+(B6-3),
(A-13)+(B6-4),(A-13)+(B6-5),(A-13)+(B6-6),(A-13)+(B6-7),(A-13)+(B6-8),
(A-13)+(B6-9),(A-13)+(B6-10),(A-13)+(B6-11),(A-13)+(B6-12),
(A-13)+(B6-13),(A-13)+(B6-14),(A-13)+(B7-1),(A-13)+(B7-2),(A-13)+(B7-3),
(A-13)+(B7-4),(A-13)+(B7-5),(A-13)+(B7-6),(A-13)+(B7-7),(A-13)+(B7-8),
(A-13)+(B7-9),(A-13)+(B7-10),(A-13)+(B7-11),(A-13)+(B7-12),
(A-13)+(B7-13),(A-13)+(B7-14),(A-13)+(B7-15),(A-13)+(B7-16),
(A-13)+(B7-17),(A-13)+(B7-18),(A-13)+(B7-19),(A-13)+(B7-20),
(A-13)+(B7-21),(A-13)+(B7-22),(A-13)+(B7-23),(A-13)+(B7-24),
(A-13)+(B7-25),(A-13)+(B7-26),(A-13)+(B7-27),(A-13)+(B7-28),
(A-13)+(B7-29),(A-13)+(B7-30),(A-13)+(B-31),(A-13)+(B7-32),
(A-13)+(B7-33),(A-13)+(B7-34),(A-13)+(B7-35),(A-13)+(B7-36),
(A-13)+(B7-37),(A-13)+(B7-38),(A-13)+(B7-39),(A-13)+(B8-1),
(A-13)+(B8-2),(A-13)+(B8-3),(A-13)+(B9-1),(A-13)+(B9-2),(A-13)+(B9-3),
(A-13)+(B9-4),(A-13)+(B9-5),(A-13)+(B9-6),(A-13)+(B9-7).
(A-14)+(B1-1),(A-14)+(B1-2),(A-14)+(B1-3),(A-14)+(B1-4),(A-14)+(B1-5),
(A-14)+(B1-6),(A-14)+(B1-7),(A-14)+(B1-8),(A-14)+(B2-1),(A-14)+(B2-2),
(A-14)+(B3-1),(A-14)+(B3-2),(A-14)+(B3-3),(A-14)+(B3-4),(A-14)+(B3-5),
(A-14)+(B3-6),(A-14)+(B-3-7),(A-14)+(B3-8),(A-14)+(B3-9),(A-14)+(B4-1),
(A-14)+(B4-2),(A-14)+(B4-3),(A-14)+(B4-4),(A-14)+(B4-5),(A-14)+(B4-6),
(A-14)+(B4-7),(A-14)+(B4-8),(A-14)+(B4-9),(A-14)+(B4-10),(A-14)+(B4-11),
(A-14)+(B5-1),(A-14)+(B5-2),(A-14)+(B5-3),(A-14)+(B5-4),(A-14)+(B5-5),
(A-14)+(B5-6),(A-14)+(B5-7),(A-14)+(B6-1),(A-14)+(B6-2),(A-14)+(B6-3),
(A-14)+(B6-4),(A-14)+(B6-5),(A-14)+(B6-6),(A-14)+(B6-7),(A-14)+(B6-8),
(A-14)+(B6-9),(A-14)+(B6-10),(A-14)+(B6-11),(A-14)+(B6-12),
(A-14)+(B6-13),(A-14)+(B6-14),(A-14)+(B7-1),(A-14)+(B7-2),(A-14)+(B7-3),
(A-14)+(B7-4),(A-14)+(B7-5),(A-14)+(B7-6),(A-14)+(B7-7),(A-14)+(B7-8),
(A-14)+(B7-9),(A-14)+(B7-10),(A-14)+(B7-11),(A-14)+(B7-12),
(A-14)+(B7-13),(A-14)+(B7-14),(A-14)+(B7-15),(A-14)+(B7-16),
(A-14)+(B7-17),(A-14)+(B7-18),(A-14)+(B7-19),(A-14)+(B7-20),
(A-14)+(B7-21),(A-14)+(B7-22),(A-14)+(B7-23),(A-14)+(B7-24),
(A-14)+(B7-25),(A-14)+(B7-26),(A-14)+(B7-27),(A-14)+(B7-28),
(A-14)+(B7-29),(A-14)+(B7-30),(A-14)+(B-31),(A-14)+(B7-32),
(A-14)+(B7-33),(A-14)+(B7-34),(A-14)+(B7-35),(A-14)+(B7-36),
(A-14)+(B7-37),(A-14)+(B7-38),(A-14)+(B7-39),(A-14)+(B8-1),
(A-14)+(B8-2),(A-14)+(B8-3),(A-14)+(B9-1),(A-14)+(B9-2),(A-14)+(B9-3),
(A-14)+(B9-4),(A-14)+(B9-5),(A-14)+(B9-6),(A-14)+(B9-7).
(A-15)+(B1-1),(A-15)+(B1-2),(A-15)+(B1-3),(A-15)+(B1-4),(A-15)+(B1-5),
(A-15)+(B1-6),(A-15)+(B1-7),(A-15)+(B1-8),(A-15)+(B2-1),(A-15)+(B2-2),
(A-15)+(B3-1),(A-15)+(B3-2),(A-15)+(B3-3),(A-15)+(B3-4),(A-15)+(B3-5),
(A-15)+(B3-6),(A-15)+(B-3-7),(A-15)+(B3-8),(A-15)+(B3-9),(A-15)+(B4-1),
(A-15)+(B4-2),(A-15)+(B4-3),(A-15)+(B4-4),(A-15)+(B4-5),(A-15)+(B4-6),
(A-15)+(B4-7),(A-15)+(B4-8),(A-15)+(B4-9),(A-15)+(B4-10),(A-15)+(B4-11),
(A-15)+(B5-1),(A-15)+(B5-2),(A-15)+(B5-3),(A-15)+(B5-4),(A-15)+(B5-5),
(A-15)+(B5-6),(A-15)+(B5-7),(A-15)+(B6-1),(A-15)+(B6-2),(A-15)+(B6-3),
(A-15)+(B6-4),(A-15)+(B6-5),(A-15)+(B6-6),(A-15)+(B6-7),(A-15)+(B6-8),
(A-15)+(B6-9),(A-15)+(B6-10),(A-15)+(B6-11),(A-15)+(B6-12),
(A-15)+(B6-13),(A-15)+(B6-14),(A-15)+(B7-1),(A-15)+(B7-2),(A-15)+(B7-3),
(A-15)+(B7-4),(A-15)+(B7-5),(A-15)+(B7-6),(A-15)+(B7-7),(A-15)+(B7-8),
(A-15)+(B7-9),(A-15)+(B7-10),(A-15)+(B7-11),(A-15)+(B7-12),
(A-15)+(B7-13),(A-15)+(B7-14),(A-15)+(B7-15),(A-15)+(B7-16),
(A-15)+(B7-17),(A-15)+(B7-18),(A-15)+(B7-19),(A-15)+(B7-20),
(A-15)+(B7-21),(A-15)+(B7-22),(A-15)+(B7-23),(A-15)+(B7-24),
(A-15)+(B7-25),(A-15)+(B7-26),(A-15)+(B7-27),(A-15)+(B7-28),
(A-15)+(B7-29),(A-15)+(B7-30),(A-15)+(B-31),(A-15)+(B7-32),
(A-15)+(B7-33),(A-15)+(B7-34),(A-15)+(B7-35),(A-15)+(B7-36),
(A-15)+(B7-37),(A-15)+(B7-38),(A-15)+(B7-39),(A-15)+(B8-1),
(A-15)+(B8-2),(A-15)+(B8-3),(A-15)+(B9-1),(A-15)+(B9-2),(A-15)+(B9-3),
(A-15)+(B9-4),(A-15)+(B9-5),(A-15)+(B9-6),(A-15)+(B9-7).
(A-16)+(B1-1),(A-16)+(B1-2),(A-16)+(B1-3),(A-16)+(B1-4),(A-16)+(B1-5),
(A-16)+(B1-6),(A-16)+(B1-7),(A-16)+(B1-8),(A-16)+(B2-1),(A-16)+(B2-2),
(A-16)+(B3-1),(A-16)+(B3-2),(A-16)+(B3-3),(A-16)+(B3-4),(A-16)+(B3-5),
(A-16)+(B3-6),(A-16)+(B-3-7),(A-16)+(B3-8),(A-16)+(B3-9),(A-16)+(B4-1),
(A-16)+(B4-2),(A-16)+(B4-3),(A-16)+(B4-4),(A-16)+(B4-5),(A-16)+(B4-6),
(A-16)+(B4-7),(A-16)+(B4-8),(A-16)+(B4-9),(A-16)+(B4-10),(A-16)+(B4-11),
(A-16)+(B5-1),(A-16)+(B5-2),(A-16)+(B5-3),(A-16)+(B5-4),(A-16)+(B5-5),
(A-16)+(B5-6),(A-16)+(B5-7),(A-16)+(B6-1),(A-16)+(B6-2),(A-16)+(B6-3),
(A-16)+(B6-4),(A-16)+(B6-5),(A-16)+(B6-6),(A-16)+(B6-7),(A-16)+(B6-8),
(A-16)+(B6-9),(A-16)+(B6-10),(A-16)+(B6-11),(A-16)+(B6-12),
(A-16)+(B6-13),(A-16)+(B6-14),(A-16)+(B7-1),(A-16)+(B7-2),(A-16)+(B7-3),
(A-16)+(B7-4),(A-16)+(B7-5),(A-16)+(B7-6),(A-16)+(B7-7),(A-16)+(B7-8),
(A-16)+(B7-9),(A-16)+(B7-10),(A-16)+(B7-11),(A-16)+(B7-12),
(A-16)+(B7-13),(A-16)+(B7-14),(A-16)+(B7-15),(A-16)+(B7-16),
(A-16)+(B7-17),(A-16)+(B7-18),(A-16)+(B7-19),(A-16)+(B7-20),
(A-16)+(B7-21),(A-16)+(B7-22),(A-16)+(B7-23),(A-16)+(B7-24),
(A-16)+(B7-25),(A-16)+(B7-26),(A-16)+(B7-27),(A-16)+(B7-28),
(A-16)+(B7-29),(A-16)+(B7-30),(A-16)+(B-31),(A-16)+(B7-32),
(A-16)+(B7-33),(A-16)+(B7-34),(A-16)+(B7-35),(A-16)+(B7-36),
(A-16)+(B7-37),(A-16)+(B7-38),(A-16)+(B7-39),(A-16)+(B8-1),
(A-16)+(B8-2),(A-16)+(B8-3),(A-16)+(B9-1),(A-16)+(B9-2),(A-16)+(B9-3),
(A-16)+(B9-4),(A-16)+(B9-5),(A-16)+(B9-6),(A-16)+(B9-7).
(A-17)+(B1-1),(A-17)+(B1-2),(A-17)+(B1-3),(A-17)+(B1-4),(A-17)+(B1-5),
(A-17)+(B1-6),(A-17)+(B1-7),(A-17)+(B1-8),(A-17)+(B2-1),(A-17)+(B2-2),
(A-17)+(B3-1),(A-17)+(B3-2),(A-17)+(B3-3),(A-17)+(B3-4),(A-17)+(B3-5),
(A-17)+(B3-6),(A-17)+(B-3-7),(A-17)+(B3-8),(A-17)+(B3-9),(A-17)+(B4-1),
(A-17)+(B4-2),(A-17)+(B4-3),(A-17)+(B4-4),(A-17)+(B4-5),(A-17)+(B4-6),
(A-17)+(B4-7),(A-17)+(B4-8),(A-17)+(B4-9),(A-17)+(B4-10),(A-17)+(B4-11),
(A-17)+(B5-1),(A-17)+(B5-2),(A-17)+(B5-3),(A-17)+(B5-4),(A-17)+(B5-5),
(A-17)+(B5-6),(A-17)+(B5-7),(A-17)+(B6-1),(A-17)+(B6-2),(A-17)+(B6-3),
(A-17)+(B6-4),(A-17)+(B6-5),(A-17)+(B6-6),(A-17)+(B6-7),(A-17)+(B6-8),
(A-17)+(B6-9),(A-17)+(B6-10),(A-17)+(B6-11),(A-17)+(B6-12),
(A-17)+(B6-13),(A-17)+(B6-14),(A-17)+(B7-1),(A-17)+(B7-2),(A-17)+(B7-3),
(A-17)+(B7-4),(A-17)+(B7-5),(A-17)+(B7-6),(A-17)+(B7-7),(A-17)+(B7-8),
(A-17)+(B7-9),(A-17)+(B7-10),(A-17)+(B7-11),(A-17)+(B7-12),
(A-17)+(B7-13),(A-17)+(B7-14),(A-17)+(B7-15),(A-17)+(B7-16),
(A-17)+(B7-17),(A-17)+(B7-18),(A-17)+(B7-19),(A-17)+(B7-20),
(A-17)+(B7-21),(A-17)+(B7-22),(A-17)+(B7-23),(A-17)+(B7-24),
(A-17)+(B7-25),(A-17)+(B7-26),(A-17)+(B7-27),(A-17)+(B7-28),
(A-17)+(B7-29),(A-17)+(B7-30),(A-17)+(B-31),(A-17)+(B7-32),
(A-17)+(B7-33),(A-17)+(B7-34),(A-17)+(B7-35),(A-17)+(B7-36),
(A-17)+(B7-37),(A-17)+(B7-38),(A-17)+(B7-39),(A-17)+(B8-1),
(A-17)+(B8-2),(A-17)+(B8-3),(A-17)+(B9-1),(A-17)+(B9-2),(A-17)+(B9-3),
(A-17)+(B9-4),(A-17)+(B9-5),(A-17)+(B9-6),(A-17)+(B9-7).
(A-18)+(B1-1),(A-18)+(B1-2),(A-18)+(B1-3),(A-18)+(B1-4),(A-18)+(B1-5),
(A-18)+(B1-6),(A-18)+(B1-7),(A-18)+(B1-8),(A-18)+(B2-1),(A-18)+(B2-2),
(A-18)+(B3-1),(A-18)+(B3-2),(A-18)+(B3-3),(A-18)+(B3-4),(A-18)+(B3-5),
(A-18)+(B3-6),(A-18)+(B-3-7),(A-18)+(B3-8),(A-18)+(B3-9),(A-18)+(B4-1),
(A-18)+(B4-2),(A-18)+(B4-3),(A-18)+(B4-4),(A-18)+(B4-5),(A-18)+(B4-6),
(A-18)+(B4-7),(A-18)+(B4-8),(A-18)+(B4-9),(A-18)+(B4-10),(A-18)+(B4-11),
(A-18)+(B5-1),(A-18)+(B5-2),(A-18)+(B5-3),(A-18)+(B5-4),(A-18)+(B5-5),
(A-18)+(B5-6),(A-18)+(B5-7),(A-18)+(B6-1),(A-18)+(B6-2),(A-18)+(B6-3),
(A-18)+(B6-4),(A-18)+(B6-5),(A-18)+(B6-6),(A-18)+(B6-7),(A-18)+(B6-8),
(A-18)+(B6-9),(A-18)+(B6-10),(A-18)+(B6-11),(A-18)+(B6-12),
(A-18)+(B6-13),(A-18)+(B6-14),(A-18)+(B7-1),(A-18)+(B7-2),(A-18)+(B7-3),
(A-18)+(B7-4),(A-18)+(B7-5),(A-18)+(B7-6),(A-18)+(B7-7),(A-18)+(B7-8),
(A-18)+(B7-9),(A-18)+(B7-10),(A-18)+(B7-11),(A-18)+(B7-12),
(A-18)+(B7-13),(A-18)+(B7-14),(A-18)+(B7-15),(A-18)+(B7-16),
(A-18)+(B7-17),(A-18)+(B7-18),(A-18)+(B7-19),(A-18)+(B7-20),
(A-18)+(B7-21),(A-18)+(B7-22),(A-18)+(B7-23),(A-18)+(B7-24),
(A-18)+(B7-25),(A-18)+(B7-26),(A-18)+(B7-27),(A-18)+(B7-28),
(A-18)+(B7-29),(A-18)+(B7-30),(A-18)+(B-31),(A-18)+(B7-32),
(A-18)+(B7-33),(A-18)+(B7-34),(A-18)+(B7-35),(A-18)+(B7-36),
(A-18)+(B7-37),(A-18)+(B7-38),(A-18)+(B7-39),(A-18)+(B8-1),
(A-18)+(B8-2),(A-18)+(B8-3),(A-18)+(B9-1),(A-18)+(B9-2),(A-18)+(B9-3),
(A-18)+(B9-4),(A-18)+(B9-5),(A-18)+(B9-6),(A-18)+(B9-7).
(A-19)+(B1-1),(A-19)+(B1-2),(A-19)+(B1-3),(A-19)+(B1-4),(A-19)+(B1-5),
(A-19)+(B1-6),(A-19)+(B1-7),(A-19)+(B1-8),(A-19)+(B2-1),(A-19)+(B2-2),
(A-19)+(B3-1),(A-19)+(B3-2),(A-19)+(B3-3),(A-19)+(B3-4),(A-19)+(B3-5),
(A-19)+(B3-6),(A-19)+(B-3-7),(A-19)+(B3-8),(A-19)+(B3-9),(A-19)+(B4-1),
(A-19)+(B4-2),(A-19)+(B4-3),(A-19)+(B4-4),(A-19)+(B4-5),(A-19)+(B4-6),
(A-19)+(B4-7),(A-19)+(B4-8),(A-19)+(B4-9),(A-19)+(B4-10),(A-19)+(B4-11),
(A-19)+(B5-1),(A-19)+(B5-2),(A-19)+(B5-3),(A-19)+(B5-4),(A-19)+(B5-5),
(A-19)+(B5-6),(A-19)+(B5-7),(A-19)+(B6-1),(A-19)+(B6-2),(A-19)+(B6-3),
(A-19)+(B6-4),(A-19)+(B6-5),(A-19)+(B6-6),(A-19)+(B6-7),(A-19)+(B6-8),
(A-19)+(B6-9),(A-19)+(B6-10),(A-19)+(B6-11),(A-19)+(B6-12),
(A-19)+(B6-13),(A-19)+(B6-14),(A-19)+(B7-1),(A-19)+(B7-2),(A-19)+(B7-3),
(A-19)+(B7-4),(A-19)+(B7-5),(A-19)+(B7-6),(A-19)+(B7-7),(A-19)+(B7-8),
(A-19)+(B7-9),(A-19)+(B7-10),(A-19)+(B7-11),(A-19)+(B7-12),
(A-19)+(B7-13),(A-19)+(B7-14),(A-19)+(B7-15),(A-19)+(B7-16),
(A-19)+(B7-17),(A-19)+(B7-18),(A-19)+(B7-19),(A-19)+(B7-20),
(A-19)+(B7-21),(A-19)+(B7-22),(A-19)+(B7-23),(A-19)+(B7-24),
(A-19)+(B7-25),(A-19)+(B7-26),(A-19)+(B7-27),(A-19)+(B7-28),
(A-19)+(B7-29),(A-19)+(B7-30),(A-19)+(B-31),(A-19)+(B7-32),
(A-19)+(B7-33),(A-19)+(B7-34),(A-19)+(B7-35),(A-19)+(B7-36),
(A-19)+(B7-37),(A-19)+(B7-38),(A-19)+(B7-39),(A-19)+(B8-1),
(A-19)+(B8-2),(A-19)+(B8-3),(A-19)+(B9-1),(A-19)+(B9-2),(A-19)+(B9-3),
(A-19)+(B9-4),(A-19)+(B9-5),(A-19)+(B9-6),(A-19)+(B9-7).
