CN116802177A - 二氨基三嗪化合物 - Google Patents
二氨基三嗪化合物 Download PDFInfo
- Publication number
- CN116802177A CN116802177A CN202280011877.3A CN202280011877A CN116802177A CN 116802177 A CN116802177 A CN 116802177A CN 202280011877 A CN202280011877 A CN 202280011877A CN 116802177 A CN116802177 A CN 116802177A
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- Prior art keywords
- methyl
- alkyl
- showed
- alkoxy
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- WEWFIUPOLKEEJP-UHFFFAOYSA-N triazine-4,6-diamine Chemical class NC1=CC(N)=NN=N1 WEWFIUPOLKEEJP-UHFFFAOYSA-N 0.000 title abstract description 64
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- 229910052736 halogen Inorganic materials 0.000 claims description 34
- 150000002367 halogens Chemical class 0.000 claims description 34
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 31
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- 125000000217 alkyl group Chemical group 0.000 claims description 17
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- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 15
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- NVGOPFQZYCNLDU-UHFFFAOYSA-N norflurazon Chemical compound O=C1C(Cl)=C(NC)C=NN1C1=CC=CC(C(F)(F)F)=C1 NVGOPFQZYCNLDU-UHFFFAOYSA-N 0.000 description 1
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- VZCCHPAEDSPPDG-UHFFFAOYSA-N pentyl 2-(2,4-dichlorophenoxy)acetate Chemical compound CCCCCOC(=O)COC1=CC=C(Cl)C=C1Cl VZCCHPAEDSPPDG-UHFFFAOYSA-N 0.000 description 1
- ALEKBMQVKFWMOR-UHFFFAOYSA-N pentyl 2-phenoxyacetate Chemical compound CCCCCOC(=O)COC1=CC=CC=C1 ALEKBMQVKFWMOR-UHFFFAOYSA-N 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- PWXJULSLLONQHY-UHFFFAOYSA-N phenylcarbamic acid Chemical class OC(=O)NC1=CC=CC=C1 PWXJULSLLONQHY-UHFFFAOYSA-N 0.000 description 1
- 150000008048 phenylpyrazoles Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 108010082527 phosphinothricin N-acetyltransferase Proteins 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000003032 phytopathogenic effect Effects 0.000 description 1
- IBBMAWULFFBRKK-UHFFFAOYSA-N picolinamide Chemical class NC(=O)C1=CC=CC=N1 IBBMAWULFFBRKK-UHFFFAOYSA-N 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000004483 piperidin-3-yl group Chemical group N1CC(CCC1)* 0.000 description 1
- 125000004482 piperidin-4-yl group Chemical group N1CCC(CC1)* 0.000 description 1
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- XSWHNYGMWWVAIE-UHFFFAOYSA-N pipradrol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1CCCCN1 XSWHNYGMWWVAIE-UHFFFAOYSA-N 0.000 description 1