(A-20)+(B1-1),(A-20)+(B1-2),(A-20)+(B1-3),(A-20)+(B1-4),(A-20)+(B1-5),
(A-20)+(B1-6),(A-20)+(B1-7),(A-20)+(B1-8),(A-20)+(B2-1),(A-20)+(B2-2),
(A-20)+(B3-1),(A-20)+(B3-2),(A-20)+(B3-3),(A-20)+(B3-4),(A-20)+(B3-5),
(A-20)+(B3-6),(A-20)+(B-3-7),(A-20)+(B3-8),(A-20)+(B3-9),(A-20)+(B4-1),
(A-20)+(B4-2),(A-20)+(B4-3),(A-20)+(B4-4),(A-20)+(B4-5),(A-20)+(B4-6),
(A-20)+(B4-7),(A-20)+(B4-8),(A-20)+(B4-9),(A-20)+(B4-10),(A-20)+(B4-11),
(A-20)+(B5-1),(A-20)+(B5-2),(A-20)+(B5-3),(A-20)+(B5-4),(A-20)+(B5-5),
(A-20)+(B5-6),(A-20)+(B5-7),(A-20)+(B6-1),(A-20)+(B6-2),(A-20)+(B6-3),
(A-20)+(B6-4),(A-20)+(B6-5),(A-20)+(B6-6),(A-20)+(B6-7),(A-20)+(B6-8),
(A-20)+(B6-9),(A-20)+(B6-10),(A-20)+(B6-11),(A-20)+(B6-12),
(A-20)+(B6-13),(A-20)+(B6-14),(A-20)+(B7-1),(A-20)+(B7-2),(A-20)+(B7-3),
(A-20)+(B7-4),(A-20)+(B7-5),(A-20)+(B7-6),(A-20)+(B7-7),(A-20)+(B7-8),
(A-20)+(B7-9),(A-20)+(B7-10),(A-20)+(B7-11),(A-20)+(B7-12),
(A-20)+(B7-13),(A-20)+(B7-14),(A-20)+(B7-15),(A-20)+(B7-16),
(A-20)+(B7-17),(A-20)+(B7-18),(A-20)+(B7-19),(A-20)+(B7-20),
(A-20)+(B7-21),(A-20)+(B7-22),(A-20)+(B7-23),(A-20)+(B7-24),
(A-20)+(B7-25),(A-20)+(B7-26),(A-20)+(B7-27),(A-20)+(B7-28),
(A-20)+(B7-29),(A-20)+(B7-30),(A-20)+(B-31),(A-20)+(B7-32),
(A-20)+(B7-33),(A-20)+(B7-34),(A-20)+(B7-35),(A-20)+(B7-36),
(A-20)+(B7-37),(A-20)+(B7-38),(A-20)+(B7-39),(A-20)+(B8-1),
(A-20)+(B8-2),(A-20)+(B8-3),(A-20)+(B9-1),(A-20)+(B9-2),(A-20)+(B9-3),
(A-20)+(B9-4),(A-20)+(B9-5),(A-20)+(B9-6),(A-20)+(B9-7).
(A-21)+(B1-1),(A-21)+(B1-2),(A-21)+(B1-3),(A-21)+(B1-4),(A-21)+(B1-5),
(A-21)+(B1-6),(A-21)+(B1-7),(A-21)+(B1-8),(A-21)+(B2-1),(A-21)+(B2-2),
(A-21)+(B3-1),(A-21)+(B3-2),(A-21)+(B3-3),(A-21)+(B3-4),(A-21)+(B3-5),
(A-21)+(B3-6),(A-21)+(B-3-7),(A-21)+(B3-8),(A-21)+(B3-9),(A-21)+(B4-1),
(A-21)+(B4-2),(A-21)+(B4-3),(A-21)+(B4-4),(A-21)+(B4-5),(A-21)+(B4-6),
(A-21)+(B4-7),(A-21)+(B4-8),(A-21)+(B4-9),(A-21)+(B4-10),(A-21)+(B4-11),
(A-21)+(B5-1),(A-21)+(B5-2),(A-21)+(B5-3),(A-21)+(B5-4),(A-21)+(B5-5),
(A-21)+(B5-6),(A-21)+(B5-7),(A-21)+(B6-1),(A-21)+(B6-2),(A-21)+(B6-3),
(A-21)+(B6-4),(A-21)+(B6-5),(A-21)+(B6-6),(A-21)+(B6-7),(A-21)+(B6-8),
(A-21)+(B6-9),(A-21)+(B6-10),(A-21)+(B6-11),(A-21)+(B6-12),
(A-21)+(B6-13),(A-21)+(B6-14),(A-21)+(B7-1),(A-21)+(B7-2),(A-21)+(B7-3),
(A-21)+(B7-4),(A-21)+(B7-5),(A-21)+(B7-6),(A-21)+(B7-7),(A-21)+(B7-8),
(A-21)+(B7-9),(A-21)+(B7-10),(A-21)+(B7-11),(A-21)+(B7-12),
(A-21)+(B7-13),(A-21)+(B7-14),(A-21)+(B7-15),(A-21)+(B7-16),
(A-21)+(B7-17),(A-21)+(B7-18),(A-21)+(B7-19),(A-21)+(B7-20),
(A-21)+(B7-21),(A-21)+(B7-22),(A-21)+(B7-23),(A-21)+(B7-24),
(A-21)+(B7-25),(A-21)+(B7-26),(A-21)+(B7-27),(A-21)+(B7-28),
(A-21)+(B7-29),(A-21)+(B7-30),(A-21)+(B-31),(A-21)+(B7-32),
(A-21)+(B7-33),(A-21)+(B7-34),(A-21)+(B7-35),(A-21)+(B7-36),
(A-21)+(B7-37),(A-21)+(B7-38),(A-21)+(B7-39),(A-21)+(B8-1),
(A-21)+(B8-2),(A-21)+(B8-3),(A-21)+(B9-1),(A-21)+(B9-2),(A-21)+(B9-3),
(A-21)+(B9-4),(A-21)+(B9-5),(A-21)+(B9-6),(A-21)+(B9-7).
(A-22)+(B1-1),(A-22)+(B1-2),(A-22)+(B1-3),(A-22)+(B1-4),(A-22)+(B1-5),
(A-22)+(B1-6),(A-22)+(B1-7),(A-22)+(B1-8),(A-22)+(B2-1),(A-22)+(B2-2),
(A-22)+(B3-1),(A-22)+(B3-2),(A-22)+(B3-3),(A-22)+(B3-4),(A-22)+(B3-5),
(A-22)+(B3-6),(A-22)+(B-3-7),(A-22)+(B3-8),(A-22)+(B3-9),(A-22)+(B4-1),
(A-22)+(B4-2),(A-22)+(B4-3),(A-22)+(B4-4),(A-22)+(B4-5),(A-22)+(B4-6),
(A-22)+(B4-7),(A-22)+(B4-8),(A-22)+(B4-9),(A-22)+(B4-10),(A-22)+(B4-11),
(A-22)+(B5-1),(A-22)+(B5-2),(A-22)+(B5-3),(A-22)+(B5-4),(A-22)+(B5-5),
(A-22)+(B5-6),(A-22)+(B5-7),(A-22)+(B6-1),(A-22)+(B6-2),(A-22)+(B6-3),
(A-22)+(B6-4),(A-22)+(B6-5),(A-22)+(B6-6),(A-22)+(B6-7),(A-22)+(B6-8),
(A-22)+(B6-9),(A-22)+(B6-10),(A-22)+(B6-11),(A-22)+(B6-12),
(A-22)+(B6-13),(A-22)+(B6-14),(A-22)+(B7-1),(A-22)+(B7-2),(A-22)+(B7-3),
(A-22)+(B7-4),(A-22)+(B7-5),(A-22)+(B7-6),(A-22)+(B7-7),(A-22)+(B7-8),
(A-22)+(B7-9),(A-22)+(B7-10),(A-22)+(B7-11),(A-22)+(B7-12),
(A-22)+(B7-13),(A-22)+(B7-14),(A-22)+(B7-15),(A-22)+(B7-16),
(A-22)+(B7-17),(A-22)+(B7-18),(A-22)+(B7-19),(A-22)+(B7-20),
(A-22)+(B7-21),(A-22)+(B7-22),(A-22)+(B7-23),(A-22)+(B7-24),
(A-22)+(B7-25),(A-22)+(B7-26),(A-22)+(B7-27),(A-22)+(B7-28),
(A-22)+(B7-29),(A-22)+(B7-30),(A-22)+(B-31),(A-22)+(B7-32),
(A-22)+(B7-33),(A-22)+(B7-34),(A-22)+(B7-35),(A-22)+(B7-36),
(A-22)+(B7-37),(A-22)+(B7-38),(A-22)+(B7-39),(A-22)+(B8-1),
(A-22)+(B8-2),(A-22)+(B8-3),(A-22)+(B9-1),(A-22)+(B9-2),(A-22)+(B9-3),
(A-22)+(B9-4),(A-22)+(B9-5),(A-22)+(B9-6),(A-22)+(B9-7).
(A-23)+(B1-1),(A-23)+(B1-2),(A-23)+(B1-3),(A-23)+(B1-4),(A-23)+(B1-5),
(A-23)+(B1-6),(A-23)+(B1-7),(A-23)+(B1-8),(A-23)+(B2-1),(A-23)+(B2-2),
(A-23)+(B3-1),(A-23)+(B3-2),(A-23)+(B3-3),(A-23)+(B3-4),(A-23)+(B3-5),
(A-23)+(B3-6),(A-23)+(B-3-7),(A-23)+(B3-8),(A-23)+(B3-9),(A-23)+(B4-1),
(A-23)+(B4-2),(A-23)+(B4-3),(A-23)+(B4-4),(A-23)+(B4-5),(A-23)+(B4-6),
(A-23)+(B4-7),(A-23)+(B4-8),(A-23)+(B4-9),(A-23)+(B4-10),(A-23)+(B4-11),
(A-23)+(B5-1),(A-23)+(B5-2),(A-23)+(B5-3),(A-23)+(B5-4),(A-23)+(B5-5),
(A-23)+(B5-6),(A-23)+(B5-7),(A-23)+(B6-1),(A-23)+(B6-2),(A-23)+(B6-3),
(A-23)+(B6-4),(A-23)+(B6-5),(A-23)+(B6-6),(A-23)+(B6-7),(A-23)+(B6-8),
(A-23)+(B6-9),(A-23)+(B6-10),(A-23)+(B6-11),(A-23)+(B6-12),
(A-23)+(B6-13),(A-23)+(B6-14),(A-23)+(B7-1),(A-23)+(B7-2),(A-23)+(B7-3),
(A-23)+(B7-4),(A-23)+(B7-5),(A-23)+(B7-6),(A-23)+(B7-7),(A-23)+(B7-8),
(A-23)+(B7-9),(A-23)+(B7-10),(A-23)+(B7-11),(A-23)+(B7-12),
(A-23)+(B7-13),(A-23)+(B7-14),(A-23)+(B7-15),(A-23)+(B7-16),
(A-23)+(B7-17),(A-23)+(B7-18),(A-23)+(B7-19),(A-23)+(B7-20),
(A-23)+(B7-21),(A-23)+(B7-22),(A-23)+(B7-23),(A-23)+(B7-24),
(A-23)+(B7-25),(A-23)+(B7-26),(A-23)+(B7-27),(A-23)+(B7-28),
(A-23)+(B7-29),(A-23)+(B7-30),(A-23)+(B-31),(A-23)+(B7-32),
(A-23)+(B7-33),(A-23)+(B7-34),(A-23)+(B7-35),(A-23)+(B7-36),
(A-23)+(B7-37),(A-23)+(B7-38),(A-23)+(B7-39),(A-23)+(B8-1),
(A-23)+(B8-2),(A-23)+(B8-3),(A-23)+(B9-1),(A-23)+(B9-2),(A-23)+(B9-3),
(A-23)+(B9-4),(A-23)+(B9-5),(A-23)+(B9-6),(A-23)+(B9-7).
(A-24)+(B1-1),(A-24)+(B1-2),(A-24)+(B1-3),(A-24)+(B1-4),(A-24)+(B1-5),
(A-24)+(B1-6),(A-24)+(B1-7),(A-24)+(B1-8),(A-24)+(B2-1),(A-24)+(B2-2),
(A-24)+(B3-1),(A-24)+(B3-2),(A-24)+(B3-3),(A-24)+(B3-4),(A-24)+(B3-5),
(A-24)+(B3-6),(A-24)+(B-3-7),(A-24)+(B3-8),(A-24)+(B3-9),(A-24)+(B4-1),
(A-24)+(B4-2),(A-24)+(B4-3),(A-24)+(B4-4),(A-24)+(B4-5),(A-24)+(B4-6),
(A-24)+(B4-7),(A-24)+(B4-8),(A-24)+(B4-9),(A-24)+(B4-10),(A-24)+(B4-11),
(A-24)+(B5-1),(A-24)+(B5-2),(A-24)+(B5-3),(A-24)+(B5-4),(A-24)+(B5-5),
(A-24)+(B5-6),(A-24)+(B5-7),(A-24)+(B6-1),(A-24)+(B6-2),(A-24)+(B6-3),
(A-24)+(B6-4),(A-24)+(B6-5),(A-24)+(B6-6),(A-24)+(B6-7),(A-24)+(B6-8),
(A-24)+(B6-9),(A-24)+(B6-10),(A-24)+(B6-11),(A-24)+(B6-12),
(A-24)+(B6-13),(A-24)+(B6-14),(A-24)+(B7-1),(A-24)+(B7-2),(A-24)+(B7-3),
(A-24)+(B7-4),(A-24)+(B7-5),(A-24)+(B7-6),(A-24)+(B7-7),(A-24)+(B7-8),
(A-24)+(B7-9),(A-24)+(B7-10),(A-24)+(B7-11),(A-24)+(B7-12),
(A-24)+(B7-13),(A-24)+(B7-14),(A-24)+(B7-15),(A-24)+(B7-16),
(A-24)+(B7-17),(A-24)+(B7-18),(A-24)+(B7-19),(A-24)+(B7-20),
(A-24)+(B7-21),(A-24)+(B7-22),(A-24)+(B7-23),(A-24)+(B7-24),
(A-24)+(B7-25),(A-24)+(B7-26),(A-24)+(B7-27),(A-24)+(B7-28),
(A-24)+(B7-29),(A-24)+(B7-30),(A-24)+(B-31),(A-24)+(B7-32),
(A-24)+(B7-33),(A-24)+(B7-34),(A-24)+(B7-35),(A-24)+(B7-36),
(A-24)+(B7-37),(A-24)+(B7-38),(A-24)+(B7-39),(A-24)+(B8-1),
(A-24)+(B8-2),(A-24)+(B8-3),(A-24)+(B9-1),(A-24)+(B9-2),(A-24)+(B9-3),
(A-24)+(B9-4),(A-24)+(B9-5),(A-24)+(B9-6),(A-24)+(B9-7).
(A-25)+(B1-1),(A-25)+(B1-2),(A-25)+(B1-3),(A-25)+(B1-4),(A-25)+(B1-5),
(A-25)+(B1-6),(A-25)+(B1-7),(A-25)+(B1-8),(A-25)+(B2-1),(A-25)+(B2-2),
(A-25)+(B3-1),(A-25)+(B3-2),(A-25)+(B3-3),(A-25)+(B3-4),(A-25)+(B3-5),
(A-25)+(B3-6),(A-25)+(B-3-7),(A-25)+(B3-8),(A-25)+(B3-9),(A-25)+(B4-1),
(A-25)+(B4-2),(A-25)+(B4-3),(A-25)+(B4-4),(A-25)+(B4-5),(A-25)+(B4-6),
(A-25)+(B4-7),(A-25)+(B4-8),(A-25)+(B4-9),(A-25)+(B4-10),(A-25)+(B4-11),
(A-25)+(B5-1),(A-25)+(B5-2),(A-25)+(B5-3),(A-25)+(B5-4),(A-25)+(B5-5),
(A-25)+(B5-6),(A-25)+(B5-7),(A-25)+(B6-1),(A-25)+(B6-2),(A-25)+(B6-3),
(A-25)+(B6-4),(A-25)+(B6-5),(A-25)+(B6-6),(A-25)+(B6-7),(A-25)+(B6-8),
(A-25)+(B6-9),(A-25)+(B6-10),(A-25)+(B6-11),(A-25)+(B6-12),
(A-25)+(B6-13),(A-25)+(B6-14),(A-25)+(B7-1),(A-25)+(B7-2),(A-25)+(B7-3),
(A-25)+(B7-4),(A-25)+(B7-5),(A-25)+(B7-6),(A-25)+(B7-7),(A-25)+(B7-8),
(A-25)+(B7-9),(A-25)+(B7-10),(A-25)+(B7-11),(A-25)+(B7-12),
(A-25)+(B7-13),(A-25)+(B7-14),(A-25)+(B7-15),(A-25)+(B7-16),
(A-25)+(B7-17),(A-25)+(B7-18),(A-25)+(B7-19),(A-25)+(B7-20),
(A-25)+(B7-21),(A-25)+(B7-22),(A-25)+(B7-23),(A-25)+(B7-24),
(A-25)+(B7-25),(A-25)+(B7-26),(A-25)+(B7-27),(A-25)+(B7-28),
(A-25)+(B7-29),(A-25)+(B7-30),(A-25)+(B-31),(A-25)+(B7-32),
(A-25)+(B7-33),(A-25)+(B7-34),(A-25)+(B7-35),(A-25)+(B7-36),
(A-25)+(B7-37),(A-25)+(B7-38),(A-25)+(B7-39),(A-25)+(B8-1),
(A-25)+(B8-2),(A-25)+(B8-3),(A-25)+(B9-1),(A-25)+(B9-2),(A-25)+(B9-3),
(A-25)+(B9-4),(A-25)+(B9-5),(A-25)+(B9-6),(A-25)+(B9-7).
(A-26)+(B1-1),(A-26)+(B1-2),(A-26)+(B1-3),(A-26)+(B1-4),(A-26)+(B1-5),
(A-26)+(B1-6),(A-26)+(B1-7),(A-26)+(B1-8),(A-26)+(B2-1),(A-26)+(B2-2),
(A-26)+(B3-1),(A-26)+(B3-2),(A-26)+(B3-3),(A-26)+(B3-4),(A-26)+(B3-5),
(A-26)+(B3-6),(A-26)+(B-3-7),(A-26)+(B3-8),(A-26)+(B3-9),(A-26)+(B4-1),
(A-26)+(B4-2),(A-26)+(B4-3),(A-26)+(B4-4),(A-26)+(B4-5),(A-26)+(B4-6),
(A-26)+(B4-7),(A-26)+(B4-8),(A-26)+(B4-9),(A-26)+(B4-10),(A-26)+(B4-11),
(A-26)+(B5-1),(A-26)+(B5-2),(A-26)+(B5-3),(A-26)+(B5-4),(A-26)+(B5-5),
(A-26)+(B5-6),(A-26)+(B5-7),(A-26)+(B6-1),(A-26)+(B6-2),(A-26)+(B6-3),
(A-26)+(B6-4),(A-26)+(B6-5),(A-26)+(B6-6),(A-26)+(B6-7),(A-26)+(B6-8),
(A-26)+(B6-9),(A-26)+(B6-10),(A-26)+(B6-11),(A-26)+(B6-12),
(A-26)+(B6-13),(A-26)+(B6-14),(A-26)+(B7-1),(A-26)+(B7-2),(A-26)+(B7-3),
(A-26)+(B7-4),(A-26)+(B7-5),(A-26)+(B7-6),(A-26)+(B7-7),(A-26)+(B7-8),
(A-26)+(B7-9),(A-26)+(B7-10),(A-26)+(B7-11),(A-26)+(B7-12),
(A-26)+(B7-13),(A-26)+(B7-14),(A-26)+(B7-15),(A-26)+(B7-16),
(A-26)+(B7-17),(A-26)+(B7-18),(A-26)+(B7-19),(A-26)+(B7-20),
(A-26)+(B7-21),(A-26)+(B7-22),(A-26)+(B7-23),(A-26)+(B7-24),
(A-26)+(B7-25),(A-26)+(B7-26),(A-26)+(B7-27),(A-26)+(B7-28),
(A-26)+(B7-29),(A-26)+(B7-30),(A-26)+(B-31),(A-26)+(B7-32),
(A-26)+(B7-33),(A-26)+(B7-34),(A-26)+(B7-35),(A-26)+(B7-36),
(A-26)+(B7-37),(A-26)+(B7-38),(A-26)+(B7-39),(A-26)+(B8-1),
(A-26)+(B8-2),(A-26)+(B8-3),(A-26)+(B9-1),(A-26)+(B9-2),(A-26)+(B9-3),
(A-26)+(B9-4),(A-26)+(B9-5),(A-26)+(B9-6),(A-26)+(B9-7).
(A-27)+(B1-1),(A-27)+(B1-2),(A-27)+(B1-3),(A-27)+(B1-4),(A-27)+(B1-5),
(A-27)+(B1-6),(A-27)+(B1-7),(A-27)+(B1-8),(A-27)+(B2-1),(A-27)+(B2-2),
(A-27)+(B3-1),(A-27)+(B3-2),(A-27)+(B3-3),(A-27)+(B3-4),(A-27)+(B3-5),
(A-27)+(B3-6),(A-27)+(B-3-7),(A-27)+(B3-8),(A-27)+(B3-9),(A-27)+(B4-1),
(A-27)+(B4-2),(A-27)+(B4-3),(A-27)+(B4-4),(A-27)+(B4-5),(A-27)+(B4-6),
(A-27)+(B4-7),(A-27)+(B4-8),(A-27)+(B4-9),(A-27)+(B4-10),(A-27)+(B4-11),
(A-27)+(B5-1),(A-27)+(B5-2),(A-27)+(B5-3),(A-27)+(B5-4),(A-27)+(B5-5),
(A-27)+(B5-6),(A-27)+(B5-7),(A-27)+(B6-1),(A-27)+(B6-2),(A-27)+(B6-3),
(A-27)+(B6-4),(A-27)+(B6-5),(A-27)+(B6-6),(A-27)+(B6-7),(A-27)+(B6-8),
(A-27)+(B6-9),(A-27)+(B6-10),(A-27)+(B6-11),(A-27)+(B6-12),
(A-27)+(B6-13),(A-27)+(B6-14),(A-27)+(B7-1),(A-27)+(B7-2),(A-27)+(B7-3),
(A-27)+(B7-4),(A-27)+(B7-5),(A-27)+(B7-6),(A-27)+(B7-7),(A-27)+(B7-8),
(A-27)+(B7-9),(A-27)+(B7-10),(A-27)+(B7-11),(A-27)+(B7-12),
(A-27)+(B7-13),(A-27)+(B7-14),(A-27)+(B7-15),(A-27)+(B7-16),
(A-27)+(B7-17),(A-27)+(B7-18),(A-27)+(B7-19),(A-27)+(B7-20),
(A-27)+(B7-21),(A-27)+(B7-22),(A-27)+(B7-23),(A-27)+(B7-24),
(A-27)+(B7-25),(A-27)+(B7-26),(A-27)+(B7-27),(A-27)+(B7-28),
(A-27)+(B7-29),(A-27)+(B7-30),(A-27)+(B-31),(A-27)+(B7-32),
(A-27)+(B7-33),(A-27)+(B7-34),(A-27)+(B7-35),(A-27)+(B7-36),
(A-27)+(B7-37),(A-27)+(B7-38),(A-27)+(B7-39),(A-27)+(B8-1),
(A-27)+(B8-2),(A-27)+(B8-3),(A-27)+(B9-1),(A-27)+(B9-2),(A-27)+(B9-3),
(A-27)+(B9-4),(A-27)+(B9-5),(A-27)+(B9-6),(A-27)+(B9-7).
(A-28)+(B1-1),(A-28)+(B1-2),(A-28)+(B1-3),(A-28)+(B1-4),(A-28)+(B1-5),
(A-28)+(B1-6),(A-28)+(B1-7),(A-28)+(B1-8),(A-28)+(B2-1),(A-28)+(B2-2),
(A-28)+(B3-1),(A-28)+(B3-2),(A-28)+(B3-3),(A-28)+(B3-4),(A-28)+(B3-5),
(A-28)+(B3-6),(A-28)+(B-3-7),(A-28)+(B3-8),(A-28)+(B3-9),(A-28)+(B4-1),
(A-28)+(B4-2),(A-28)+(B4-3),(A-28)+(B4-4),(A-28)+(B4-5),(A-28)+(B4-6),
(A-28)+(B4-7),(A-28)+(B4-8),(A-28)+(B4-9),(A-28)+(B4-10),(A-28)+(B4-11),
(A-28)+(B5-1),(A-28)+(B5-2),(A-28)+(B5-3),(A-28)+(B5-4),(A-28)+(B5-5),
(A-28)+(B5-6),(A-28)+(B5-7),(A-28)+(B6-1),(A-28)+(B6-2),(A-28)+(B6-3),
(A-28)+(B6-4),(A-28)+(B6-5),(A-28)+(B6-6),(A-28)+(B6-7),(A-28)+(B6-8),
(A-28)+(B6-9),(A-28)+(B6-10),(A-28)+(B6-11),(A-28)+(B6-12),
(A-28)+(B6-13),(A-28)+(B6-14),(A-28)+(B7-1),(A-28)+(B7-2),(A-28)+(B7-3),
(A-28)+(B7-4),(A-28)+(B7-5),(A-28)+(B7-6),(A-28)+(B7-7),(A-28)+(B7-8),
(A-28)+(B7-9),(A-28)+(B7-10),(A-28)+(B7-11),(A-28)+(B7-12),
(A-28)+(B7-13),(A-28)+(B7-14),(A-28)+(B7-15),(A-28)+(B7-16),
(A-28)+(B7-17),(A-28)+(B7-18),(A-28)+(B7-19),(A-28)+(B7-20),
(A-28)+(B7-21),(A-28)+(B7-22),(A-28)+(B7-23),(A-28)+(B7-24),
(A-28)+(B7-25),(A-28)+(B7-26),(A-28)+(B7-27),(A-28)+(B7-28),
(A-28)+(B7-29),(A-28)+(B7-30),(A-28)+(B-31),(A-28)+(B7-32),
(A-28)+(B7-33),(A-28)+(B7-34),(A-28)+(B7-35),(A-28)+(B7-36),
(A-28)+(B7-37),(A-28)+(B7-38),(A-28)+(B7-39),(A-28)+(B8-1),
(A-2B)+(B8-2),(A-28)+(B8-3),(A-28)+(B9-1),(A-28)+(B9-2),(A-28)+(B9-3),
(A-28)+(B9-4),(A-28)+(B9-5),(A-28)+(B9-6),(A-28)+(B9-7).
(A-29)+(B1-1),(A-29)+(B1-2),(A-29)+(B1-3),(A-29)+(B1-4),(A-29)+(B1-5),
(A-29)+(B1-6),(A-29)+(B1-7),(A-29)+(B1-8),(A-29)+(B2-1),(A-29)+(B2-2),
(A-29)+(B3-1),(A-29)+(B3-2),(A-29)+(B3-3),(A-29)+(B3-4),(A-29)+(B3-5),
(A-29)+(B3-6),(A-29)+(B-3-7),(A-29)+(B3-8),(A-29)+(B3-9),(A-29)+(B4-1),
(A-29)+(B4-2),(A-29)+(B4-3),(A-29)+(B4-4),(A-29)+(B4-5),(A-29)+(B4-6),
(A-29)+(B4-7),(A-29)+(B4-8),(A-29)+(B4-9),(A-29)+(B4-10),(A-29)+(B4-11),
(A-29)+(B5-1),(A-29)+(B5-2),(A-29)+(B5-3),(A-29)+(B5-4),(A-29)+(B5-5),
(A-29)+(B5-6),(A-29)+(B5-7),(A-29)+(B6-1),(A-29)+(B6-2),(A-29)+(B6-3),
(A-29)+(B6-4),(A-29)+(B6-5),(A-29)+(B6-6),(A-29)+(B6-7),(A-29)+(B6-8),
(A-29)+(B6-9),(A-29)+(B6-10),(A-29)+(B6-11),(A-29)+(B6-12),
(A-29)+(B6-13),(A-29)+(B6-14),(A-29)+(B7-1),(A-29)+(B7-2),(A-29)+(B7-3),
(A-29)+(B7-4),(A-29)+(B7-5),(A-29)+(B7-6),(A-29)+(B7-7),(A-29)+(B7-8),
(A-29)+(B7-9),(A-29)+(B7-10),(A-29)+(B7-11),(A-29)+(B7-12),
(A-29)+(B7-13),(A-29)+(B7-14),(A-29)+(B7-15),(A-29)+(B7-16),
(A-29)+(B7-17),(A-29)+(B7-18),(A-29)+(B7-19),(A-29)+(B7-20),
(A-29)+(B7-21),(A-29)+(B7-22),(A-29)+(B7-23),(A-29)+(B7-24),
(A-29)+(B7-25),(A-29)+(B7-26),(A-29)+(B7-27),(A-29)+(B7-28),
(A-29)+(B7-29),(A-29)+(B7-30),(A-29)+(B-31),(A-29)+(B7-32),
(A-29)+(B7-33),(A-29)+(B7-34),(A-29)+(B7-35),(A-29)+(B7-36),
(A-29)+(B7-37),(A-29)+(B7-38),(A-29)+(B7-39),(A-29)+(B8-1),
(A-29)+(B8-2),(A-29)+(B8-3),(A-29)+(B9-1),(A-29)+(B9-2),(A-29)+(B9-3),
(A-29)+(B9-4),(A-29)+(B9-5),(A-29)+(B9-6),(A-29)+(B9-7).
(A-30)+(B1-1),(A-30)+(B1-2),(A-30)+(B1-3),(A-30)+(B1-4),(A-30)+(B1-5),
(A-30)+(B1-6),(A-30)+(B1-7),(A-30)+(B1-8),(A-30)+(B2-1),(A-30)+(B2-2),
(A-30)+(B3-1),(A-30)+(B3-2),(A-30)+(B3-3),(A-30)+(B3-4),(A-30)+(B3-5),
(A-30)+(B3-6),(A-30)+(B-3-7),(A-30)+(B3-8),(A-30)+(B3-9),(A-30)+(B4-1),
(A-30)+(B4-2),(A-30)+(B4-3),(A-30)+(B4-4),(A-30)+(B4-5),(A-30)+(B4-6),
(A-30)+(B4-7),(A-30)+(B4-8),(A-30)+(B4-9),(A-30)+(B4-10),(A-30)+(B4-11),
(A-30)+(B5-1),(A-30)+(B5-2),(A-30)+(B5-3),(A-30)+(B5-4),(A-30)+(B5-5),
(A-30)+(B5-6),(A-30)+(B5-7),(A-30)+(B6-1),(A-30)+(B6-2),(A-30)+(B6-3),
(A-30)+(B6-4),(A-30)+(B6-5),(A-30)+(B6-6),(A-30)+(B6-7),(A-30)+(B6-8),
(A-30)+(B6-9),(A-30)+(B6-10),(A-30)+(B6-11),(A-30)+(B6-12),
(A-30)+(B6-13),(A-30)+(B6-14),(A-30)+(B7-1),(A-30)+(B7-2),
(A-30)+(B7-3),(A-30)+(B7-4),(A-30)+(B7-5),(A-30)+(B7-6),(A-30)+(B7-7),
(A-30)+(B7-8),(A-30)+(B7-9),(A-30)+(B7-10),(A-30)+(B7-11),
(A-30)+(B7-12),(A-30)+(B7-13),(A-30)+(B7-14),(A-30)+(B7-15),
(A-30)+(B7-16),(A-30)+(B7-17),(A-30)+(B7-18),(A-30)+(B7-19),
(A-30)+(B7-20),(A-30)+(B7-21),(A-30)+(B7-22),(A-30)+(B7-23),
(A-30)+(B7-24),(A-30)+(B7-25),(A-30)+(B7-26),(A-30)+(B7-27),
(A-30)+(B7-28),(A-30)+(B7-29),(A-30)+(B7-30),(A-30)+(B-31),
(A-30)+(B7-32),(A-30)+(B7-33),(A-30)+(B7-34),(A-30)+(B7-35),
(A-30)+(B7-36),(A-30)+(B7-37),(A-30)+(B7-38),(A-30)+(B7-39),
(A-30)+(B8-1),(A-30)+(B8-2),(A-30)+(B8-3),(A-30)+(B9-1),(A-30)+(B9-2),
(A-30)+(B9-3),(A-30)+(B9-4),(A-30)+(B9-5),(A-30)+(B9-6),(A-30)+(B9-7).
(A-31)+(B1-1),(A-31)+(B1-2),(A-31)+(B1-3),(A-31)+(B1-4),(A-31)+(B1-5),
(A-31)+(B1-6),(A-31)+(B1-7),(A-31)+(B1-8),(A-31)+(B2-1),(A-31)+(B2-2),
(A-31)+(B3-1),(A-31)+(B3-2),(A-31)+(B3-3),(A-31)+(B3-4),(A-31)+(B3-5),
(A-31)+(B3-6),(A-31)+(B-3-7),(A-31)+(B3-8),(A-31)+(B3-9),(A-31)+(B4-1),
(A-31)+(B4-2),(A-31)+(B4-3),(A-31)+(B4-4),(A-31)+(B4-5),(A-31)+(B4-6),
(A-31)+(B4-7),(A-31)+(B4-8),(A-31)+(B4-9),(A-31)+(B4-10),(A-31)+(B4-11),
(A-31)+(B5-1),(A-31)+(B5-2),(A-31)+(B5-3),(A-31)+(B5-4),(A-31)+(B5-5),
(A-31)+(B5-6),(A-31)+(B5-7),(A-31)+(B6-1),(A-31)+(B6-2),(A-31)+(B6-3),
(A-31)+(B6-4),(A-31)+(B6-5),(A-31)+(B6-6),(A-31)+(B6-7),(A-31)+(B6-8),
(A-31)+(B6-9),(A-31)+(B6-10),(A-31)+(B6-11),(A-31)+(B6-12),
(A-31)+(B6-13),(A-31)+(B6-14),(A-31)+(B7-1),(A-31)+(B7-2),(A-31)+(B7-3),
(A-31)+(B7-4),(A-31)+(B7-5),(A-31)+(B7-6),(A-31)+(B7-7),(A-31)+(B7-8),
(A-31)+(B7-9),(A-31)+(B7-10),(A-31)+(B7-11),(A-31)+(B7-12),
(A-31)+(B7-13),(A-31)+(B7-14),(A-31)+(B7-15),(A-31)+(B7-16),
(A-31)+(B7-17),(A-31)+(B7-18),(A-31)+(B7-19),(A-31)+(B7-20),
(A-31)+(B7-21),(A-31)+(B7-22),(A-31)+(B7-23),(A-31)+(B7-24),
(A-31)+(B7-25),(A-31)+(B7-26),(A-31)+(B7-27),(A-31)+(B7-28),
(A-31)+(B7-29),(A-31)+(B7-30),(A-31)+(B-31),(A-31)+(B7-32),
(A-31)+(B7-33),(A-31)+(B7-34),(A-31)+(B7-35),(A-31)+(B7-36),
(A-31)+(B7-37),(A-31)+(B7-38),(A-31)+(B7-39),(A-31)+(B8-1),
(A-31)+(B8-2),(A-31)+(B8-3),(A-31)+(B9-1),(A-31)+(B9-2),(A-31)+(B9-3),
(A-31)+(B9-4),(A-31)+(B9-5),(A-31)+(B9-6),(A-31)+(B9-7).