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000004481 post-translational protein modification Effects 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- HKSBGIRAPYUOPP-UHFFFAOYSA-M potassium;2,6-dibromo-4-cyanophenolate Chemical compound [K+].[O-]C1=C(Br)C=C(C#N)C=C1Br HKSBGIRAPYUOPP-UHFFFAOYSA-M 0.000 description 1
- SIVJKMBJGCUUNS-UHFFFAOYSA-M potassium;2-(2,4-dichlorophenoxy)propanoate Chemical compound [K+].[O-]C(=O)C(C)OC1=CC=C(Cl)C=C1Cl SIVJKMBJGCUUNS-UHFFFAOYSA-M 0.000 description 1
- AFEOSTAENQJQJQ-UHFFFAOYSA-M potassium;2-chloropropanoate Chemical compound [K+].CC(Cl)C([O-])=O AFEOSTAENQJQJQ-UHFFFAOYSA-M 0.000 description 1
- RLQCYSVYYHHLIL-UHFFFAOYSA-M potassium;3,6-dichloropyridine-2-carboxylate Chemical compound [K+].[O-]C(=O)C1=NC(Cl)=CC=C1Cl RLQCYSVYYHHLIL-UHFFFAOYSA-M 0.000 description 1
- ZRHANBBTXQZFSP-UHFFFAOYSA-M potassium;4-amino-3,5,6-trichloropyridine-2-carboxylate Chemical compound [K+].NC1=C(Cl)C(Cl)=NC(C([O-])=O)=C1Cl ZRHANBBTXQZFSP-UHFFFAOYSA-M 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000013823 prenylation Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
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- ISEUFVQQFVOBCY-UHFFFAOYSA-N prometon Chemical compound COC1=NC(NC(C)C)=NC(NC(C)C)=N1 ISEUFVQQFVOBCY-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BOEYMHRHUPNCAQ-UHFFFAOYSA-N propan-2-yl 2-(4-chloro-2-methylphenoxy)acetate Chemical group CC(C)OC(=O)COC1=CC=C(Cl)C=C1C BOEYMHRHUPNCAQ-UHFFFAOYSA-N 0.000 description 1
- IKVXBIIHQGXQRQ-UHFFFAOYSA-N propan-2-yl 2-(n-benzoyl-3-chloro-4-fluoroanilino)propanoate Chemical group C=1C=C(F)C(Cl)=CC=1N(C(C)C(=O)OC(C)C)C(=O)C1=CC=CC=C1 IKVXBIIHQGXQRQ-UHFFFAOYSA-N 0.000 description 1
- FKLQIONHGSFYJY-UHFFFAOYSA-N propan-2-yl 5-[4-bromo-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-chloro-4-fluorobenzoate Chemical compound C1=C(Cl)C(C(=O)OC(C)C)=CC(C=2C(=C(N(C)N=2)C(F)(F)F)Br)=C1F FKLQIONHGSFYJY-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 108020001580 protein domains Proteins 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- FKERUJTUOYLBKB-UHFFFAOYSA-N pyrazoxyfen Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=O)C=1C(C)=NN(C)C=1OCC(=O)C1=CC=CC=C1 FKERUJTUOYLBKB-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- KWMWSMACCCIVRO-UHFFFAOYSA-N pyrimidin-2-yl benzoate Chemical class C=1C=CC=CC=1C(=O)OC1=NC=CC=N1 KWMWSMACCCIVRO-UHFFFAOYSA-N 0.000 description 1
- 150000008512 pyrimidinediones Chemical class 0.000 description 1
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical compound OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical class C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- ABOOPXYCKNFDNJ-SNVBAGLBSA-N quizalofop-P Chemical compound C1=CC(O[C@H](C)C(O)=O)=CC=C1OC1=CN=C(C=C(Cl)C=C2)C2=N1 ABOOPXYCKNFDNJ-SNVBAGLBSA-N 0.000 description 1