(A-32)+(B1-1),(A-32)+(B1-2),(A-32)+(B1-3),(A-32)+(B1-4),(A-32)+(B1-5),
(A-32)+(B1-6),(A-32)+(B1-7),(A-32)+(B1-8),(A-32)+(B2-1),(A-32)+(B2-2),
(A-32)+(B3-1),(A-32)+(B3-2),(A-32)+(B3-3),(A-32)+(B3-4),(A-32)+(B3-5),
(A-32)+(B3-6),(A-32)+(B-3-7),(A-32)+(B3-8),(A-32)+(B3-9),(A-32)+(B4-1),
(A-32)+(B4-2),(A-32)+(B4-3),(A-32)+(B4-4),(A-32)+(B4-5),(A-32)+(B4-6),
(A-32)+(B4-7),(A-32)+(B4-8),(A-32)+(B4-9),(A-32)+(B4-10),(A-32)+(B4-11),
(A-32)+(B5-1),(A-32)+(B5-2),(A-32)+(B5-3),(A-32)+(B5-4),(A-32)+(B5-5),
(A-32)+(B5-6),(A-32)+(B5-7),(A-32)+(B6-1),(A-32)+(B6-2),(A-32)+(B6-3),
(A-32)+(B6-4),(A-32)+(B6-5),(A-32)+(B6-6),(A-32)+(B6-7),(A-32)+(B6-8),
(A-32)+(B6-9),(A-32)+(B6-10),(A-32)+(B6-11),(A-32)+(B6-12),
(A-32)+(B6-13),(A-32)+(B6-14),(A-32)+(B7-1),(A-32)+(B7-2),(A-32)+(B7-3),
(A-32)+(B7-4),(A-32)+(B7-5),(A-32)+(B7-6),(A-32)+(B7-7),(A-32)+(B7-8),
(A-32)+(B7-9),(A-32)+(B7-10),(A-32)+(B7-11),(A-32)+(B7-12),
(A-32)+(B7-13),(A-32)+(B7-14),(A-32)+(B7-15),(A-32)+(B7-16),
(A-32)+(B7-17),(A-32)+(B7-18),(A-32)+(B7-19),(A-32)+(B7-20),
(A-32)+(B7-21),(A-32)+(B7-22),(A-32)+(B7-23),(A-32)+(B7-24),
(A-32)+(B7-25),(A-32)+(B7-26),(A-32)+(B7-27),(A-32)+(B7-28),
(A-32)+(B7-29),(A-32)+(B7-30),(A-32)+(B-31),(A-32)+(B7-32),
(A-32)+(B7-33),(A-32)+(B7-34),(A-32)+(B7-35),(A-32)+(B7-36),
(A-32)+(B7-37),(A-32)+(B7-38),(A-32)+(B7-39),(A-32)+(B8-1),
(A-32)+(B8-2),(A-32)+(B8-3),(A-32)+(B9-1),(A-32)+(B9-2),(A-32)+(B9-3),
(A-32)+(B9-4),(A-32)+(B9-5),(A-32)+(B9-6),(A-32)+(B9-7).
(A-33)+(B1-1),(A-33)+(B1-2),(A-33)+(B1-3),(A-33)+(B1-4),(A-33)+(B1-5),
(A-33)+(B1-6),(A-33)+(B1-7),(A-33)+(B1-8),(A-33)+(B2-1),(A-33)+(B2-2),
(A-33)+(B3-1),(A-33)+(B3-2),(A-33)+(B3-3),(A-33)+(B3-4),(A-33)+(B3-5),
(A-33)+(B3-6),(A-33)+(B-3-7),(A-33)+(B3-8),(A-33)+(B3-9),(A-33)+(B4-1),
(A-33)+(B4-2),(A-33)+(B4-3),(A-33)+(B4-4),(A-33)+(B4-5),(A-33)+(B4-6),
(A-33)+(B4-7),(A-33)+(B4-8),(A-33)+(B4-9),(A-33)+(B4-10),(A-33)+(B4-11),
(A-33)+(B5-1),(A-33)+(B5-2),(A-33)+(B5-3),(A-33)+(B5-4),(A-33)+(B5-5),
(A-33)+(B5-6),(A-33)+(B5-7),(A-33)+(B6-1),(A-33)+(B6-2),(A-33)+(B6-3),
(A-33)+(B6-4),(A-33)+(B6-5),(A-33)+(B6-6),(A-33)+(B6-7),(A-33)+(B6-8),
(A-33)+(B6-9),(A-33)+(B6-10),(A-33)+(B6-11),(A-33)+(B6-12),
(A-33)+(B6-13),(A-33)+(B6-14),(A-33)+(B7-1),(A-33)+(B7-2),(A-33)+(B7-3),
(A-33)+(B7-4),(A-33)+(B7-5),(A-33)+(B7-6),(A-33)+(B7-7),(A-33)+(B7-8),
(A-33)+(B7-9),(A-33)+(B7-10),(A-33)+(B7-11),(A-33)+(B7-12),
(A-33)+(B7-13),(A-33)+(B7-14),(A-33)+(B7-15),(A-33)+(B7-16),
(A-33)+(B7-17),(A-33)+(B7-18),(A-33)+(B7-19),(A-33)+(B7-20),
(A-33)+(B7-21),(A-33)+(B7-22),(A-33)+(B7-23),(A-33)+(B7-24),
(A-33)+(B7-25),(A-33)+(B7-26),(A-33)+(B7-27),(A-33)+(B7-28),
(A-33)+(B7-29),(A-33)+(B7-30),(A-33)+(B-31),(A-33)+(B7-32),
(A-33)+(B7-33),(A-33)+(B7-34),(A-33)+(B7-35),(A-33)+(B7-36),
(A-33)+(B7-37),(A-33)+(B7-38),(A-33)+(B7-39),(A-33)+(B8-1),
(A-33)+(B8-2),(A-33)+(B8-3),(A-33)+(B9-1),(A-33)+(B9-2),(A-33)+(B9-3),
(A-33)+(B9-4),(A-33)+(B9-5),(A-33)+(B9-6),(A-33)+(B9-7).
(A-34)+(B1-1),(A-34)+(B1-2),(A-34)+(B1-3),(A-34)+(B1-4),(A-34)+(B1-5),
(A-34)+(B1-6),(A-34)+(B1-7),(A-34)+(B1-8),(A-34)+(B2-1),(A-34)+(B2-2),
(A-34)+(B3-1),(A-34)+(B3-2),(A-34)+(B3-3),(A-34)+(B3-4),(A-34)+(B3-5),
(A-34)+(B3-6),(A-34)+(B-3-7),(A-34)+(B3-8),(A-34)+(B3-9),(A-34)+(B4-1),
(A-34)+(B4-2),(A-34)+(B4-3),(A-34)+(B4-4),(A-34)+(B4-5),(A-34)+(B4-6),
(A-34)+(B4-7),(A-34)+(B4-8),(A-34)+(B4-9),(A-34)+(B4-10),(A-34)+(B4-11),
(A-34)+(B5-1),(A-34)+(B5-2),(A-34)+(B5-3),(A-34)+(B5-4),(A-34)+(B5-5),
(A-34)+(B5-6),(A-34)+(B5-7),(A-34)+(B6-1),(A-34)+(B6-2),(A-34)+(B6-3),
(A-34)+(B6-4),(A-34)+(B6-5),(A-34)+(B6-6),(A-34)+(B6-7),(A-34)+(B6-8),
(A-34)+(B6-9),(A-34)+(B6-10),(A-34)+(B6-11),(A-34)+(B6-12),
(A-34)+(B6-13),(A-34)+(B6-14),(A-34)+(B7-1),(A-34)+(B7-2),(A-34)+(B7-3),
(A-34)+(B7-4),(A-34)+(B7-5),(A-34)+(B7-6),(A-34)+(B7-7),(A-34)+(B7-8),
(A-34)+(B7-9),(A-34)+(B7-10),(A-34)+(B7-11),(A-34)+(B7-12),
(A-34)+(B7-13),(A-34)+(B7-14),(A-34)+(B7-15),(A-34)+(B7-16),
(A-34)+(B7-17),(A-34)+(B7-18),(A-34)+(B7-19),(A-34)+(B7-20),
(A-34)+(B7-21),(A-34)+(B7-22),(A-34)+(B7-23),(A-34)+(B7-24),
(A-34)+(B7-25),(A-34)+(B7-26),(A-34)+(B7-27),(A-34)+(B7-28),
(A-34)+(B7-29),(A-34)+(B7-30),(A-34)+(B-31),(A-34)+(B7-32),
(A-34)+(B7-33),(A-34)+(B7-34),(A-34)+(B7-35),(A-34)+(B7-36),
(A-34)+(B7-37),(A-34)+(B7-38),(A-34)+(B7-39),(A-34)+(B8-1),
(A-34)+(B8-2),(A-34)+(B8-3),(A-34)+(B9-1),(A-34)+(B9-2),(A-34)+(B9-3),
(A-34)+(B9-4),(A-34)+(B9-5),(A-34)+(B9-6),(A-34)+(B9-7).
(A-35)+(B1-1),(A-35)+(B1-2),(A-35)+(B1-3),(A-35)+(B1-4),(A-35)+(B1-5),
(A-35)+(B1-6),(A-35)+(B1-7),(A-35)+(B1-8),(A-35)+(B2-1),(A-35)+(B2-2),
(A-35)+(B3-1),(A-35)+(B3-2),(A-35)+(B3-3),(A-35)+(B3-4),(A-35)+(B3-5),
(A-35)+(B3-6),(A-35)+(B-3-7),(A-35)+(B3-8),(A-35)+(B3-9),(A-35)+(B4-1),
(A-35)+(B4-2),(A-35)+(B4-3),(A-35)+(B4-4),(A-35)+(B4-5),(A-35)+(B4-6),
(A-35)+(B4-7),(A-35)+(B4-8),(A-35)+(B4-9),(A-35)+(B4-10),(A-35)+(B4-11),
(A-35)+(B5-1),(A-35)+(B5-2),(A-35)+(B5-3),(A-35)+(B5-4),(A-35)+(B5-5),
(A-35)+(B5-6),(A-35)+(B5-7),(A-35)+(B6-1),(A-35)+(B6-2),(A-35)+(B6-3),
(A-35)+(B6-4),(A-35)+(B6-5),(A-35)+(B6-6),(A-35)+(B6-7),(A-35)+(B6-8),
(A-35)+(B6-9),(A-35)+(B6-10),(A-35)+(B6-11),(A-35)+(B6-12),
(A-35)+(B6-13),(A-35)+(B6-14),(A-35)+(B7-1),(A-35)+(B7-2),(A-35)+(B7-3),
(A-35)+(B7-4),(A-35)+(B7-5),(A-35)+(B7-6),(A-35)+(B7-7),(A-35)+(B7-8),
(A-35)+(B7-9),(A-35)+(B7-10),(A-35)+(B7-11),(A-35)+(B7-12),
(A-35)+(B7-13),(A-35)+(B7-14),(A-35)+(B7-15),(A-35)+(B7-16),
(A-35)+(B7-17),(A-35)+(B7-18),(A-35)+(B7-19),(A-35)+(B7-20),
(A-35)+(B7-21),(A-35)+(B7-22),(A-35)+(B7-23),(A-35)+(B7-24),
(A-35)+(B7-25),(A-35)+(B7-26),(A-35)+(B7-27),(A-35)+(B7-28),
(A-35)+(B7-29),(A-35)+(B7-30),(A-35)+(B-31),(A-35)+(B7-32),
(A-35)+(B7-33),(A-35)+(B7-34),(A-35)+(B7-35),(A-35)+(B7-36),
(A-35)+(B7-37),(A-35)+(B7-38),(A-35)+(B7-39),(A-35)+(B8-1),
(A-35)+(B8-2),(A-35)+(B8-3),(A-35)+(B9-1),(A-35)+(B9-2),(A-35)+(B9-3),
(A-35)+(B9-4),(A-35)+(B9-5),(A-35)+(B9-6),(A-35)+(B9-7).
本发明的除草剂结合物还可以包括各种农业化学活性化合物,例如安全剂、杀菌剂、杀虫剂、结构不同于除草剂(A)和(B)的除草剂以及植物生长调节剂,或者作物保护中常用的制剂助剂和添加剂。
因此,其他适合的除草剂为,例如下述结构不同于除草剂(A)和(B)的除草剂,优选其作用为基于对以下酶或生物合成的抑制的除草剂活性化合物,所述酶或生物合成例如乙酰乳酸合酶、乙酰辅酶A羧化酶、PSI、PS II、HPPDO、八氢番茄红素去饱和酶、初卟啉原氧化酶、谷氨酰胺合成酶、纤维素生物合成、5-烯醇丙酮酰莽草酸-3-磷酸合酶,例如在下述文献中所述:Weed Research 26,441-445(1986);“The PesticideManual”,第13版,The British Crop Protection Council,2003或2006/2007第14版;由the British Crop Protection Council出版的相应“e-Pesticide Manual”第四版(2006)(下文中简称为“PM”);以及其中所引用的文献。在互联网上的“杀虫剂通用名纲要(The compendium ofPesticide Common Names)”中也可找到通用名列表。从所述文献中获知的可结合2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺和通式(I)化合物的除草剂为例如下列活性化合物:(注:除草剂可使用国际标准化组织(ISO)的“通用名”或使用化学名,如果适合的话还可以一起使用常用代号,并且除非在上下文中另有说明,否则在每种情况下均包含所有的使用形式,例如酸、盐、酯和异构体,例如立体异构体和旋光异构体,特别是商品化形式。磺酰胺如磺酰脲还包括通过将磺酰胺基团处的氢原子交换为阳离子而形成的盐。本文中,提到一种使用形式并且在某些情况下提到两种或多种使用形式):
苯并噻二唑(acibenzolar-S-methyl);三氟羧草醚(acifluorfen(-sodium));苯草醚(aclonifen);AD-67;AKH 7088,即[[[1-[5-[2-氯-4-(三氟甲基)苯氧基]-2-硝基苯基]-2-甲氧基亚乙基]氨基]氧基]乙酸和[[[1-[5-[2-氯-4-(三氟甲基)苯氧基]-2-硝基苯基]-2-甲氧基亚乙基]氨基]氧基]乙酸甲酯;禾草灭(alloxydim(-sodium));莠灭净(ametryn);氨唑草酮(amicarbazone),先甲草胺(amidochlor),氯氨吡啶酸(aminopyralid);杀草强(amitrol);壬酸铵;AMS,即氨基磺酸铵;环丙嘧啶醇(ancimidol);莎稗磷(anilofos);莠去津(atrazine);艾维激素(aviglycine);唑啶草酮(azafenidin),叠氮津(aziprotryn);燕麦灵(barban);BAS 516H,即5-氟-2-苯基-4H-3,1-苯并噁嗪-4-酮;草除灵(benazolin(-ethyl));bencarbazone;乙丁氟灵(benfluralin);呋草黄(benfuresate);地散磷(bensulide);灭草松(bentazone);双苯嘧草酮(benzfendizone);双环磺草酮(benzobicyclon),吡草酮(benzofenap);氟磺胺草(benzofluor);新燕灵(benzoylprop(-ethyl));苯噻隆(benzthiazuron);双丙氨酰膦(bilanaphos);甲羧除草醚(bifenox);双草醚(bispyribac(-sodium))(KIH-2023);四硼酸钠(borax);除草定(bromacil);溴酚肟(bromofenoxim);溴苯腈(bromoxynil);bromuron;特克草(buminafos);羟草酮(busoxinone);氟丙嘧草酯(butafenacil);抑草磷(butamifos);丁烯草胺(butenachlor)(KH-218);特咪唑草(buthidazole);仲丁灵(butralin);丁苯草酮(butroxydim);唑草胺(cafenstrole)(CH-900);醌肟草(caloxydim);唑草酯(carfentrazone(-ethyl));儿茶素(catechin);CDAA,即2-氯-N,N-二-2-丙烯基乙酰胺;CDEC,即二乙基二硫代氨基甲酸2-氯烯丙酯;磺草酮(chlormesulon);甲氧除草醚(chlomethoxyfen);草灭畏(chloramben);chlorazifop-butyl;氯溴隆(chlorbromuron);氯炔灵(chlorbufam);伐草克(chlorfenac);燕麦酯(chlorfenprop);氯甲丹(chlorflurecol(-methyl));整形素(chlorflurenol(-methyl));氯草敏(chloridazon);矮壮素(chlormequat(chloride));草枯醚(chlornitrofen);chlorophthalim(MK-616);绿麦隆(chlorotoluron);枯草隆(chloroxuron);氯酞酸甲酯(chlorthal-dimethyl);氯硫酰草胺(chlorthiamid);绿麦隆(chlortoluron);和吲哚酮草酯(cinidon(-methyl、-ethyl));环庚草醚(cinmethylin);环苯草酮(clefoxydim);烯草酮(clethodim);炔草酸(clodinafop)及其酯衍生物(例如clodinafop-propargyl);杀雄嗪酸(clofencet);异恶草松(clomazone);氯甲酰草胺(clomeprop);调果酸(cloprop);环己烯草酮(cloproxydim);二氯吡啶酸(clopyralid);氯酯磺草酸(clopyrasulfuron(-methyl));苄草隆(cumyluron)(JC 940);氰胺(cyanamide);氰草津(cyanazine);噻草酮(cycloxydim);环莠隆(cycluron);cyhalofop及其酯衍生物(例如丁基酯,DEH-112);莎草快(cyperquat);环丙津(cyprazine);环唑草胺(cyprazole);杀草隆(daimuron);2,4-D;2,4-DB;茅草枯(dalapon);丁酰肼(daminozide);棉隆(dazomet);正癸醇;敌草净(desmetryn);燕麦敌(di-allate);麦草畏(dicamba);敌草腈(dichlobenil);烯丙酰草胺(dichlormid);2,4-滴丙酸(精2,4-滴丙酸)(dichlorprop(-P))盐;禾草灵(diclofop)及其酯,例如禾草灵(diclofop-methyl);diclofop-P(-methyl);乙酰甲草胺(diethatyl(-ethyl));枯莠隆(difenoxuron);野燕枯(difenzoquat(metilsulfate));氟吡草腙(钠)(diflufenzopyr(-sodium));恶唑隆(dimefuron);异戊乙净(dimethametryn);异恶草松(dimethazone);二甲胂酸(dimethylarsinic acid);噻节因(dimethipin);dimetrasulfuron;dimexyflam;氨氟灵(dinitramine);地乐酚(dinoseb);特乐酚(dinoterb);异丙净(dipropetryn);敌草快(diquat)盐;氟硫草定(dithiopyr);敌草隆(diuron);DNOC;草止津(eglinazine-ethyl);EL 77,即5-氰基-1-(1,1-二甲基乙基)-N-甲基-1H-吡唑-4-甲酰胺;茵多酸(endothal);epoprodan;乙丁烯氟灵(ethalfluralin);乙烯利(ethephon);磺噻隆(ethidimuron);乙嗪草酮(ethiozin);乙氧呋草黄(ethofumesate);ethoxyfen及其酯(例如其乙酯,HN-252);F5231,即N-[2-氯-4-氟-5-[4-(3氟丙基)-4,5-二氢-5-氧代-1H-四唑-1-基]苯基]乙烷磺酰胺;解草唑(fenchlorazole(-ethyl));解草啶(fenclorim);2,4,5-涕丙酸(fenoprop);fenoxan、恶唑禾草灵(fenoxaprop)和精恶唑禾草灵(fenoxaprop-P)及其酯,例如精恶唑禾草灵(fenoxaprop-P-ethyl)和恶唑禾草灵(fenoxaprop-ethyl);fenoxydim;四唑酰草胺(fentrazamide);非草隆(fenuron);硫酸亚铁;麦草氟甲酯(flamprop-methyl)或麦草氟异丙酯(flamprop-isopropyl)或flamprop-isopropyl-L;麦草氟(flamprop-M(-methyl or-isopropyl));floazulate(JV-485);吡氟合草灵(fluazifop)和精吡氟合草灵(fluazifop-P)及其酯,例如吡氟合草灵(fluazifop-butyl)和精吡氟合草灵(fluazifop-P-butyl);异丙吡草酯(fluazolate);氯乙氟灵(fluchloralin);氟哒嗪草酯(flufenpyr(-ethyl));氟节胺(flumetralin);伏草隆(flumeturon);酰亚胺苯氧乙酸(戊酯)(flumiclorac(-pentyl));丙炔氟草胺(flumioxazin)(S-482);flumipropyn;氟草隆(fluometuron);氟咯草酮(fluorochloridone);三氟硝草醚(fluorodifen);乙羧氟草醚(fluoroglycofen(-ethyl));氟胺草唑(flupoxam)(KNW-739);flupropacil(UBIC-4243);flupropanoate;芴丁酯(flurenol(-butyl));氟啶草酮(fluridone);flurochloridone;氟草烟(氟氯胺啶)((fluroxypyr(-meptyl));呋嘧醇(flurprimidol);呋草酮(flurtamone);氟噻乙草酯(fluthiacet(-methyl))(KIH-9201);噻唑草酰胺(fluthiamide);氟草肟(fluxofenim);氟磺胺草醚(fomesafen);氯吡脲(forchlorfenuron);杀木膦(fosamine);呋氧草醚(foryloxyfen);赤霉素(gibberillic acid);草铵膦(glufosinate(-ammonium));草甘膦(异丙胺盐)(glyphosate(-isopropylammonium));氟硝磺酰胺(halosafen);氟吡禾灵(haloxyfop)及其酯;精氟吡禾灵(haloxyfop-P(=R-haloxyfop))及其酯;HC-252;环嗪酮(hexazinone);咪草酸(imazamethabenz(-methyl));甲氧咪草烟(imazamox);imazapic;咪唑烟酸(imazapyr);咪唑喹啉酸(imazaquin)及其盐,例如其铵盐;咪唑乙烟酸(imazethapyr);抗倒胺(inabenfide);茚草酮(indanofan);碘苯腈(ioxynil);丁脒酰胺(isocarbamid);异丙乐灵(isopropalin);异丙隆(isoproturon);异恶隆(isouron);异恶酰草胺(isoxaben);异恶氯草酮(isoxachlortole);异恶唑草酮(isoxaflutole);异恶草醚(isoxapyrifop);特胺灵(karbutilate);乳氟禾草灵(lactofen);环草定(lenacil);利谷隆(linuron);抑芽丹(maleic hydrazide)(MH);MBTA;MCPA;MCPB;2甲4氯丙酸(精2甲4氯丙酸)(mecoprop(-P));mepiquat(chloride);甲基磺草酮(mesotrione);威百亩(metam);恶唑酰草胺(metamifop);苯嗪草酮(metamitron);甲基苯噻隆(methabenzthiazuron);威百亩(metham);灭草唑(methazole);苯草酮(methoxyphenone);甲基胂酸;甲基环丙烯;甲基杀草隆(methyldymron);异硫氰酸甲酯;甲基苯噻隆;吡喃隆(metobenzuron);溴谷隆(metobromuron);甲氧隆(metoxuron);嗪草酮(metribuzin);庚酰草胺(monalide);甲酰胺硫酸盐(monocarbamidedihydrogensulfate);绿谷隆(monolinuron);灭草隆(monuron);MT 128,即6-氯-N-(3-氯-2-丙烯基)-5-甲基-N-苯基-3-哒嗪胺;萘丙胺(naproanilide);NC 310,即4-(2,4-二氯苯甲酰基)-1-甲基-5-苄氧基吡唑;草不隆(neburon);氟氯草胺(nipyraclofen);甲磺乐灵(nitralin);除草醚(nitrofen);硝基酚盐混合物;硝氟草醚(nitrofluorfen);壬酸;氟草敏(norflurazon);解草腈(oxabetrinil);氨磺乐灵(oryzalin);丙炔恶草酮(oxadiargyl)(RP-020630);恶草酮(oxadiazon);恶嗪草酮(oxaziclomefone);乙氧氟草醚(oxyfluorfen);亚异砜磷(paclobutrazol);百草枯(二氯盐)(paraquat(dichloride));壬酸;二甲戊灵(pendimethalin);五氯酚;环戊恶草酮(pentoxazone);黄草伏(perfluidone);棉胺宁(phenisopham);氨氯吡啶酸(picloram);唑啉草酯(pinoxaden);哌草磷(piperophos);稗草畏(piributicarb);pirifenop-butyl;烯丙苯噻唑(probenazole);丙苯磺隆钠(procarbazone-(sodium));环丙氰津(procyazine);氨氟乐灵(prodiamine);环丙氟灵(profluralin);环苯草酮(profoxydim);调环酸(prohexadione(-calcium));茉莉酮(prohydrojasmon);甘扑津(proglinazine(-ethyl));扑灭通(prometon);扑草净(prometryn);恶草酸(propaquizafop)及其酯;扑灭津(propazine);磺亚胺草(prosulfalin);丙炔草胺(prynachlor);双唑草腈(pyraclonil);吡草醚(pyraflufen(-ethyl))(ET-751);pyrasulfotole;吡唑特(pyrazolynate);杀草敏(pyrazon);苄草唑(pyrazoxyfen);异丙酯草醚(pyribambenz-isopropyl)(ZJ 0702);pyrimbambenz-propyl(ZJ 0273);嘧啶肟草醚(pyribenzoxim);pyridafol;哒草特(pyridate);环酯草醚(pyriftalid);嘧草醚(pyriminobac(-methyl))(KIH-6127);pyrimisulfan(KIH-5996);嘧草硫醚(pyrlthiobac(-sodium))(KIH-2031);pyroxasulfone(KIH-485);pyroxofop及其酯(例如其炔丙基酯);二氯喹啉酸(quinclorac);氯甲喹啉酸(quinmerac);灭藻醌(quinoclamine);quinofop及其酯衍生物、喹禾灵(quizalofop)和精喹禾灵(quizalofop-P)及其酯衍生物,例如喹禾灵(quizalofop-ethyl);精喹禾灵(quizalofop-P-tefuryl、quizalofop-P-ethyl);renriduron;S275,即2-[4-氯-2-氟-5-(2-丙炔氧基)苯基]-4,5,6,7-四氢-2H-吲唑;仲丁通(secbumeton);烯禾啶(sethoxydim);环草隆(siduron);西玛津(simazine);西草净(simetryn);杀雄啉(sintofen);SN 106279,即2-[[7-[2-氯-4-(三氟甲基)苯氧基]-2-萘基]氧基]丙酸和2-[[7-[2-氯-4-(三氟甲基)苯氧基]-2-萘基]氧基]丙酸甲酯;磺草酮(sulcotrione);甲磺草胺(sulfentrazone)(FMC-97285,F-6285);sulfazuron;草硫膦(sulfosate)(ICI-A0224);三氯乙酸(钠)(TCA(-sodium));牧草胺(tebutam)(GCP-5544);丁噻隆(tebuthiuron);tecnacene;tefuryltrione;tembotrione;得杀草(tepraloxydim);特草定(terbacil);特草灵(terbucarb);特丁草胺(terbuchlor);特丁通(terbumeton);特丁津(terbuthylazine);特丁净(terbutryn);TFH 450,即N,N-二乙基-3-[(2-乙基-6-甲基苯基)磺酰基]-1H-1,2,4-t三唑-1-甲酰胺;thiafluamide,噻氟隆(thiazafluron);噻唑烟酸(thiazopyr)(Mon-13200);噻二唑草胺(thidiazimin)(SN-24085);噻苯隆(thidiazuron);Ti35;仲草丹(tiocarbazil);topramezone;三甲苯草酮(tralkoxydim);三嗪氟草胺(triaziflam);triazofenamide;三氯吡氧乙酸(triclopyr);灭草环(tridiphane);草达津(trietazine);氟乐灵(trifluralin);三甲隆(trimeturon);抗倒酯(trinexapac);tsitodef;烯效唑(uniconazole);WL 110547,即5-苯氧基-1-[3-(三氟甲基)苯基]-1H-四唑;D-489;ET-751;KIH-218;KIH-485;KIH-509;KPP-300;LS 82-556;NC-324;DPX-N8189;SC-0774;DOWCO-535;DK-8910;V-53482;PP-600;MBH-001;SYN-523;IDH-100;SYP-249;HOK-201;IR-6396;MTB-951;NC-620。
特别值得注意的是对有益植物作物和观赏植物中的有害植物的选择性防治。尽管已经证明除草剂(A)和(B)基本上在大多数作物中具有非常好以至于令人满意的选择性,但是在一些作物中,特别是在与其他选择性较差的除草剂混合使用的情况下,可能会对作物产生植物毒性。在这一方面,除草剂(A)和(B)的结合物中含有根据本发明结合的除草剂活性化合物和一种或多种安全剂就特别值得注意。以解毒有效量使用的安全剂可降低所采用的除草剂/杀虫剂的植物毒性副作用,例如在重要的经济作物中,如谷类(小麦、大麦、黑麦、玉米、水稻、黍类)、甜菜、甘蔗、油菜、棉花和大豆中,优选谷类。
所述安全剂优选地选自:
A)式(S-I)的化合物
其中的符号和标注具有下述含义:
nA为0-5的自然数,优选0-3的自然数;
RA 1为卤素、(C1-C4)-烷基、(C1-C4)-烷氧基、硝基或(C1-C4)-卤代烷基;
WA为未取代或取代的二价杂环基团,其选自部分不饱和的或芳香族的具有1至3个为N或O的杂环原子的五元杂环,所述环上存在至少一个氮原子和最多一个氧原子,优选地为选自下列(WA 1)至(WA 4)的基团:
mA为0或1;
RA 2为ORA 3、SRA 3或NRA 3RA 4或饱和或不饱和的具有至少一个氮原子和最多3个杂原子的3元至7元杂环,所述杂原子优选地选自O和S,所述杂环通过氮原子与(S-I)中的羰基连接,并且可为未取代的或被选自(C1-C4)-烷基、(C1-C4)-烷氧基和任选取代的苯基的基团所取代,RA 2优选地为式ORA 3、NHRA 4的基团或N(CH3)2,特别是式ORA 3的基团;
RA 3为氢或未取代的或取代的优选共具有1至18个碳原子的脂族烃基;
RA 4为氢、(C1-C6)-烷基、(C1-C6)-烷氧基或取代的或未取代的苯基;
RA 5为H、(C1-C8)-烷基、(C1-C8)-卤代烷基、(C1-C4)-烷氧基-(C1-C8)-烷基、氰基或COORA 9,其中RA 9为氢、(C1-C8)-烷基、(C1-C8)-卤代烷基、(C1-C4)-烷氧基-(C1-C4)-烷基、(C1-C6)-羟基烷基、(C3-C12)-环烷基或三(C1-C4)-烷基甲硅烷基;
RA 6、RA 7、RA 8可以相同或不同,为氢、(C1-C8)-烷基、(C1-C8)-卤代烷基、(C3-C12)-环烷基或取代的或未取代的苯基;
其中优选的化合物为:
a)二氯苯基吡唑啉-3-羧酸类化合物,优选的化合物例如1-(2,4-二氯苯基)-5-(乙氧基羰基)-5-甲基-2-吡唑啉-3-羧酸乙酯(S1-1)(“吡唑解草酯(mefenpyr-diethyl”,见Pestic.Man.)及相关化合物,记载于WO91/07874中;
b)二氯苯基吡唑羧酸的衍生物,优选的化合物例如:1-(2,4-二氯苯基)-5-甲基吡唑-3-羧酸乙酯(S1-2)、1-(2,4-二氯苯基)-5-异丙基吡唑-3-羧酸乙酯(S1-3)、1-(2,4-二氯苯基)-5-(1,1-二甲基乙基)吡唑-3-羧酸乙酯(S1-4)、1-(2,4-二氯苯基)-5-苯基吡唑-3-羧酸乙酯(S1-5)及相关化合物,记载于EP-A-333 131和EP-A-269 806中;
c)三唑羧酸类化合物,优选的化合物例如解草唑(fenchlorazole(-ethyl)),即1-(2,4-二氯苯基)-5-三氯甲基-(1H)-1,2,4-三唑-3-羧酸乙酯(S1-6)及相关化合物,记载于EP-A-174 562和EP-A-346 620中;
d)5-苯甲基-2-异噁唑啉-3-羧酸或5-苯基-2-异噁唑啉-3-羧酸或5,5-二苯基-2-异噁唑啉-3-羧酸类的化合物,优选的化合物例如:5-(2,4-二氯苯甲基)-2-异噁唑啉-3-羧酸乙酯(S1-7)或5-苯基-2-异噁唑啉-3-羧酸乙酯(S1-8)及相关化合物,记载于WO 91/08202中;或5,5-二苯基-2-异噁唑啉羧酸乙酯(S1-9)(“双苯噁唑酸(isoxadifen-ethyl)”)或5,5-二苯基-2-异噁唑啉羧酸正丙酯(S1-10)或5-(4-氟苯基)-5-苯基-2-异噁唑啉-3-羧酸乙酯(S1-11),记载于专利申请WO-A-95/07897中。
B)式(S-II)的喹啉衍生物
其中的符号和标记具有下述含义:
RB 1为卤素、(C1-C4)-烷基、(C1-C4)-烷氧基、硝基或(C1-C4)-卤代烷基;
nB为0至5的自然数、优选地为0至3的自然数;
RB 2为ORB 3、SRB 3或NRB 3RB 4或饱和或不饱和的具有至少一个氮原子和最多3个杂原子的3元至7元杂环,所述杂原子优选地选自O和S,所述杂环通过氮原子与(S-II)中的羰基连接,并且可为未取代的或被选自(C1-C4)-烷基、(C1-C4)-烷氧基和任选地取代的苯基的基团所取代,RB 2优选地为式ORB 3、NHRB 4的基团或N(CH3)2,特别是式ORB 3的基团;
RB 3为氢或未取代的或取代的优选共具有1至18个碳原子的脂族烃基;
RB 4为氢、(C1-C6)-烷基、(C1-C6)-烷氧基或取代的或未取代的苯基;
TB为(C1-或C2)-亚烷基,其可为未取代的或被一个或两个(C1-C4)-烷基基团取代或被[(C1-C3)-烷氧基]羰基取代;
其中优选的化合物为:
a)8-喹啉氧乙酸类的化合物(S2)、优选(5-氯-8-喹啉氧基)乙酸1-甲基己酯(通用名为“解毒喹(cloquintocet-mexyl)”),(S2-1)(见Pestic.Man.),
(5-氯-8-喹啉氧基)乙酸1,3-二甲基丁-1-酯(S2-2),
(5-氯-8-喹啉氧基)乙酸4-烯丙氧基丁酯(S2-3),
(5-氯-8-喹啉氧基)乙酸1-烯丙氧基丙-2-酯(S2-4),
(5-氯-8-喹啉氧基)乙酸乙酯(S2-5),
(5-氯-8-喹啉氧基)乙酸甲酯(S2-6),
(5-氯-8-喹啉氧基)乙酸烯丙酯(S2-7),
(5-氯-8-喹啉氧基)乙酸2-(2-亚丙基亚氨基氧基)-1-乙酯(S2-8)、(5-氯-8-喹啉氧基)乙酸2-氧丙-1-酯(S2-9)及其相关化合物,记载于EP-A-86 750、EP-A-94 349和EP-A-191 736或EP-A-0 492 366中,以及它们的水合物和盐,记载于WO-A-2002/034048中。