- BBKDWPHJZANJGB-IKJXHCRLSA-N quizalofop-P-tefuryl Chemical group O=C([C@H](OC=1C=CC(OC=2N=C3C=CC(Cl)=CC3=NC=2)=CC=1)C)OCC1CCCO1 BBKDWPHJZANJGB-IKJXHCRLSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 108020003175 receptors Proteins 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 239000003001 serine protease inhibitor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- RTWIRLHWLMNVCC-WQYNNSOESA-M sodium (2S)-2-[[(2S)-2-[[(2S)-2-amino-4-[hydroxy(methyl)phosphoryl]butanoyl]amino]propanoyl]amino]propanoate Chemical compound [Na+].[O-]C(=O)[C@H](C)NC(=O)[C@H](C)NC(=O)[C@@H](N)CCP(C)(O)=O RTWIRLHWLMNVCC-WQYNNSOESA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- RFOHRSIAXQACDB-UHFFFAOYSA-M sodium;2-(2,4-dichlorophenoxy)acetate Chemical compound [Na+].[O-]C(=O)COC1=CC=C(Cl)C=C1Cl RFOHRSIAXQACDB-UHFFFAOYSA-M 0.000 description 1
- XWAFIZUTHLRWBE-UHFFFAOYSA-M sodium;2-(2,4-dichlorophenoxy)propanoate Chemical compound [Na+].[O-]C(=O)C(C)OC1=CC=C(Cl)C=C1Cl XWAFIZUTHLRWBE-UHFFFAOYSA-M 0.000 description 1
- STAPBGVGYWCRTF-UHFFFAOYSA-M sodium;2-(4-chloro-2-methylphenoxy)acetate Chemical compound [Na+].CC1=CC(Cl)=CC=C1OCC([O-])=O STAPBGVGYWCRTF-UHFFFAOYSA-M 0.000 description 1
- DHJHUXNTNSRSEX-UHFFFAOYSA-M sodium;2-(4-chloro-2-methylphenoxy)propanoate Chemical compound [Na+].[O-]C(=O)C(C)OC1=CC=C(Cl)C=C1C DHJHUXNTNSRSEX-UHFFFAOYSA-M 0.000 description 1
- RPOHBMAQTOJHKM-UHFFFAOYSA-M sodium;2-chloropropanoate Chemical compound [Na+].CC(Cl)C([O-])=O RPOHBMAQTOJHKM-UHFFFAOYSA-M 0.000 description 1
- NZYOAGBNMCVQIV-UHFFFAOYSA-N sodium;chloro-(4-methylphenyl)sulfonylazanide;trihydrate Chemical compound O.O.O.[Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 NZYOAGBNMCVQIV-UHFFFAOYSA-N 0.000 description 1
- 239000004550 soluble concentrate Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000007103 stamina Effects 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000000021 stimulant Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- AHBGXTDRMVNFER-FCHARDOESA-L strontium-89(2+);dichloride Chemical compound [Cl-].[Cl-].[89Sr+2] AHBGXTDRMVNFER-FCHARDOESA-L 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- OORLZFUTLGXMEF-UHFFFAOYSA-N sulfentrazone Chemical compound O=C1N(C(F)F)C(C)=NN1C1=CC(NS(C)(=O)=O)=C(Cl)C=C1Cl OORLZFUTLGXMEF-UHFFFAOYSA-N 0.000 description 1
- ZDXMLEQEMNLCQG-UHFFFAOYSA-N sulfometuron methyl Chemical group COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(C)=CC(C)=N1 ZDXMLEQEMNLCQG-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 125000005537 sulfoxonium group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- BCQMBFHBDZVHKU-UHFFFAOYSA-N terbumeton Chemical compound CCNC1=NC(NC(C)(C)C)=NC(OC)=N1 BCQMBFHBDZVHKU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- LOQQVLXUKHKNIA-UHFFFAOYSA-N thifensulfuron Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C2=C(SC=C2)C(O)=O)=N1 LOQQVLXUKHKNIA-UHFFFAOYSA-N 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- 125000004014 thioethyl group Chemical group [H]SC([H])([H])C([H])([H])* 0.000 description 1