b)(5-氯-8-喹啉氧基)丙二酸类的化合物、优选的化合物例如:(5-氯-8-喹啉氧基)丙二酸二乙酯、(5-氯-8喹啉氧基)丙二酸二烯丙酯、(5-氯-8-喹啉氧基)丙二酸甲乙酯及相关化合物,记载于EP-A-0 582 198中。
C)式(S-III)的化合物
其中的符号和标记具有下述含义:
RC 1为(C1-C4)-烷基、(C1-C4)-卤代烷基、(C2-C4)-烯基、(C2-C4)-卤代烯基、(C3-C7)-环烷基,优选地为二氯甲基;
RC 2、RC 3可以相同或不同,分别为氢、(C1-C4)-烷基、(C2-C4)-烯基、(C2-C4)-炔基、(C1-C4)-卤代烷基、(C2-C4)-卤代烯基、(C1-C4)-烷基氨基甲酰基-(C1-C4)-烷基、(C2-C4)-烯基氨基甲酰基-(C1-C4)-烷基、(C1-C4)-烷氧基-(C1-C4)-烷基、二氧戊环基-(C1-C4)-烷基、噻唑基、呋喃基、呋喃基烷基、噻吩基、哌啶基、取代的或未取代的苯基;或者RC 2和RC 3一起形成一个取代的或未取代的杂环,优选地为噁唑烷、噻唑烷、哌啶、吗啉、六氢嘧啶环或苯并噁嗪;
其中优选的化合物为:
常用作出苗前安全剂(土壤作用安全剂)的二氯乙酰胺类活性化合物,例如:
“烯丙酰草胺(dichlormid)”(见Pestic.Man.)(=N,N-二烯丙基-2,2-二氯乙酰胺),
“R-29148”(=3-二氯乙酰基-2,2,5-三甲基-1,3-噁唑烷,Stauffer公司生产),
“R-28725”(=3-二氯乙酰基-2,2,-二甲基-1,3-噁唑烷,Stauffer公司生产),
“解草酮(benoxacor)”(见Pestic.Man.)(=4-二氯乙酰基-3,4-二氢-3-甲基-2H-1,4-苯并噁嗪),
“PPG-1292”(=N-烯丙基-N-[(1,3-二氧戊环-2-基)甲基]二氯乙酰胺,PPG Industries公司生产),
“DKA-24”(=N-烯丙基-N-[(烯丙基氨基羰基)甲基]二氯乙酰胺,Sagro-Chem公司生产),
“AD-67”或“MON 4660”(=3-二氯乙酰基-1-氧杂-3-氮杂-螺[4,5]癸烷,由Nitrokemia或Monsanto公司生产),
“TI-35”(=1-二氯乙酰基氮杂环庚烷,TRI Chemical RT公司生产),
“diclonon”(dicyclonone)或“BAS145138”或“LAB145138”(=3-二氯乙酰基-2,5,5-三甲基-1,3-二氮杂二环[4.3.0]壬烷,BASF公司生产)以及
“解草噁唑(furilazole)”或“MON 13900”(见Pestic.Man.)(=(RS)-3-二氯乙酰基-5-(2-呋喃基)-2,2-二甲基噁唑烷)。
D)式(S-IV)的N-酰基磺酰胺类化合物及其盐
其中
XD为CH或N;
RD 1为CO-NRD 5RD 6或NHCO-RD 7;
RD 2为卤素、(C1-C4)-卤代烷基、(C1-C4)-卤代烷氧基、硝基、(C1-C4)-烷基、(C1-C4)-烷氧基、(C1-C4)-烷基磺酰基、(C1-C4)-烷氧基羰基或(C1-C4)-烷基羰基;
RD 3为氢、(C1-C4)-烷基、(C2-C4)-烯基或(C2-C4)-炔基;
RD 4为卤素、硝基、(C1-C4)-烷基、(C1-C4)-卤代烷基、(C1-C4)-卤代烷氧基、(C3-C6)-环烷基、苯基、(C1-C4)-烷氧基、氰基、(C1-C4)-烷基硫基、(C1-C4)-烷基亚磺酰基、(C1-C4)-烷基磺酰基、(C1-C4)-烷氧基羰基或(C1-C4)-烷基羰基;
RD 5为氢、(C1-C6)-烷基、(C3-C6)-环烷基、(C2-C6)-烯基、(C2-C6)-炔基、(C5-C6)-环烯基、苯基或含有vD个杂原子的3元至6元杂环基,所述杂原子选自氮、氧和硫,其中最后提及的七个基团被选自下列的vD个取代基所取代:卤素、(C1-C6)-烷氧基、(C1-C6)-卤代烷氧基、(C1-C2)-烷基亚磺酰基、(C1-C2)-烷基磺酰基、(C3-C6)-环烷基、(C1-C4)-烷氧基羰基、(C1-C4)-烷基羰基和苯基,并且对于环状基团所述取代基还可为(C1-C4)-烷基和(C1-C4)-卤代烷基;
RD 6为氢、(C1-C6)-烷基、(C2-C6)-烯基或(C2-C6)-炔基、其中最后提及的三个基团被选自下列的vD个取代基所取代:卤素、羟基、(C1-C4)-烷基、(C1C4)-烷氧基和(C1-C4)-烷基硫基,或者
RD 5和RD 6与携带它们的氮原子一起形成一个吡咯烷基或哌啶基;
RD 7为氢、(C1-C4)-烷基氨基、二-(C1-C4)-烷基氨基、(C1-C6)-烷基、(C3-C6)-环烷基、其中最后提及的2个基团被选自下列的vD个取代基所取代:卤素、(C1-C4)-烷氧基、卤素-(C1-C6)-烷氧基和(C1-C4)-烷基硫基,并且对于环状基团所述取代基还可为(C1-C4)-烷基和(C1-C4)-卤代烷基;
nD为0、1或2;
mD为1或2;
vD为0、1、2或3;
在上述化合物中,优选N-酰基磺酰胺类化合物,例如下式(S-V)的化合物,该化合物可从例如WO 97/45016中知晓,
其中
RD 7为(C1-C6)-烷基、(C3-C6)-环烷基、其中最后提及的两个基团被选自下列的vD取代基所取代:卤素、(C1-C4)-烷氧基、卤素-(C1-C6)-烷氧基和(C1-C4)-烷基硫基,对于环状基团所述取代基还可为(C1-C4)-烷基和(C1-C4)-卤代烷基;
RD 4为卤素、(C1-C4)-烷基、(C1-C4)-烷氧基、CF3;
mD为1或2;
vD为0、1、2或3;
还有
酰基氨磺酰基苯甲酰胺,例如下式(S-VI)的化合物,该化合物可从例如WO 99/16744中知晓,
例如下列化合物,其中
RD 5=环丙基且(RD 4)=2-OMe(“cyprosulfamide”,S3-1),
RD 5=环丙基且(RD 4)=5-Cl-2-OMe(S3-2),
RD 5=乙基且(RD 4)=2-OMe(S3-3),
RD 5=异丙基且(RD 4)=5-Cl-2-OMe(S3-4),以及
RD 5=异丙基且(RD 4)=2-OMe(S3-5);
还有
式(S-VII)的N-酰基氨磺酰基苯基脲类化合物,该化合物可从例如EP-A-365484中知晓,
其中
RD 8和RD 9彼此独立地为氢、(C1-C8)-烷基、(C3-C8)-环烷基、(C3-C6)-烯基、(C3-C6)-炔基,
RD 4为卤素、(C1-C4)-烷基、(C1-C4)-烷氧基、CF3;
mD为1或2;
其中特别地可以提及:
1-[4-(N-2-甲氧基苯甲酰基氨磺酰基)苯基]-3-甲基脲,
1-[4-(N-2-甲氧基苯甲酰基氨磺酰基)苯基]-3,3-二甲基脲,
1-[4-(N-4,5-二甲基苯甲酰基氨磺酰基)苯基]-3-甲基脲,
1-[4-(N-萘甲酰基氨磺酰基)苯基]-3,3-二甲基脲;
G)羟基芳香族化合物和芳香族-脂族羧酸衍生物类的活性化合物,例如:3,4,5-三乙酰氧基苯甲酸乙酯、3,5-二甲氧基-4-羟基苯甲酸、3,5-二羟基苯甲酸、4-羟基水杨酸、4-氟水杨酸、1,2-二氢-2-氧-6-三氟甲基吡啶-3-甲酰胺、2-羟基肉桂酸、2,4-二氯肉桂酸,上述化合物记载于WO 2004084631、WO 2005015994、WO 2006007981、WO 2005016001;
H)1,2-二氢喹喔啉-2-酮类的活性化合物,例如:1-甲基-3-(2-噻吩基)-1,2-二氢喹喔啉-2-酮、1-甲基-3-(2-噻吩基)-1,2-二氢喹喔啉-2-硫酮、1-(2-氨基乙基)-3-(2-噻吩基)-1,2-二氢喹喔啉-2-酮盐酸盐、1-(2-甲基磺酰基氨基乙基)-3-(2-噻吩基)-1,2-二氢-喹喔啉-2-酮,上述化合物记载于WO 2005112630,
I)不仅对有害植物具有除草活性、同时还对作物植物(例如水稻)具有安全剂作用的活性化合物,例如:
“哌草丹”或“MY-93”(见Pestic.Man.)(=哌啶-1-硫代羧酸S-1-甲基-1-苯基乙酯),已知该化合物能够作为安全剂,用于防止水稻受到除草剂禾草敌的损害,
“杀草隆”或“SK 23”(见Pestic.Man.)(=1-(1-甲基-1-苯基乙基)-3-对甲苯基脲),已知该化合物能够作为安全剂,用于防止水稻受到除草剂唑吡嘧磺隆(imazosulfuron)的损害,
“苄草隆”=“JC-940”(=3-(2-氯苯基甲基)-1-(1-甲基-1-苯基-乙基)脲,见JP-A-60087254),已知该化合物能够作为安全剂,用于防止水稻受到多种除草剂的损害,
“苯草酮”或“NK 049”(=3,3’-二甲基-4-甲氧基二苯甲酮),已知该化合物能够作为安全剂,用于防止水稻受到多种除草剂的损害,
“CSB”(=1-溴-4-(氯甲基磺酰基)苯)(CAS Reg.No.54091-06-4,由Kumiai生产),已知该化合物能够作为安全剂,用于防止水稻受到多种除草剂的损害;
K)式(S-IX)的化合物,记载于WO-A-1998/38856,
其中的符号和标记具有下述含义:
RK 1、RK 2彼此独立地为卤素、(C1-C4)-烷基、(C1-C4)-烷氧基、(C1-C4)-卤代烷基、(C1-C4)-烷基氨基、二-(C1-C4)-烷基氨基、硝基;
AK为COORK 3或COORK 4
RK 3、RK 4彼此独立地为氢、(C1-C4)-烷基、(C2-C6)-烯基、(C2-C4)-炔基、氰基烷基、(C1-C4)-卤代烷基、苯基、硝基苯基、苯甲基、卤代苯甲基、吡啶基烷基或烷基铵,
nK 1为0或1,
nK 2、nK 3彼此独立地为0、1或2,
其中优选的化合物为:(二苯基甲氧基)乙酸甲酯(CAS Reg.No.:41858-19-9),
L)式(S-X)的化合物或其盐,记载于WO A-98/27049,
其中的符号和标记具有下述含义:
XL为CH或N,
nL当X=N时,nL为0至4的整数;当X=CH时,nL为0至5的整数;
RL 1为卤素、(C1-C4)-烷基、(C1-C4)-卤代烷基、(C1-C4)-烷氧基、(C1-C4)-卤代烷氧基、硝基、(C1-C4)-烷基硫基、(C1-C4)-烷基磺酰基、(C1-C4)-烷氧基羰基、任选取代的苯基、任选取代的苯氧基,
RL 2为氢或(C1-C4)-烷基,
RL 3为氢、(C1-C8)-烷基、(C2-C4)-烯基、(C2-C4)-炔基或芳基、其中上述每一个含碳基团可为未取代的或被一个或多个(优选地最多3个)选自卤素和烷氧基的基团所取代。
M)3-(5-四唑基羰基)-2-喹诺酮(quinolone)类的活性化合物,例如:
1,2-二氢-4-羟基-1-乙基-3-(5-四唑基羰基)-2-喹诺酮(CAS Reg.No.:219479-18-2)、1,2-二氢-4-羟基-1-甲基-3-(5-四唑基羰基)-2-喹诺酮(CASReg.No.:95855-00-8),上述化合物记载于WO-A-1999000020,
N)式(S-XI)或(S-XII)的化合物,记载于WO-A-2007023719和WO-A-2007023764,
其中
RN 1为卤素、(C1-C4)-烷基、甲氧基、硝基、氰基、CF3、OCF3,
Y、Z彼此独立地为O或S,
nN为0至4之间的整数,
RN 2为(C1-C16)-烷基、(C2-C6)-烯基、(C3-C6)-环烷基、芳基、苯甲基、卤代苯甲基,
RN 3为氢、(C1-C6)烷基,
O)选自下列的一种或多种化合物:
1,8-萘二甲酸酐,
S-2-乙基硫乙基二硫代磷酸O,O-二乙酯(二硫松(disulfoton)),
甲基氨基甲酸4-氯苯酯(mephenate),
O-苯基硫代磷酸O,O-二乙酯(dietholate),
4-羧基-3,4-二氢-2H-1-苯并吡喃-4-乙酸(CL-304415、CAS Reg.No.:31541-57-8),
1-氧杂-4-氮杂螺[4.5]癸烷-4-二硫代羧酸2-丙烯酯(MG-838、CASReg.No.:133993-74-5),
[(3-氧-1H-2-苯并硫代噻喃-4(3H)-亚基)甲氧基]乙酸甲酯(记载于WO-A-98/13361;CAS Reg.No.:205121-04-6),
氰基甲氧基亚氨基(苯基)乙腈(解草胺腈(cyometrinil)),
1,3-二氧戊环-2-基甲氧基亚氨基(苯基)乙腈(解草腈(oxabetrinil)),
4’-氯-2,2,2-三氟乙酰苯O-1,3-二氧戊环-2-基甲基肟(肟草安(fluxofenim)),
4,6-二氯-2-苯基嘧啶(解草啶(fenclorim)),
2-氯-4-三氟甲基-1,3-噻唑-5-羧酸苯甲酯(解草安(flurazole)),
2-二氯甲基-2-甲基-1,3-二氧戊环(MG-191),
包括它们在农业中常用的立体异构体和盐。
也可以与其他已知的活性化合物相混合,例如杀真菌剂、杀昆虫剂、杀螨剂、杀线虫剂、驱鸟剂、植物营养剂和土壤结构改进剂。
一些安全剂也已知可作为除草剂,因此,它们不但对有害植物具有除草活性,还能够保护作物植物。
除草剂(混合物)与安全剂的重量比通常取决于所述除草剂的施用率和所使用的安全剂的效力,并可在宽范围内变化,例如其范围为200∶1至1∶200、优选地为100∶1至1∶100、特别是20∶1至1∶20。与式(I)的化合物或其混合物类似,所述安全剂也可以与其他除草剂/杀虫剂配制为制剂,并以即用制剂或以与除草剂的桶混物的形式提供和使用。本发明的结合物(=除草剂组合物)针对宽范围的具有经济学重要性的单子叶和双子叶有害植物如杂草——包括对除草剂活性化合物(例如草甘膦、草铵膦、莠去津或咪唑啉酮除草剂)具有抗性的种——具有优良的除草剂活性。所述活性化合物还可有效作用于由根茎、根状茎或其他多年生器官发芽的并且难以防治的多年生杂草。本文中,可以采用播种前法、出苗前法或出苗后法施用所述物质,例如联合施用或分别施用。优选地,例如采用出苗后法施用,特别是用于出苗的有害植物。
可提及的具体实例为一些可用本发明的化合物防治的代表性单子叶和双子叶杂草植物群,但不应被限制于某些种。
所述除草剂组合物可有效作用于其上的杂草种的实例为,在单子叶杂草种中,一年生的燕麦属(Avena spp.)、看麦娘属(Alopecurus spp.)、Apera spp.、臂形草属(Brachiaria spp.)、雀麦属(Bromus spp.)、马唐属(Digitaria spp.)、黑麦草属(Lolium spp.)、稗属(Echinochloa spp.)、黍属(Panicum spp.)、虉草属(Phalaris spp.)、早熟禾属(Poa spp.)、狗尾草属(Setaria spp.),以及莎草属(Cyperus spp.);以及多年生种的冰草属(Agropyron spp.)、狗牙根属(Cynodon spp.)、白茅属(Imperata spp.)和高粱属(Sorghum spp.),还有多年生的莎草属。
对于双子叶杂草种,作用范围扩展至例如以下属:一年生杂草,白麻属(Abutilon spp.)、苋属(Amaranthus spp.)、藜属(Chenopodium spp.)、菊花属(Chrysanthemum spp.)、拉拉藤属(Galium spp.)、番薯属(Ipomoea spp.)、地肤属(Kochia spp.)、野芝麻属(Lamium spp.)、母菊属(Matricaria spp.)、牵牛属(Pharbitis spp.)、蓼属(Polygonum spp.)、黄花稔属(Sida spp.)、白芥属(Sinapis spp.)、茄属(Solanum spp.)、繁缕属(Stellaria spp.)、婆婆纳属(Veronica spp.)和堇菜属(Viola spp.)、苍耳属(Xanthium spp.);和多年生杂草,旋花属(Convolvulus spp.)、蓟属(Cirsiumspp.)、酸模属(Rumex spp.)和苦艾属(Artemisia spp.)。
如果在萌芽前将本发明的化合物施用至土壤表面,可以完全阻止杂草种子的出苗,或者使得杂草种子生长至子叶期,但之后停止生长,从而最终在三至四周后完全死亡。
如果在出苗后将所述活性化合物施用至植物的绿色部分,植物也会在处理后的极短时间内骤然停止生长,并且所述杂草植物会停留在施用时间点时的生长阶段或者在一段时间后完全死亡,这样就使得在非常早的时期和以持续的方式除去了与作物植物竞争并对作物植物有害的杂草。
本发明的除草剂组合物具有快速开始和长效的除草剂作用。通常,本发明结合物中的活性化合物有利地具有耐雨水冲刷能力。一个特别的优势是可以将所述结合物的使用剂量以及化合物(A)和(B)的有效剂量调整至这样一个低水平,即它们的土壤作用理想地较低。首先,这不仅使它们可以用于敏感性作物,而且可以基本上避免地下水污染。本发明活性化合物的结合物使得所述活性化合物的所需施用率被极大地降低。
当(A)组的除草剂与(B)组的除草剂结合施用时,优选地存在超加和性(=协同)作用。本文中,所述结合物的活性高于所用各个除草剂活性的预期之和。所述协同作用使得可以降低施用率、防治宽谱的阔叶杂草和杂草、除草作用开始得更快、持续时间更长、仅一次或数次施用即可更好的防治有害植物,以及施用周期变宽。通过使用所述组合物,在某种程度上也降低了有害成分(例如氮或油酸)的量以及将它们引入土壤中的量。
上述特性和优势是保持农业作物和林业作物中不含不想要的竞争植物的杂草防治实践所必需的,并且因此可以从质量和产量的角度确保和/或增加产量水平。这些新的结合物由于所述特性方面而明显超越本领域中的技术现状。
特别关注的是使用包括下述除草活性化合物的除草组合物:(A)+(B);(A)+(B)+(C)(在结构上与(A)和(B)不同的除草活性化合物,均以其“通用名”或组(B)中所列代码示出);和/或除草组合物与安全剂(S),其含有下列化合物组成(A)+(B)+(C)+(S):
(A-0)+(B7-17)+(B7-16);(A-2)+(B7-17)+(B7-16);
(A-0)+(B7-17)+(B7-16)+(S1-1);(A-2)+(B7-17)+(B7-16)+(S1-1);
(A-0)+(B7-1)+(B7-16);(A-2)+(B7-1)+(B7-16);
(A-0)+(B7-1)+(B7-16)+(S1-1);(A-2)+(B7-1)+(B7-16)+(S1-1);
(A-0)+(B7-1)+(B3-1);(A-2)+(B7-1)+(B3-1);
(A-0)+(B7-1)+(B3-1)+(S1-1);(A-2)+(B7-1)+(B3-1)+(S1-1);
(A-0)+(B7-17)+(B3-1);(A-2)+(B7-17)+(B3-1);
(A-0)+(B7-17)+(B3-1)+(S1-1);(A-2)+(B7-17)+(B3-1)+(S1-1);
(A-0)+(B7-16)+(B3-1);(A-2)+(B7-16)+(B3-1);
(A-0)+(B7-16)+(B3-1)+(S1-1);(A-2)+(B7-16)+(B3-1)+(S1-1);
(A-0)+(B7-1)+(B9-5);(A-2)+(B7-1)+(B9-5);
(A-0)+(B7-1)+(B9-5)+(S1-1);(A-2)+(B7-1)+(B9-5)+(S1-1);
(A-0)+(B7-1)+(pyrasulfutole);(A-2)+(B7-1)+(pyrasulfutole);
(A-0)+(B7-1)+(pyrasulfutole)+(S1-1);(A-2)+(B7-1)+(pyrasulfutole)+(S1-1)。
由于所述组合物具有除草活性和植物生长调节特性,它们可被用于防治已知植物作物或者待开发出的耐受或基因修饰作物中的有害植物。除对本发明的组合物的抗性外,转基因植物通常还具有一些特别有利的性质,例如对于某些植物疾病或导致植物疾病的生物的抗性,所述导致植物疾病的生物例如某些昆虫或微生物,例如真菌、细菌或病毒。其他特别的性质与例如收获产物的数量、质量、储存性、组成或特殊成分相关。因此,已知一些具有提高的淀粉含量或改变的淀粉质量的转基因植物,或者收获的产物中具有不同的脂肪酸组成的转基因植物。类似地,由于所述活性化合物具有除草活性和植物生长调节活性,它们可被用于防治已知植物作物或仍待通过突变筛选开发出的植物作物中的有害植物。
产生与目前已有植物相比具有改变的特性的新植物的常规方法包括例如常规育种方法和产生突变体的方法。或者可以借助于重组方法产生具有改变的特性的新植物(参见例如,EP-A-0221044、EP-A-0131624)。例如,已有一些申请描述了下列一些方法:
-通过重组技术修饰作物植物以改变植物中的淀粉合成(例如WO 92/11376、WO 92/14827、WO 91/19806);
-对除草剂例如磺酰脲类除草剂(EP-A-0257993、US-A-5013659)具有抗性的转基因作物植物;
-能够产生苏云金杆菌毒素(Bacillus thuringiensis toxin,Bt毒素)的转基因作物植物,其使植物对某些害虫具有抗性(EP-A-0142924、EP-A-0193259);
-具有改变的脂肪酸组成的转基因作物植物(WO 91/13972)。
原理上已知多种分子生物学技术可以用于产生具有改进性质的新转基因植物,可参见例如:Sambrook et al.,1989,Molecular Cloning,ALaboratory Manual,2nd ed.Cold Spring Harbor Laboratory Press,ColdSpring Harbor,NY;或Winnacker“Gene und Klone”[Genes andClones],VCH Weinheim,2nd edition 1996;或Christou,“Trends in PlantScience”1(1996)423-431)。
为了进行这类重组操作,可以将核酸分子导入质粒,所述核酸分子能够通过DNA序列的重组而产生诱变或序列突变。例如,使用上述标准方法能够置换碱基、移除部分序列或加入天然的或合成的序列。为了将DNA片段彼此连接,可以在片段上添加接头或连接子。
例如,基因产物活性降低的植物细胞可以通过下列方法制备:通过表达至少一种对应的反义RNA和正义RNA来实现共抑制效应,或者通过表达至少一种能够特异性切割上述基因产物的转录物并且具有适宜结构的核酶。
为此目的,可以使用含有所述基因产物的完整编码序列(包括所有可能存在的侧翼序列)的DNA分子,也可以使用仅含有部分编码序列的DNA分子,但是所述部分序列必须足够长,以便在细胞中产生反义效果。也可以使用与所述基因产物的编码序列具有高度同源性但并不完全相同的DNA序列。
当在植物中表达核酸分子时,所合成的蛋白可位于所述植物细胞的任何所需区室中。然而,为了将其定位于某一特定区室中,可以例如将编码区与能够保证定位于某一特定区室的DNA序列相连接。这种序列是本领域中技术人员已知的(参见例如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)。
可以使用已知的技术使转基因植物细胞再生为完整的植物。原则上,所述转基因植物可为任何所需植物品种的植物,即既可为单子叶植物,也可为双子叶植物。因此,可以获得通过对同源(即天然)基因或基因序列的过表达、抑制或阻止,或者通过表达异源(即外源)基因或基因序列而特性改变的转基因植物。
本发明还提供了一种——优选地在作物植物中——防治不想要的植物的方法,包括将本发明的除草剂结合物的除草剂(A)和(B)例如一起或单独地施用于植物(例如有害植物,如单子叶或双子叶杂草或不想要的作物植物)、种子(例如谷粒、种子或植物繁殖器官,如块茎或带芽的新枝部分)或者植物生长的区域(例如栽培区域)。可以将一种或多种除草剂(A)在除草剂(B)之前、之后或与之同时施用于植物、种子或植物生长的区域(例如栽培区域)。
应理解,不想要的植物是指所有在不想要其生长的地方生长的植物。这可以为例如,有害植物(例如单子叶或双子叶杂草或者不想要的作物植物),包括例如那些对某些除草剂活性化合物(如草甘膦、莠去津、草铵膦或咪唑啉酮除草剂)具有抗性的植物。
本发明的除草剂结合物可用于选择性防治不想要的植物,例如于作物植物如农作物中,例如单子叶农作物如谷类(例如小麦、大麦、黑麦、燕麦)、水稻、玉米、黍类,或者双子叶农作物如甜菜、油菜、棉花、向日葵;和豆科植物,例如大豆属(Glycine)(例如大豆(Glycine max.,soybean)如非转基因大豆(例如常规品种,如STS品种),或者转基因大豆(例如RR-大豆或LL-大豆),以及它们的杂种)、菜豆属(Phaseolus)、豌豆属(Pisum)、蚕豆属(Vicia)和花生属(Arachis);或者不同植物属的蔬菜作物,如马铃薯、韭葱、甘蓝、胡萝卜、西红柿、洋葱。优选地,施用针对出苗的有害植物(例如杂草或不想要的作物植物)进行,特别是在(想要的)作物植物出苗之前。
本发明还提供了本发明的除草剂结合物用于防治不想要植物的用途,优选在作物植物中。
本发明的除草剂结合物可通过已知方法制备,为例如单独组分的混合制剂形式,如果适合的话还含其他活性化合物、添加剂和/或常规制剂助剂,然后所述结合物以用水稀释的常规方式施用;或者以桶混物的形式施用,所述桶混物是通过用水将单独配制或部分单独配制的各组分共同稀释。还可以分开施用所述单独配制或部分单独配制的单个组分。
还可以分成多个部分的形式施用(序贯施用)所述除草剂或除草剂结合物,例如出苗前使用,然后是出苗后使用;或者出苗后早期施用,然后是出苗后中或晚期施用。优选将所研究的结合物的各活性化合物联合施用或几乎同时施用。
除草剂(A)和(B)可被共同转化或单独转化为常规制剂,如溶液、乳液、悬液、粉末、泡沫、糊剂、颗粒、气溶胶、浸渍有活性化合物的天然及合成材料,以及聚合材料的微胶囊。所述制剂可包括常规助剂和添加剂。
这些制剂可通过已知的方式来生产,例如通过将所述活性化合物与填充剂(即液体溶剂、加压液化空气和/或固体载体)混合,合适地使用表面活性剂(即乳化剂和/或分散剂和/或发泡剂)。
如果所用的填充剂为水,则还可能使用例如有机溶剂作为辅助溶剂。适合的液体溶剂主要有:芳族化合物,例如二甲苯、甲苯、烷基萘、氯代芳族化合物或氯代脂族烃,例如氯苯、氯乙烯或二氯甲烷;脂族烃,例如环己烷或石蜡,如矿物油级分、矿物油和植物油;醇类,例如丁醇或二醇,以及它们的醚和酯;酮类,例如丙酮、甲乙酮、甲基异丁基酮或环己酮;强极性溶剂,例如二甲基甲酰胺或二甲基亚砜;以及水。
适合的固体载体为:例如铵盐和压碎的天然矿物(例如高岭土、粘土、滑石、白垩、石英、绿坡缕石、蒙脱石或硅藻土)和压碎的合成材料(例如细分的二氧化硅、氧化铝和硅酸盐);适合用于颗粒剂的固体载体为:例如,粉碎的并分级的天然岩石(例如方解石、大理石、浮石、海泡石和白云石),以及合成的无机和有机粉颗粒,以及有机材料(例如锯屑、椰子壳、玉米棒子和烟秆)的颗粒;适合的乳化剂和/或发泡剂为:例如非离子和阴离子乳化剂(如聚氧乙烯脂肪酸醚、聚氧乙烯脂肪醇酯,例如烷基芳基聚乙二醇醚、烷基磺酸盐、烷基硫酸盐、芳基磺酸盐),以及蛋白质水解产物;适合的分散剂为:例如木素亚硫酸盐废液和甲基纤维素。
所述制剂中可以使用增粘剂,例如羧甲基纤维素和粉末、颗粒或胶乳形式的天然和合成聚合物(例如阿拉伯胶、聚乙烯醇和聚乙酸乙烯酯),以及天然磷脂(例如脑磷脂和卵磷脂)和合成磷脂。其他可能的添加剂为矿物油和植物油。
可以使用例如表面活性剂(优选地为脂肪醇聚乙二醇醚类的润湿剂)来改进本发明的除草剂结合物的除草活性。所述脂肪醇聚乙二醇醚类优选地在其脂肪醇基团中含有10-18个碳原子,在其聚乙二醇醚部分中含有2-20个环氧乙烷单元。所述脂肪醇聚乙二醇醚类可以为非离子型或离子型的形式,例如可以使用脂肪醇聚乙二醇醚硫酸盐的形式,所述硫酸盐例如可为碱金属盐(例如钠盐和钾盐)或铵盐,甚或可以为碱土金属盐例如镁盐,例如C12/C14-脂肪醇二甘醇醚硫酸钠(LRO,ClariantGmbH);参见例如EP-A-0476555、EP-A-0048436、EP-A-0336151或US-A-4,400,196以及Proc.EWRS Symp.“Factors Affecting HerbicidalActivity and Selectivity“,227-232(1988)。非离子型脂肪醇聚乙二醇醚类例如为含有例如2-20个、优选为3-15个环氧乙烷单元的(C10-C18)-、优选地为(C10-C14)-脂肪醇聚乙二醇醚类(例如异十三烷基醇聚乙二醇醚类),例如X系列产品,例如X-030、X-060、X-080或X-150(均产自Clariant GmbH公司)。
本发明还包括组分A和组分B与上述脂肪醇聚乙二醇醚类润湿剂联合的结合物,所述脂肪醇聚乙二醇醚类优选地在其脂肪醇基团中含有10-18个碳原子,在其聚乙二醇醚部分中含有2-20个环氧乙烷单元,所述脂肪醇聚乙二醇醚类可以为非离子型或离子型的形式(例如脂肪醇聚乙二醇醚硫酸盐的形式)。优选的脂肪醇聚乙二醇醚类为C12/C14-脂肪醇二甘醇醚硫酸钠(LRO,Clariant GmbH)和含有3-15个环氧乙烷单元的异十三烷基醇聚乙二醇醚,例如X系列产品,例如X-030、X-060、X-080或X-150(均产自Clariant GmbH公司)。此外,还已知脂肪醇聚乙二醇醚类例如非离子型或离子型脂肪醇聚乙二醇醚类(例如脂肪醇聚乙二醇醚硫酸盐)也适于用作多种其他除草剂的增透剂和活性增强剂(参见例如EP-A-0502014)。
此外,还已知脂肪醇聚乙二醇醚类例如非离子型或离子型脂肪醇聚乙二醇醚类(例如脂肪醇聚乙二醇醚硫酸盐)也适于用作多种其他除草剂的增透剂和活性增强剂(参见例如EP-A-0502014)。
还可以使用植物油来增强本发明的除草剂结合物的除草活性。术语“植物油”应被理解为产油植物的油,例如大豆油、油菜籽油、玉米油、葵花籽油、棉籽油、亚麻籽油、椰子油、棕榈油、蓟油或蓖麻油,特别是油菜籽油及其转酯化产物,例如烷基酯类,例如油菜籽油甲基酯或油菜籽油乙基酯。
所述植物油优选地为C10-C22-、优选地为C12-C20-脂肪酸的酯类。所述C10-C22-脂肪酸酯类例如为不饱和的或饱和的C10-C22-脂肪酸的酯类,特别是具有偶数个碳原子的脂肪酸的酯类,例如芥子酸、月桂酸、棕榈酸以及特别是C18-脂肪酸的酯类,例如硬脂酸、油酸、亚油酸或亚麻酸的酯类。
C10-C22-脂肪酸的酯类的实例为通过将甘油或乙二醇与例如产油植物中的油中所含有的C10-C22-脂肪酸反应而获得的酯类,或者为上述获得的C10-C22-脂肪酸甘油酯或乙二醇酯与C1-C20-醇类(例如甲醇、乙醇、丙醇或丁醇)进行转酯化反应而获得的C1-C20-烷基-C10-C22-脂肪酸酯类。所述转酯化反应可以通过已知方法进行,所述方法在例如ChemieLexikon,9th edition,Volume 2,page 1343,Thieme Verlag Stuttgart中有所描述。
优选的C1-C20-烷基-C10-C22-脂肪酸酯类为甲基酯类、乙基酯类、丙基酯类、丁基酯类、2-乙基己基酯类和十二烷基酯类。优选的C10-C22-脂肪酸甘油酯和乙二醇酯类为C10-C22-脂肪酸甘油酯和乙二醇酯的单一酯类或混合酯类,特别是具有偶数个碳原子的脂肪酸的酯类,例如芥子酸、月桂酸、棕榈酸以及特别是C18-脂肪酸的酯类,例如硬脂酸、油酸、亚油酸或亚麻酸的酯类。
在本发明的除草组合物中,所述植物油可以以例如市售的含油制剂添加剂的形式存在,特别是基于油菜籽油的添加剂,例如(Victorian Chemical Company,Australia,下文简称为Hasten;其主要成分为油菜籽油乙基酯)、B(Novance,France,下文简称为ActirobB;其主要成分为油菜籽油甲基酯)、Rako-(Bayer AG,Germany,下文简称为Rako-Binol;其主要成分为油菜籽油)、(Stefes,Germany,下文简称为Renol,其中植物油成分为油菜籽油甲基酯)或Stefes(Stefes,Germany,下文简称为Mero;其主要成分为油菜籽油甲基酯)。
在另一个实施方案中,本发明包括具有上述的植物油例如油菜籽油的结合物,所述植物油优选地以市售的含油制剂添加剂的形式存在,特别是基于油菜籽油的添加剂,例如(Victorian ChemicalCompany,Australia,下文简称为Hasten;其主要成分为油菜籽油乙基酯)、B(Novance,France,下文简称为ActirobB;其主要成分为油菜籽油甲基酯)、Rako-(Bayer AG,Germany,下文简称为Rako-Binol;其主要成分为油菜籽油)、(Stefes,Germany,下文简称为Renol,其中植物油成分为油菜籽油甲基酯)或Stefes(Stefes,Germany,下文简称为Mero;其主要成分为油菜籽油甲基酯)。
可使用着色剂,例如无机颜料(例如氧化铁、氧化钛和普鲁士蓝)和有机染料(例如茜素染料、偶氮染料和金属酞菁染料),以及微量营养素,例如铁盐、锰盐、硼盐、铜盐、钴盐、钼盐和锌盐。
所述制剂通常包括0.1-95重量%的活性化合物,优选0.5-90重量%。
除草剂(A)和(B)的本身或其制剂可以以与其他农业化学活性化合物(例如已知的除草剂)的混合物形式使用,用于防治不想要的植物,例如用于防治杂草或用于防治不想要的作物,例如可以为即用制剂或桶混合物的形式。
也可以与其他已知的活性化合物相混合,例如杀真菌剂、杀昆虫剂、杀螨剂、杀线虫剂、安全剂、驱鸟剂、植物营养剂和土壤结构改进剂。
除草剂(A)和(B)可以其本身形式使用,以其制剂形式使用或者以通过进一步稀释制备的使用形式使用,例如即用溶液、悬液、乳液、粉末、糊剂和颗粒。施用可以通过常规方式进行,例如通过浸水、喷雾、雾化或撒播进行。
可以将所述活性化合物施用于植物(例如有害植物,如单子叶或双子叶杂草或不想要的作物植物)、种子(例如谷粒、种子或植物繁殖器官,如块茎或带芽的新枝)或者栽培区域(例如土壤),优选用于植物的绿色植株和部分,并且如果适宜的话还有土壤。一个可能的使用方式是所述活性化合物以桶混合物形式联合施用,此时将单个活性化合物的经最优化配制的浓缩制剂在桶中与水混合在一起,并且施用所获得的喷雾液。
本发明的除草剂(A)和(B)的结合物的联合除草剂制剂的优势在于其易于施用,因为所述组分的量已经为最适的比例。此外,可以调整所述制剂中的助剂以使其彼此比例最优化。
生物实施例
1.出苗前除草作用
将单子叶和双子叶杂草植物的种子或根茎部分置于盛有沙质肥土的纸盆中,并用土壤覆盖。然后将可湿性粉末或乳油制剂形式的活性化合物(A)和(B)以水性悬液或乳液的形式以不同剂量施用至覆盖土的表面,水施用率为100至800升/公顷(换算值)。
在处理后,将盆置于温室中,并将温室条件保持为适于杂草生长的条件。在3至4周的测试期后,待测试植物出苗后,通过与未处理的对照比较,目测评估植物的受损程度或出苗的受损程度。结果显示,所述测试除草剂结合物对于宽范围的杂草和阔叶杂草都具有良好的出苗前除草活性。2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺与表A中所述式(I)的化合物和B组化合物的除草剂结合物在以每公顷100g活性物质或更低的施用率在出苗前施用时,对于例如以下有害植物具有极好的协同除草活性,所述有害植物例如白芥(Sinapis alba)、南茼蒿(Chrysanthemum segetum)、燕麦(Avena sativa)、繁缕(Stellariamedia)、稗草(Echinochloa crus-galli)、黑麦草(Lolium multiflorum)、狗尾草(Setaria viridis)、苘麻(Abutilon theophrasti)、反枝苋(Amaranthus retroflexus)和黍(Panicum miliaceum)。
2.出苗后抗杂草作用
将单子叶和双子叶杂草的种子或根茎部分置于盛有沙质肥土的塑料盆中,用土壤覆盖并置于温室中,在良好生长条件下生长。在播种三周后,对生长至二至四叶期的测试植物进行处理。将可湿性粉末或乳油制剂形式的本发明化合物以不同剂量喷洒至植物的绿色部分,水施用率100至800升水/公顷(换算值)。使测试植物处于最佳温室生长条件下放置10至28天后,通过与未处理的对照植物相比较,目测评估制剂的效果。
总体而言,本发明的除草剂结合物对于宽谱的具有经济学重要性的杂草和阔叶杂草都具有很好的出苗后除草活性。2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺与表A中所述式(I)的化合物和B组化合物的除草剂结合物在以每公顷100g活性物质或更低的施用率在出苗后施用时,对于例如以下有害植物具有极好的协同除草活性,所述有害植物例如白芥、稗草、马唐(Digitaria sanguinalis)、黑麦草、南茼蒿、狗尾草、卷茎蓼(Polygonum convolvulus)、苘麻、反枝苋、黍和燕麦。
示例性地,下表1示出了通过施用本发明的除草剂结合物改善了对杂草卷茎蓼的防治,使用的结合物为化合物A-2(2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺的钠盐)和选自组B的除草剂的结合物,下表1-1至1-15显示出对杂草卷茎蓼的改进的防治,所述组B的除草剂,即例如除草剂丙苯磺隆(=B8-2)、氟酮磺隆(=B8-1)、甲磺胺磺隆(=B7-17)、甲基噻烯卡巴腙(=B8-3)、甲酰氨磺隆(=B7-13)、碘甲磺隆钠盐(B7-16)、甲氧磺草胺(B9-7)、磺酰磺隆(B7-28)、噻吩磺隆(B7-29)、苯磺隆(B7-31)、三氟甲磺隆(B7-34)、甲磺隆(B7-18)、TH-547(B7-38)、双氟磺草胺(B9-3)和甜菜安(B5-5)。在喷洒施用后11天进行评估。在与B7-16(表1-15)的结合物的情况下,杂草为蓼属,评估在施用20天后进行。
杂草的防治根据以下方案进行评估。
0%=无防治
100%=完全防治
表1-1
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
A-2 | 2.5 | 10 |
B8-2 | 10 | 38 |
A-2+B8-2 | 2.5+10 | 83 |
表1-2
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
A-2 | 2.5 | 10 |
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
B8-1 | 10 | 55 |
A-2+B8-1 | 2.5+10 | 70 |
表1-3
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
A-2 | 2.5 | 10 |
B7-17 | 5 | 20 |
A-2+B7-17 | 2.5+5 | 73 |
表1-4