- 229960001196 thiotepa Drugs 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XOPFESVZMSQIKC-UHFFFAOYSA-N triasulfuron Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)OCCCl)=N1 XOPFESVZMSQIKC-UHFFFAOYSA-N 0.000 description 1
- BFGQTWYXWNCTSX-UHFFFAOYSA-N triazine-4,5-dione Chemical class O=C1C=NN=NC1=O BFGQTWYXWNCTSX-UHFFFAOYSA-N 0.000 description 1
- YWBFPKPWMSWWEA-UHFFFAOYSA-O triazolopyrimidine Chemical compound BrC1=CC=CC(C=2N=C3N=CN[N+]3=C(NCC=3C=CN=CC=3)C=2)=C1 YWBFPKPWMSWWEA-UHFFFAOYSA-O 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- KRTNITDCKAVIFI-UHFFFAOYSA-N tridecyl benzenesulfonate Chemical class CCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 KRTNITDCKAVIFI-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- AKTQJCBOGPBERP-UHFFFAOYSA-N triflusulfuron Chemical compound FC(F)(F)COC1=NC(N(C)C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2C)C(O)=O)=N1 AKTQJCBOGPBERP-UHFFFAOYSA-N 0.000 description 1
- NRZWQKGABZFFKE-UHFFFAOYSA-N trimethylsulfonium Chemical compound C[S+](C)C NRZWQKGABZFFKE-UHFFFAOYSA-N 0.000 description 1
- KVEQCVKVIFQSGC-UHFFFAOYSA-N tritosulfuron Chemical compound FC(F)(F)C1=NC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(F)(F)F)=N1 KVEQCVKVIFQSGC-UHFFFAOYSA-N 0.000 description 1
- 239000002753 trypsin inhibitor Substances 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 230000003612 virological effect Effects 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
- C07D251/18—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
- A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
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Abstract
本发明涉及二氨基三嗪化合物及其作为除草剂的用途。本发明还涉及用于作物保护的农业化学组合物和一种控制不希望的植物生长的方法。
Description
本发明涉及二氨基三嗪化合物及其作为除草剂的用途。本发明还涉及用于作物保护的农业化学组合物和一种控制不希望的植物生长的方法。
二氨基三嗪类及其作为除草剂的用途例如由WO 2015/155272和WO 2015/162166已知。
然而,例如对于已知除草化合物的活性、活性范围以及与有用植物的相容性仍然存在改进的余地。
因此,本发明的目的是要提供具有改进除草作用,尤其是在低施用率下具有良好除草剂活性的化合物。此外,除草剂应可与商业利用的农作物充分相容。
这些和其他目的由如下所定义的式(I)的二氨基三嗪化合物及其可农用盐实现。
因此,本发明涉及式(I)的二氨基三嗪化合物:
R1为Cl、Br、I、CR1A;
其中R1A为H或卤素;
R2选自H、卤素、CR2A;
其中R2A为H或卤素;
R3为H、卤素;
R4选自卤素、CR4A;
其中R4A为H或卤素;
R5选自H、卤素、CN、C1-C6烷基、(C1-C6烷氧基)-C1-C6烷基、C3-C6环烷基、(C3-C6环烷基)-C1-C4烷基、C1-C6烷氧基、C2-C6链烯氧基、C2-C6炔氧基、C3-C6环烷氧基、(C3-C6环烷基)-C1-C4烷氧基,其中所述基团的脂族和环脂族部分未被取代、部分或完全被卤化;
R6选自H、卤素、CN、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基和C1-C6卤代烷氧基;
R7选自卤素、CN、C1-C6烷基、C2-C6链烯基、C3-C6炔基、C3-C6环烷基、(C3-C6环烷基)-C1-C4烷基、C3-C6环烯基和C1-C6烷氧基-C1-C6烷基,其中所述基团的脂族和环脂族部分未被取代、部分或完全被卤化;
R6和R7与其所连接的碳原子一起形成选自羰基、C3-C6环烷基、C3-C6环烯基、3-6员饱和或部分不饱和的杂环基的结构部分,和结构部分>C=CRxRy,其中Rx和Ry为氢、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基或者CRxRy形成3-6员环烷基;
R8选自C1-C6烷基、C2-C6链烯基、C2-C6炔基、(C1-C6烷氧基)-C1-C6烷基、(C1-C6烷氧基)-C2-C6链烯基、(C1-C6烷氧基)-C2-C6炔基、(C1-C6环烷基)-C2-C6炔基、(C3-C6环烷基)-C1-C4烷基、(C3-C6环烷氧基)-C1-C4烷基,其中上述基团未被取代、部分或完全被卤化,并且其中后提到的6个基团的环脂族部分可以带有1、2、3、4、5或6个甲基,包括其可农用盐。
本发明还涉及包含至少一种式(I)的二氨基三嗪化合物和常用于配制作物保护剂的助剂的农业化学组合物。
本发明还涉及式(I)的二氨基三嗪化合物作为除草剂,即防治不想要和/或有害植物生长或植物的用途。
此外,本发明提供了一种防治不想要的植物的方法。该方法包括使除草有效量的至少一种式(I)的二氨基三嗪化合物作用于不想要的植物或植物生长、其种子和/或其生长地。施用可以在不想要的植物出苗之前、之中和/或之后,优选出苗之中和/或之后进行。
此外,本发明涉及制备式(I)的二氨基三嗪化合物的方法和中间体。
本发明的其他实施方案由权利要求书、说明书和实施例明了。应理解的是本发明主题的上面提到且下文仍要说明的特征在不背离本发明范围下不仅可以以在每种特定情况下给出的组合使用,而且可以以其他组合使用。
本文所用术语“防治”和“防除”是同义词。
本文所用术语“不希望的植物生长”、“不想要的植物生长”、“不想要的植物”和“有害植物”是同义词。
就取代基而言,术语“一个或多个取代基”意指取代基数为例如1-10,尤其是1、2、3、4、5、6、7或8。
若本文所述式(I)的二氨基三嗪化合物能够形成几何异构体,例如E/Z异构体,则本发明涉及纯异构体及其混合物二者。同样地,本发明涉及纯异构体的用途及其混合物的用途,以及含有纯异构体或其混合物的组合物。
若本文所述式(I)的二氨基三嗪化合物具有一个或多个手性中心且因此作为对映体或非对映体存在,则本发明涉及纯对映体或非对映体及其混合物二者。同样地,本发明涉及纯对映体或非对映体的用途及其混合物的用途,以及含有纯对映体或非对映体及其混合物的组合物。
若本文所述式(I)的二氨基三嗪化合物具有可离子化官能基团,则它们还可以以其可农用盐形式使用。合适的通常是其阳离子和阴离子分别对活性化合物的活性没有不利影响的那些阳离子的盐和那些酸的酸加成盐。
优选的阳离子是碱金属的离子,优选锂、钠和钾离子,碱土金属的离子,优选钙和镁离子,以及过渡金属的离子,优选锰、铜、锌和铁离子,此外还有铵和其中1-4个氢原子被C1-C4烷基、羟基-C1-C4烷基、C1-C4烷氧基-C1-C4烷基、羟基-C1-C4烷氧基-C1-C4烷基、苯基或苄基替代的取代铵,优选铵、甲基铵、异丙基铵、二甲基铵、二异丙基铵、三甲基铵、庚基铵、十二烷基铵、十四烷基铵、四甲基铵、四乙基铵、四丁基铵、2-羟基乙基铵(醇胺盐)、2-(2-羟基乙-1-氧基)乙-1-基铵(二甘醇胺盐)、二(2-羟基乙-1-基)铵(二醇胺盐)、三(2-羟基乙基)铵(三醇胺盐)、三(2-羟基丙基)铵、苄基三甲基铵、苄基三乙基铵、N,N,N-三甲基乙醇铵(胆碱盐),此外还有离子,锍离子,优选三(C1-C4烷基)锍,如三甲基锍,以及氧化锍离子,优选三(C1-C4烷基)氧化锍,最后还有多元胺如N,N-二(3-氨基丙基)甲基胺和二亚乙基三胺的盐。
有用酸加成盐的阴离子主要是氯离子、溴离子、氟离子、碘离子、硫酸氢根、甲基硫酸根、硫酸根、磷酸二氢根、磷酸氢根、硝酸根、碳酸氢根、碳酸根、六氟硅酸根、六氟磷酸根、苯甲酸根以及还有C1-C4链烷酸的阴离子,优选甲酸根、乙酸根、丙酸根和丁酸根。
本发明的其他实施方案由权利要求书、说明书和实施例明了。应理解的是本发明主题的上面提到且下文仍要说明的特征在不背离本发明范围下不仅可以以在每种特定情况下给出的组合使用,而且可以以其他组合使用。
在变量,例如R1、R2、R2A、R3、R4、R4A、R5、R6、R7、R8的定义中提到的有机结构部分象术语卤素一样为各基团成员的单独列举的集合性术语。术语卤素在每种情况下表示氟、氯、溴或碘。所有烃链,即所有烷基、卤代烷基、链烯基、炔基、烷氧基、链烯氧基、炔氧基、烷硫基、烷基亚磺酰基、烷基磺酰基、(烷基)氨基、二(烷基)氨基、烷氧基烷基、烷氧基烷氧基、(烷基)羰基、(烷氧基)羰基链,可以是直链或支化的,前缀Cn-Cm在每种情况下表示该基团中的可能碳原子数目。同样适用于复杂基团,例如环烷基烷基和苯基烷基。
该类含义的实例为:
-C1-C4烷基以及还有C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基磺酰基、(C1-C4烷基)羰基、(C1-C4烷基)羰基、(C1-C4烷氧基)羰基、(C1-C4烷基)羰氧基、C1-C4烷氧基-C1-C4烷基、C3-C6环烷基-C1-C4烷基、(C1-C4烷基氨基)羰基、二(C1-C4烷基)氨基羰基、(C1-C4烷基氨基)磺酰基、二(C1-C4烷基)氨基磺酰基或苯基-C1-C4烷基的C1-C4烷基结构部分:例如CH3、C2H5、正丙基、CH(CH3)2、正丁基、CH(CH3)-C2H5、CH2-CH(CH3)2和C(CH3)3;
-C1-C6烷基以及还有C1-C6烷氧基、C1-C6烷硫基、C1-C6烷基磺酰基、(C1-C6烷基)羰基、(C1-C6烷基)羰基、(C1-C6烷氧基)羰基、(C1-C6烷基)羰氧基、C1-C6烷氧基-C1-C6烷基、C3-C6环烷基-C1-C6烷基、苯基(C1-C6烷基)氨基羰基、(C1-C6烷基氨基)羰基、二(C1-C6烷基)氨基羰基、(C1-C6烷基氨基)磺酰基、二(C1-C6烷基)氨基磺酰基或苯基-C1-C6烷基的C1-C6烷基结构部分:如上所述的C1-C4烷基以及还有例如正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、正己基、1,1-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基或1-乙基-2-甲基丙基,优选甲基、乙基、正丙基、1-甲基乙基、正丁基、1,1-二甲基乙基、正戊基或正己基;