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
A-2 | 2.5 | 10 |
B8-3 | 1 | 50 |
A-2+B8-3 | 2.5+1 | 68 |
表1-5
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
A-2 | 2.5 | 10 |
B7-13 | 10 | 15 |
A-2+B7-13 | 2.5+10 | 75 |
表1-6
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
A-2 | 2.5 | 0 |
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
B9-7 | 2.5 | 75 |
A-2+B9-7 | 2.5+2.5 | 85 |
表1-7
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
A-2 | 2.5 | 0 |
B7-28 | 7.5 | 78 |
A-2+B7-28 | 2.5+7.5 | 85 |
表1-8
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
A-2 | 2.5 | 0 |
B7-29 | 7.5 | 87 |
A-2+B7-29 | 2.5+7.5 | 90 |
表1-9
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
A-2 | 2.5 | 0 |
B7-31 | 10 | 80 |
A-2+B7-31 | 2.5+10 | 83 |
表1-10
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
A-2 | 2.5 | 0 |
B7-34 | 10 | 58 |
A-2+B7-34 | 2.5+10 | 83 |
表1-11
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
A-2 | 2.5 | 0 |
B7-18 | 2.5 | 70 |
A-2+B7-18 | 2.5+2.5 | 85 |
表1-12
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
A-2 | 2.5 | 0 |
B7-38 | 30 | 0 |
A-2+B7-38 | 2.5+30 | 10 |
表1-13
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
A-2 | 2.5 | 0 |
B9-3 | 2.5 | 73 |
A-2+B9-3 | 2.5+2.5 | 78 |
表1-14
活性化合物 | 活性化合物的量,g ai/ha | 卷茎蓼的防治,以%计 |
A-2 | 2.5 | 0 |
B5-5 | 50 | 28 |
A-2+B5-5 | 2.5+50 | 68 |
表1-15
活性化合物 | 活性化合物的量,g ai/ha | 蓼属的防治,以%计 |
A-2 | 2.5 | 0 |
B7-16 | 2 | 73 |
A-2+B7-16 | 2.5+2 | 83 |
示例性地,下表2-1至2-4示出了通过施用本发明的除草剂结合物改善了对杂草阿拉伯婆婆纳(Veronica persica)的防治,使用的结合物为化合物A-2(2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺的钠盐)和选自组B的除草剂的结合物,所述组B除草剂,即例如除草剂酰嘧磺隆(=B7-1)、乙氧嘧磺隆(=B7-9)、氟酮磺隆(B8-1)和磺酰磺隆(B7-28)。
喷洒施用之后10天根据以下方案进行评估:
0%=无防治
100%=完全防治
表2-1
活性化合物 | 活性化合物的量,g ai/ha | 阿拉伯婆婆纳的防治,以%计 |
A-2 | 2.5 | 10 |
B7-1 | 5 | 0 |
A-2+B7-1 | 2.5+5 | 68 |
表2-2
活性化合物 | 活性化合物的量,g ai/ha | 阿拉伯婆婆纳的防治,以%计 |
A-2 | 2.5 | 10 |
活性化合物 | 活性化合物的量,g ai/ha | 阿拉伯婆婆纳的防治,以%计 |
B7-9 | 5 | 8 |
A-2+B7-9 | 2.5+5 | 53 |
表2-3
活性化合物 | 活性化合物的量,g ai/ha | 阿拉伯婆婆纳的防治,以%计 |
A-2 | 2.5 | 10 |
B8-1 | 10 | 15 |
A-2+B8-1 | 2.5+10 | 55 |
表2-4
活性化合物 | 活性化合物的量,g ai/ha | 阿拉伯婆婆纳的防治,以%计 |
A-2 | 2.5 | 0 |
B7-28 | 7.5 | 30 |
A-2+B7-28 | 2.5+7.5 | 38 |
Claims (8)
1.一种除草剂结合物,包括组分(A)和(B),其中
(A)为一种或多种选自以下的除草剂:2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺和通式(I)的化合物
其中
阳离子(M+)为:(a)碱金属离子,优选锂、钠或钾,或者
(b)碱土金属离子,优选钙或镁,或者
(c)过渡金属离子,优选锰、铜、锌或铁,或者
(d)铵离子,其中任选地一个、两个或三个或全部四个氢原子被选自以下的相同或不同基团所取代:(C1-C4)-烷基、羟基-(C1-C4)-烷基、(C3-C6)-环烷基、(C1-C4)-烷氧基-(C1-C4)-烷基、羟基-(C1-C4)-烷氧基-(C1-C4)-烷基、(C1-C6)-巯基烷基、苯基和苯甲基,其中上述基团任选地被选自以下的一个或多个相同或不同基团所取代:卤素如F、Cl、Br或I、硝基、氰基、叠氮基、(C1-C6)-烷基、(C1-C6)-卤代烷基、(C3-C6)-环烷基、(C1-C6)-烷氧基、(C1-C6)-卤代烷氧基和苯基,并且其中在每种情况下氮原子上的两个取代基一起任选地形成一个未取代的或取代的环,或者
(e)鏻离子,或者
(f)锍离子,优选三-((C1-C4)-烷基)锍,或者
(g)氧鎓离子,优选三-((C1-C4)-烷基)氧鎓,或者
(h)任选地为单环或稠环的和/或被(C1-C4)-烷基取代的饱和或不饱和/芳香族含氮杂环离子化合物,其在所述环系统中具有1-10个碳原子,
和
(B)一种或多种(磺)酰胺类除草剂,包括:
氟丁酰草胺、溴丁酰草胺、二甲吩草胺、二甲吩草胺-P、双苯酰草胺、敌草胺、烯草胺、MT-5950、萘草胺、炔苯酰草胺、吡氟酰草胺、乙氧苯草胺、氟噻草胺、苯噻酰草胺、氯磺酰草胺、甲氯酰草胺、氟吡酰草胺、敌稗、N-苯基邻氨甲酰苯甲酸、乙草胺、甲草胺、丁草胺、二甲草胺、吡唑草胺、异丙甲草胺、S-异丙甲草胺、丙草胺、毒草胺、异丙草胺、噻吩草胺、磺草灵、甲萘威、双酰草胺、氯苯胺灵、甜菜安、甜菜宁、苯胺灵、丁草敌、环草敌、哌草丹、茵草敌、戊草丹、磺菌威、禾草敌、坪草丹、克草敌、苄草丹、稗草丹、禾草丹、野燕畏、灭草敌、酰嘧磺隆、四唑嘧磺隆、苄嘧磺隆、氯嘧磺隆、氯磺隆、醚磺隆、环丙嘧磺隆、胺苯磺隆、乙氧嘧磺隆、啶嘧磺隆、氟吡磺隆、氟啶嘧磺隆、甲酰氨磺隆、氯吡嘧磺隆、唑吡嘧磺隆、碘甲磺隆钠盐、甲磺胺磺隆、甲磺隆、单嘧磺隆、烟嘧磺隆、嘧苯胺磺隆、环氧嘧磺隆、氟嘧磺隆、氟磺隆、吡嘧磺隆、砜嘧磺隆、甲嘧磺隆、磺酰磺隆、噻吩磺隆、醚苯磺隆、苯磺隆、三氟啶磺隆、氟胺磺隆、三氟甲磺隆、HNPC-C9908(2-[[[[[4-甲氧基-6-(甲硫基)-2-嘧啶基]氨基]羰基]氨基]磺酰基]苯甲酸甲酯)、NC-330、NC-620、TH-547、monosulfuron-methyl、氟酮磺隆、丙苯磺隆、甲基噻烯卡巴腙、氯酯磺草胺、双氯磺草胺、双氟磺草胺、唑嘧磺草胺、磺草唑胺、五氟磺草胺和甲氧磺草胺。
2.权利要求1的除草剂结合物,其中组分(A)为2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺和/或其中阳离子(M+)如下的通式(I)的化合物,
(a)碱金属离子,优选锂、钠或钾,或者
(b)碱土金属离子,优选钙或镁,或者
(c)过渡金属离子,优选锰、铜、锌或铁,或者
(d)铵离子,其中任选地一个、两个、三个或全部四个氢原子被选自以下的相同或不同基团所取代:(C1-C4)-烷基、羟基-(C1-C4)-烷基、(C3-C4)-环烷基、(C1-C2)-烷氧基-(C1-C2)-烷基、羟基-(C1-C2)-烷氧基-(C1-C2)-烷基、(C1-C2)-巯基烷基、苯基和苯甲基,其中上述基团任选地被选自以下的一个或多个相同或不同基团所取代:卤素如F、Cl、Br或I、硝基、氰基、叠氮基、(C1-C2)-烷基、(C1-C2)-卤代烷基、(C3-C4)-环烷基、(C1-C2)-烷氧基、(C1-C2)-卤代烷氧基和苯基,并且其中在每种情况下氮原子上的两个取代基一起任选地形成一个未取代的或取代的环,或者
(e)季鏻离子,优选四-((C1-C4)-烷基)鏻和四苯基鏻,其中所述(C1-C4)-烷基基团和苯基基团任选地被选自以下的相同或不同基团所单取代或多取代:卤素如F、Cl、Br或I、(C1-C2)-烷基,(C1-C2)-卤代烷基、(C3-C4)-环烷基、(C1-C2)-烷氧基和(C1-C2)-卤代烷氧基,或者
(f)叔锍离子,优选三-((C1-C4)-烷基)锍或三苯基锍,其中所述(C1-C4)-烷基基团和苯基基团任选地被选自以下的相同或不同基团所单取代或多取代:卤素如F、Cl、Br或I、(C1-C2)-烷基,(C1-C2)-卤代烷基、(C3-C4)-环烷基、(C1-C2)-烷氧基和(C1-C2)-卤代烷氧基,或者
(g)叔氧鎓离子,优选三-((C1-C4)-烷基)氧鎓,其中所述(C1-C4)-烷基基团和苯基基团任选地被选自以下的相同或不同基团所单取代或多取代:卤素如F、Cl、Br或I、(C1-C2)-烷基,(C1-C2)-卤代烷基、(C3-C4)-环烷基、(C1-C2)-烷氧基和(C1-C2)-卤代烷氧基,或者
(h)以下杂环化合物的阳离子,例如吡啶、喹啉、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、2,4-二甲基吡啶、2,5-二甲基吡啶、2,6-二甲基吡啶、5-乙基-2-二甲基吡啶、哌啶、吡咯烷、吗啉、硫吗啉、吡咯、咪唑、1,5-二氮杂双环[4.3.0]壬-5-烯(DBN)、1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)。
3.权利要求1的除草剂结合物,其包括2-碘-N-[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基甲酰基]苯磺酰胺和/或其中阳离子(M+)如下的通式(I)化合物作为组分(A):
钠离子、钾离子、锂离子、镁离子、钙离子、NH4 +离子、(2-羟基乙-1-基)铵离子、双-N,N-(2-羟基乙-1-基)铵离子、三-N,N,N-(2-羟基乙-1-基)铵离子、甲基铵离子、二甲基铵离子、三甲基铵离子、四甲基铵离子、乙基铵离子、二乙基铵离子、三乙基铵离子、四乙基铵离子、异丙基铵离子、二异丙基铵离子、四丙基铵离子、四丁基铵离子、2-(2-羟基乙-1-氧基)乙-1-基铵离子、二(2-羟基乙-1-基)铵离子、三甲基苯甲基铵离子、三-((C1-C4)-烷基)锍离子或三-((C1-C4)-烷基)氧鎓离子、苯甲基铵离子、1-苯基乙基铵离子、2-苯基乙基铵离子、二异丙基乙基铵离子、吡啶鎓离子、哌啶鎓离子、咪唑鎓离子、吗啉鎓离子、1,8-二氮杂双环[5.4.0]十一碳-7-烯鎓离子。
4.权利要求1-3中任一项要求保护的除草剂结合物,其含有一种或多种选自以下提及的化合物作为组分(B):
二甲吩草胺-P、敌草胺、吡氟酰草胺、氟噻草胺、苯噻酰草胺、乙草胺、吡唑草胺、S-异丙甲草胺、磺草灵、甜菜安、甜菜宁、禾草敌、苄草丹、酰嘧磺隆、乙氧嘧磺隆、甲酰氨磺隆、碘甲磺隆钠盐、甲磺胺磺隆、甲磺隆、磺酰磺隆、噻吩磺隆、苯磺隆、三氟甲磺隆、氟酮磺隆、丙苯磺隆、甲基噻烯卡巴腙、双氟磺草胺、磺草唑胺、甲氧磺草胺。
5.权利要求1至4任一项所述的除草剂结合物,包括有效量的组分(A)和(B)和/或一种或多种选自以下的其他组分:不同类型的农业化学活性化合物、作物保护中常用的制剂助剂和添加剂。
6.一种选择性防治不想要的植物的方法,包括将权利要求1-5中一项或多项所述的除草剂结合物的除草剂(A)和(B)一起或单独施用,优选地施用到所述植物生长的区域。
7.权利要求6的选择性防治不想要的植物的方法,利用出苗前法或出苗后法用在以下植物中:小麦(硬粒小麦和普通小麦)、玉米、大豆、甜菜、甘蔗、棉花、水稻、豆类、亚麻、大麦、燕麦、黑麦、小黑麦、油菜、马铃薯和黍类(高粱)、牧草地和青草/草坪区域。
8.权利要求1-5任一项所述的除草剂结合物用于选择性防治不想要的植物的用途。
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-
2007
- 2007-10-24 EP EP07020810A patent/EP2052606A1/de not_active Withdrawn
-
2008
- 2008-10-22 CN CN200880113301A patent/CN101835383A/zh active Pending
- 2008-10-22 US US12/738,777 patent/US20100248965A1/en not_active Abandoned
- 2008-10-22 CA CA2703581A patent/CA2703581A1/en not_active Abandoned
- 2008-10-22 MX MX2010004532A patent/MX2010004532A/es not_active Application Discontinuation
- 2008-10-22 WO PCT/EP2008/009031 patent/WO2009053095A2/de active Search and Examination
- 2008-10-22 EP EP08841028A patent/EP2205089A2/de not_active Withdrawn
- 2008-10-22 BR BRPI0818261-2A2A patent/BRPI0818261A2/pt not_active Application Discontinuation
- 2008-10-22 AU AU2008315645A patent/AU2008315645A1/en not_active Abandoned
- 2008-10-22 JP JP2010530346A patent/JP2011500747A/ja active Pending
- 2008-10-22 AR ARP080104597A patent/AR068958A1/es unknown
- 2008-10-22 EA EA201000523A patent/EA201000523A1/ru unknown
- 2008-10-24 CL CL2008003144A patent/CL2008003144A1/es unknown
-
2010
- 2010-04-13 ZA ZA2010/02565A patent/ZA201002565B/en unknown
- 2010-04-23 MA MA32790A patent/MA31789B1/fr unknown
- 2010-04-23 TN TN2010000183A patent/TN2010000183A1/fr unknown
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103719126A (zh) * | 2011-07-01 | 2014-04-16 | 陕西美邦农药有限公司 | 一种含氟丁酰草胺与磺酰脲类的除草组合物 |
CN103719126B (zh) * | 2011-07-01 | 2016-02-17 | 陕西美邦农药有限公司 | 一种含氟丁酰草胺与磺酰脲类的除草组合物 |
CN102302017A (zh) * | 2011-07-04 | 2012-01-04 | 陕西美邦农药有限公司 | 一种含氟丁酰草胺与唑嘧磺草胺的除草组合物 |
CN102302017B (zh) * | 2011-07-04 | 2013-11-27 | 陕西美邦农药有限公司 | 一种含氟丁酰草胺与唑嘧磺草胺的除草组合物 |
CN102326563A (zh) * | 2011-07-12 | 2012-01-25 | 陕西美邦农药有限公司 | 一种含吡氟酰草胺与唑嘧磺草胺的除草组合物 |
CN102326563B (zh) * | 2011-07-12 | 2013-10-09 | 陕西美邦农药有限公司 | 一种含吡氟酰草胺与唑嘧磺草胺的除草组合物 |
CN104206400A (zh) * | 2014-09-26 | 2014-12-17 | 青岛瀚生生物科技股份有限公司 | 甲酰氨基嘧磺隆和甲基碘磺隆钠盐复合除草剂 |
CN104206400B (zh) * | 2014-09-26 | 2015-10-07 | 青岛瀚生生物科技股份有限公司 | 甲酰氨基嘧磺隆和甲基碘磺隆钠盐复合除草剂 |
CN107372566A (zh) * | 2017-08-11 | 2017-11-24 | 北京科发伟业农药技术中心 | 一种含噻酮磺隆和iofensulfuron的除草组合物 |
Also Published As
Publication number | Publication date |
---|---|
WO2009053095A2 (de) | 2009-04-30 |
MX2010004532A (es) | 2010-06-30 |
BRPI0818261A2 (pt) | 2014-09-30 |
JP2011500747A (ja) | 2011-01-06 |
EP2052606A1 (de) | 2009-04-29 |
WO2009053095A3 (de) | 2010-05-20 |
MA31789B1 (fr) | 2010-10-01 |
EP2205089A2 (de) | 2010-07-14 |
US20100248965A1 (en) | 2010-09-30 |
ZA201002565B (en) | 2011-04-28 |
AU2008315645A1 (en) | 2009-04-30 |
TN2010000183A1 (en) | 2011-11-11 |
CL2008003144A1 (es) | 2009-03-06 |
CA2703581A1 (en) | 2009-04-30 |
EA201000523A1 (ru) | 2010-12-30 |
AR068958A1 (es) | 2009-12-16 |
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