-C2-C6链烯基以及还有(C1-C6烷氧基)-C2-C6链烯基的C2-C6链烯基结构部分:具有2-6个碳原子和处于任意位置的C=C双键的线性或支化烯属不饱和烃基,例如乙烯基、1-丙烯基、2-丙烯基、1-甲基-乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基、1-甲基-1-丁烯基、2-甲基-1-丁烯基、3-甲基-1-丁烯基、1-甲基-2-丁烯基、2-甲基-2-丁烯基、3-甲基-2-丁烯基、1-甲基-3-丁烯基、2-甲基-3-丁烯基、3-甲基-3-丁烯基、1,1-二甲基-2-丙烯基、1,2-二甲基-1-丙烯基、1,2-二甲基-2-丙烯基、1-乙基-1-丙烯基、1-乙基-2-丙烯基、1-己烯基、2-己烯基、3-己烯基、4-己烯基、5-己烯基、1-甲基-1-戊烯基、2-甲基-1-戊烯基、3-甲基-1-戊烯基、4-甲基-1-戊烯基、1-甲基-2-戊烯基、2-甲基-2-戊烯基、3-甲基-2-戊烯基、4-甲基-2-戊烯基、1-甲基-3-戊烯基、2-甲基-3-戊烯基、3-甲基-3-戊烯基、4-甲基-3-戊烯基、1-甲基-4-戊烯基、2-甲基-4-戊烯基、3-甲基-4-戊烯基、4-甲基-4-戊烯基、1,1-二甲基-2-丁烯基、1,1-二甲基-3-丁烯基、1,2-二甲基-1-丁烯基、1,2-二甲基-2-丁烯基、1,2-二甲基-3-丁烯基、1,3-二甲基-1-丁烯基、1,3-二甲基-2-丁烯基、1,3-二甲基-3-丁烯基、2,2-二甲基-3-丁烯基、2,3-二甲基-1-丁烯基、2,3-二甲基-2-丁烯基、2,3-二甲基-3-丁烯基、3,3-二甲基-1-丁烯基、3,3-二甲基-2-丁烯基、1-乙基-1-丁烯基、1-乙基-2-丁烯基、1-乙基-3-丁烯基、2-乙基-1-丁烯基、2-乙基-2-丁烯基、2-乙基-3-丁烯基、1,1,2-三甲基-2-丙烯基、1-乙基-1-甲基-2-丙烯基、1-乙基-2-甲基-1-丙烯基和1-乙基-2-甲基-2-丙烯基;
-C2-C6炔基以及还有(C1-C6烷氧基)-C2-C6炔基的C2-C6炔基结构部分:具有2-6个碳原子且含有至少一个C-C叁键的线性或支化不饱和烃基,例如乙炔基、1-丙炔基、2-丙炔基(炔丙基)、1-丁炔基、2-丁炔基、3-丁炔基、1-甲基-2-丙炔基等;
-C1-C4卤代烷基:部分或完全被氟、氯、溴和/或碘取代的如上所述的C1-C4烷基,例如氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基、氯氟甲基、二氯一氟甲基、一氯二氟甲基、溴甲基、碘甲基、2-氟乙基、2-氯乙基、2-溴乙基、2-碘乙基、2,2-二氟乙基、2,2,2-三氟乙基、2-氯-2-氟乙基、2-氯-2,2-二氟乙基、2,2-二氯-2-氟乙基、2,2,2-三氯乙基、五氟乙基、2-氟丙基、3-氟丙基、2,2-二氟丙基、2,3-二氟丙基、2-氯丙基、3-氯丙基、2,3-二氯丙基、2-溴丙基、3-溴丙基、3,3,3-三氟丙基、3,3,3-三氯丙基、2,2,3,3,3-五氟丙基、七氟丙基、1-氟甲基-2-氟乙基、1-氯甲基-2-氯乙基、1-溴甲基-2-溴乙基、4-氟丁基、4-氯丁基、4-溴丁基、九氟丁基、1,1,2,2-四氟乙基和1-三氟甲基-1,2,2,2-四氟乙基;
-C1-C6卤代烷基:如上所述的C1-C4卤代烷基以及还有例如5-氟戊基、5-氯戊基、5-溴戊基、5-碘戊基、十一氟戊基、6-氟己基、6-氯己基、6-溴己基、6-碘己基和十二氟己基;
-C3-C6环烷基:具有3-6个环成员的单环饱和烃,例如环丙基、环丁基、环戊基和环己基;
-C1-C4烷氧基:例如甲氧基、乙氧基、丙氧基、1-甲基乙氧基、丁氧基、1-甲基丙氧基、2-甲基丙氧基和1,1-二甲基乙氧基;
-C1-C6烷氧基以及还有(C1-C6烷氧基)羰基、(C1-C6烷氧基)磺酰基、(C1-C6烷氧基)-C1-C6烷基、(C1-C6烷氧基)-C1-C6烷氧基、(C1-C6烷氧基)-C2-C6链烯基、(C1-C6烷氧基)-C2-C6炔基的C1-C6烷氧基结构部分:如上所述的C1-C4烷氧基以及还有例如戊氧基、1-甲基丁氧基、2-甲基丁氧基、3-甲氧基丁氧基、1,1-二甲基丙氧基、1,2-二甲基丙氧基、2,2-二甲基丙氧基、1-乙基丙氧基、己氧基、1-甲基戊氧基、2-甲基戊氧基、3-甲基戊氧基、4-甲基戊氧基、1,1-二甲基丁氧基、1,2-二甲基丁氧基、1,3-二甲基丁氧基、2,2-二甲基丁氧基、2,3-二甲基丁氧基、3,3-二甲基丁氧基、1-乙基丁氧基、2-乙基丁氧基、1,1,2-三甲基丙氧基、1,2,2-三甲基丙氧基、1-乙基-1-甲基-丙氧基和1-乙基-2-甲基丙氧基;
-C1-C4卤代烷氧基:部分或完全被氟、氯、溴和/或碘取代的如上所述的C1-C4烷氧基,例如氯甲氧基、二氯甲氧基、三氯甲氧基、氟甲氧基、二氟甲氧基、三氟甲氧基、氯氟甲氧基、二氯一氟甲氧基、一氯二氟甲氧基2-氟乙氧基、2-氯乙氧基、2-溴乙氧基、2,2-二氟乙氧基、2,2,2-三氟乙氧基、2-氯-2-氟乙氧基、2-氯-2,2-二氟乙氧基、2,2-二氯-2-氟乙氧基、2,2,2-三氯乙氧基、五氟乙氧基、2-氟丙氧基、3-氟丙氧基、2,2-二氟丙氧基、2,3-二氟丙氧基、2-氯丙氧基、3-氯丙氧基、2,3-二氯丙氧基、3,3,3-三氟丙氧基、3,3,3-三氯丙氧基、2,2,3,3,3-五氟丙氧基、七氟丙氧基、1-(氟甲基)-2-氟乙氧基、4-氟丁氧基、九氟丁氧基、1,1,2,2,-四氟乙氧基和1-三氟甲基-1,2,2,2-四氟乙氧基;
-C1-C6卤代烷氧基:如上所述的C1-C4烷氧基:如上所述的C1-C4卤代烷氧基以及还有例如5-氟戊基、5-氯戊基、5-溴戊基、5-碘戊基、十一氟戊基、6-氟己基、6-氯己基、6-溴己基、6-碘己基和十二氟己基;
-C2-C6链烯氧基:经由氧原子键合的如上所定义的C2-C6链烯基,如乙烯氧基(乙烯基氧基)、1-丙烯氧基、2-丙烯氧基(烯丙氧基)、1-丁烯氧基、2-丁烯氧基、3-丁烯氧基、1-甲基-2-丙烯氧基等;
-C2-C6炔氧基:经由氧原子键合的如上所定义的C2-C6炔基,如乙炔氧基、1-丙炔基、2-丙炔氧基(炔丙氧基)、1-丁炔氧基、2-丁炔氧基、3-丁炔氧基、1-甲基-2-丙炔氧基等;
-C3-C6环烷基以及还有(C3-C6环烷基)羰基、(C3-C6环烷基)-C1-C6烷基、(C3-C6环烷基)羰基和(C3-C6环烷基)-C1-C6烷氧基的C3-C6环烷基结构部分:具有3-6个碳原子的环脂族基团,例如环丙基、环丁基、环戊基和环己基;
-C3-C6环烷氧基:具有3-6个碳原子且经由氧原子键合的环脂族基团,如环丙氧基、环丁氧基、环戊氧基和环己氧基;
-(C3-C6环烷基)-C1-C6烷基:如上所定义的C1-C6烷基,尤其是C1-C4烷基,如甲基或乙基,其中1个氢原子被如上所定义的C3-C6环烷基替代,实例包括环丙基甲基(CH2-环丙基)、环丁基甲基、环戊基甲基、环己基甲基、1-环丙基乙基(CH(CH3)-环丙基)、1-环丁基乙基、1-环戊基乙基、1-环己基乙基、2-环丙基乙基(CH2CH2-环丙基)、2-环丁基乙基、2-环戊基乙基或2-环己基乙基;
-(C3-C6环烷基)-C1-C6烷氧基:如上所定义的C1-C6烷氧基,尤其是C1-C4烷氧基,如甲氧基或乙氧基,其中1个氢原子被如上所定义的C3-C6环烷基替代,实例包括环丙基甲氧基(OCH2-环丙基)、环丁基甲氧基、环戊基甲氧基、环己基甲氧基、1-环丙基乙氧基(OCH(CH3)-环丙基)、1-环丁基乙氧基、1-环戊基乙氧基、1-环己基乙氧基、2-环丙基乙氧基(OCH2CH2-环丙基)、2-环丁基乙氧基、2-环戊基乙氧基或2-环己基乙氧基;
-(C1-C6烷氧基)-C1-C6烷基:如上所定义的C1-C6烷基,尤其是C1-C4烷基,如甲基、乙基或异丙基,其中1个氢原子被如上所定义的C1-C6烷氧基替代,实例包括甲氧基甲基、乙氧基甲基、正丙氧基甲基、丁氧基甲基、1-甲氧基乙基、1-乙氧基乙基、1-正丙氧基乙基、1-丁氧基乙基、2-甲氧基乙基、2-乙氧基乙基、2-正丙氧基乙基、2-丁氧基乙基、2-甲氧基丙基、2-乙氧基丙基、2-正丙氧基丙基、2-丁氧基丙基;
-(C1-C6烷氧基)-C1-C6烷氧基:如上所定义的C1-C6烷氧基,尤其是C1-C4烷氧基,如甲氧基或乙氧基,其中1个氢原子被如上所定义的C1-C6烷氧基替代,实例包括甲氧基甲氧基、乙氧基甲氧基、正丙氧基甲氧基、丁氧基甲氧基、2-甲氧基乙氧基、2-乙氧基乙氧基、2-正丙氧基乙氧基和2-丁氧基乙氧基;
-(C1-C6烷氧基)-C2-C6链烯基:如上所定义的C2-C6链烯基,尤其是C2-C4链烯基,如乙烯基、丙烯基、1-丁烯基或2-丁烯基,其中1个氢原子被如上所定义的C1-C6烷氧基替代;
-(C1-C6烷氧基)-C2-C6炔基:如上所定义的C2-C6炔基,尤其是C2-C4炔基,如乙炔基、丙炔基或2-丁炔基,其中1个氢原子被如上所定义的C1-C6烷氧基替代;
-(C1-C6烷基)羰基:通过羰基与该分子的其余部分键合的如上所述的C1-C6烷基;
-(C1-C6烷氧基)羰基:通过羰基与该分子的其余部分键合的如上所述的C1-C6烷氧基;
-3-6员杂环基:具有3-6个环成员的如上所述的单环饱和或部分不饱和烃,
其除了碳原子外含有1或2个选自O、S和N的杂原子;
例如饱和杂环如2-环氧乙烷基、2-氧杂环丁烷基、3-氧杂环丁烷基、2-氮杂环丙烷基、3-硫杂环丁烷基、1-氮杂环丁烷基、2-氮杂环丁烷基、2-四氢呋喃基、3-四氢呋喃基、2-四氢噻吩基、3-四氢噻吩基、2-吡咯烷基、
3-吡咯烷基、3-异唑烷基、4-异唑烷基、5-异唑烷基、3-异噻唑烷基、4-异噻唑烷基、5-异噻唑烷基、3-吡唑烷基、4-吡唑烷基、5-吡唑烷基、2-唑烷基、4-唑烷基、5-唑烷基、2-噻唑烷基、4-噻唑烷基、
5-噻唑烷基、2-咪唑烷基、4-咪唑烷基、2-哌啶基、3-哌啶基、4-哌啶基、
1,3-二烷-2-基、1,3-二烷-4-基、1,3-二烷-5-基、1,4-二烷-2-基、
1,3-二噻烷-2-基、1,3-二噻烷-4-基、1,4-二噻烷-2-基、1,3-二噻烷-5-基、
2-四氢吡喃基、3-四氢吡喃基、4-四氢吡喃基、2-四氢噻喃基、3-四氢噻喃基、4-四氢噻喃基、3-六氢哒嗪基、4-六氢哒嗪基、2-六氢嘧啶基、4-六氢嘧啶基、5-六氢嘧啶基、2-哌嗪基、四氢-1,3-嗪-2-基、四氢-1,3-
嗪-6-基、2-吗啉基、3-吗啉基或4-吗啉基,例如2H-吡喃-2-基、2H-吡喃
-3-基、2H-吡喃-4-基、2H-吡喃-5-基、2H-吡喃-6-基、2H-噻喃-2-基、2H-
噻喃-3-基、2H-噻喃-4-基、2H-噻喃-5-基、2H-噻喃-6-基;
-部分不饱和杂环如2,3-二氢呋喃-2-基、2,3-二氢呋喃-3-基、2,4-二氢呋喃-2-基、2,4-二氢呋喃-3-基、2,3-二氢噻吩-2-基、2,3-二氢噻吩-3-基、2,4-
二氢噻吩-2-基、2,4-二氢噻吩-3-基、4,5-二氢吡咯-2-基、4,5-二氢吡咯-3-
基、2,5-二氢吡咯-2-基、2,5-二氢吡咯-3-基、4,5-二氢异唑-3-基、2,5-
二氢异唑-3-基、2,3-二氢异唑-3-基、4,5-二氢异唑-4-基、2,5-二氢异唑-4-基、2,3-二氢异唑-4-基、4,5-二氢异唑-5-基、2,5-二氢异唑-5-基、2,3-二氢异唑-5-基、4,5-二氢异噻唑-3-基、2,5-二氢异噻唑-3-
基、2,3-二氢异噻唑-3-基、4,5-二氢异噻唑-4-基、2,5-二氢异噻唑-4-基、
2,3-二氢异噻唑-4-基、4,5-二氢异噻唑-5-基、2,5-二氢异噻唑-5-基、2,3-
二氢异噻唑-5-基、2,3-二氢吡唑-2-基、2,3-二氢吡唑-3-基、2,3-二氢吡唑-4-基、2,3-二氢吡唑-5-基、3,4-二氢吡唑-3-基、3,4-二氢吡唑-4-基、3,4-二氢吡唑-5-基、4,5-二氢吡唑-3-基、4,5-二氢吡唑-4-基、4,5-二氢吡唑-5-基、2,3-二氢咪唑-2-基、2,3-二氢咪唑-3-基、2,3-二氢咪唑-4-基、2,3-二氢咪唑-5-基、4,5-二氢咪唑-2-基、4,5-二氢咪唑-4-基、4,5-二氢咪唑-5-基、2,5-二氢咪唑-2-基、2,5-二氢咪唑-4-基、2,5-二氢咪唑-5-基、2,3-二氢唑-3-基、2,3-二氢唑-4-基、2,3-二氢唑-5-基、3,4-二氢唑-3-基、3,4-二氢唑-4-基、3,4-二氢唑-5-基、2,3-二氢噻唑-3-基、2,3-二氢噻唑-4-基、2,3-二氢噻唑-5-基、3,4-二氢噻唑-3-基、3,4-二氢噻唑-4-基、3,4-二氢噻唑-5-基、3,4-二氢噻唑-2-基、3,4-二氢噻唑-3-基、3,4-二氢噻唑-4-基、3,6-二氢-2H-吡喃-2-基、3,6-二氢-2H-吡喃-3-基、3,6-二氢-2H-吡喃-4-基、3,6-二氢-2H-吡喃-5-基、3,6-二氢-2H-吡喃-6-基、3,4-二氢-2H-吡喃-3-基、3,4-二氢-2H-吡喃-4-基、3,4-二氢-2H-吡喃-6-基、5,6-二氢-4H-1,3-嗪-2-基。
下文所述的本发明优选实施方案必须理解为相互独立地或相互组合地为优选的。特定组的本发明实施方案涉及如下那些式(I)的二氨基三嗪,其中变量R1、R2、R2A、R3、R4、R4A、R5、R6、R7、R8相互独立地或相互组合地具有如下含义:
特定组的实施方案涉及如下式(I)的二氨基三嗪化合物,其中R1为Cl、Br、I、CR1A;
其中R1A为H或卤素;优选R1为Cl、Br或CH3。
还优选如下式(I)的二氨基三嗪化合物,其中
R2选自H、卤素、CH3、C1卤代烷基;特别是H、卤素、CH3;更特别是H、F、CH3。
其他特定组的实施方案涉及如下式(I)的二氨基三嗪化合物,其中R3为H或卤素;优选H。
其他特定组的实施方案涉及如下式(I)的二氨基三嗪化合物,其中R4选自卤素、CH3、C1卤代烷基;特别是卤素、CH3;更特别是Cl、Br、CH3。
还优选如下式(I)的二氨基三嗪化合物,其中R5选自H、卤素、CN、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基和C1-C6卤代烷氧基,尤其选自氢,氟,C1-C4烷基,例如甲基、乙基、正丙基、2-丙基、正丁基、2-丁基、异丁基或叔丁基,C1-C4卤代烷基,例如二氟甲基、三氟甲基、2,2,2-三氟乙基、1,1-二氟乙基、1,1,2,2-四氟乙基或五氟乙基,C1-C4烷氧基,例如甲氧基或乙氧基,和C1-C4卤代烷氧基,例如二氟甲氧基或三氟甲氧基。
其他特定组的实施方案涉及如下式(I)的二氨基三嗪化合物,其中R6选自H、卤素、CN、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基和C1-C6卤代烷氧基,尤其选自氢、氟和C1-C4烷基,更特别是选自氢、氟和甲基,特别是选自氟和甲基。
在组(1)的实施方案中,R7如上所定义。优选
R7选自卤素、C1-C6烷基、C1-C6卤代烷基、C2-C6链烯基、C3-C6炔基、C3-C6环烷基、C3-C6环烷基-C1-C6烷基、C3-C6环烯基、C1-C6烷氧基-C1-C6烷基。
其他特定组的实施方案涉及如下式(I)的二氨基三嗪化合物,其中R6和R7与其所连接的碳原子一起形成选自羰基、C3-C6环烷烃、C3-C6环烯基、3-6员饱和或部分不饱和的杂环基的结构部分,其中碳环和杂环未被取代,部分或完全被卤化或带有1-6个C1-C6烷基,和结构部分>C=CRxRy,其中Rx和Ry为氢、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基或者CRxRy形成3-6员环烷基。优选R6和R7与其所连接的碳原子一起形成C3-C6环烷烃。
CR5R6R7的特别优选的实例为如下那些基团,其中R2、R3和R4在表1a的第1-65行中给出。
表1a:
R8选自C1-C6烷基、C2-C6链烯基、C2-C6炔基、(C1-C6烷氧基)-C1-C6烷基、(C1-C6烷氧基)-C2-C6链烯基、(C1-C6烷氧基)-C2-C6炔基、(C1-C6环烷基)-C2-C6炔基、(C3-C6环烷基)-C1-C4烷基、(C3-C6环烷氧基)-C1-C4烷基,其中上述基团未被取代、部分或完全被卤化,并且其中后提到的6个基团的环脂族部分可以带有1、2、3、4、5或6个甲基;
优选R8选自C1-C6烷基、C2-C6链烯基、C2-C6炔基、(C1-C6烷氧基)-C1-C6烷基。
特别地,R8选自CH3、CH2CCH、CH2CCCH3、CH2OCH3CH(CH3)CCH、CH(CH3)CCCH3,尤其是CH3、CH2CCH、CH2CCCH3、CH2OCH3。
化合物I的特别实施方案为如下化合物:I-A、I-B、I-C、I-D、I-E:
表1-1式I-A、I-B、I-C、I-D、I-E、I-F化合物,其中对于各单独化合物而言R2、R4和R8组合的含义在每种情况下对应于表A的一行(化合物I-A.1-1.A-1至I-A.1-1.A-192、I-B.1-1.A-1至I-B.1-1.A-192、I-C.1-1.A-1至I-C.1-1.A-192、I-D.1-1.A-1至I-D.1-1.A-192、I-E.1-1.A-1至I-E.1-1.A-192)。
表A
本发明式(I)的二氨基三嗪化合物可以通过有机化学的标准方法,例如通过下列方法制备:
方法A)
式(I)的二氨基三嗪类可以通过在惰性有机溶剂中在碱性或酸性条件下将相应的式(II)的2-烷氧基苯胺加成至式(III)的卤代三嗪来合成,如下面的方案所示:
变量R1、R2、R3和R4、R6、R7和R8具有如上面所述式(I)中的含义,尤其是优选含义,以及
Hal为卤素;优选Cl或Br;特别优选Cl;
式(III)的卤代三嗪类与式(II)的胺化合物的反应通常在50℃至反应混合物的沸点下在惰性有机溶剂中进行。
式(III)的卤代三嗪类和式(II)化合物以等摩尔量使用或者式(II)化合物相对于式(III)的卤代三嗪类过量使用。优选式(II)化合物与式(III)的卤代三嗪类的摩尔比为2:1-1:1,优选1.5:1-1:1,尤其优选1.2:1。
式(III)的卤代三嗪类与式(II)化合物的反应在有机溶剂中进行。合适的溶剂是在反应条件下能够至少部分且优选完全溶解式(III)的卤代三嗪类和式(II)的苯胺类的那些。合适溶剂的实例是脂族烃类如戊烷、己烷、环己烷、硝基甲烷,芳族烃类如苯、氯苯、甲苯、甲酚类、邻二甲苯、间二甲苯和对二甲苯,卤代烃类如二氯甲烷、1,2-二氯乙烷、氯仿、四氯化碳和氯苯,醚类如乙醚、二异丙醚、叔丁基甲基醚(TBME)、二烷、茴香醚和四氢呋喃(THF),酯类如乙酸乙酯和乙酸丁酯;腈类如乙腈和丙腈,以及偶极非质子溶剂如环丁砜、二甲亚砜、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAC)、1,3-二甲基-2-咪唑烷酮(DMI)、N,N′-二甲基亚丙基脲(DMPU)、二甲亚砜(DMSO)和1-甲基-2-吡咯烷酮(NMP)。优选的溶剂是如上所定义的醚类。本文所用术语溶剂还包括两种或更多种上述化合物的混合物。
式(III)的卤代三嗪类与式(II)化合物的反应在碱或酸存在下进行。合适碱的实例包括含金属碱和含氮碱。
合适含金属碱的实例是无机化合物如碱金属和碱土金属氢氧化物以及其他金属氢氧化物,如氢氧化锂、氢氧化钠、氢氧化钾、氢氧化镁、氢氧化钙和氢氧化铝;碱金属和碱土金属氧化物以及其他金属氧化物,如氧化锂、氧化钠、氧化钾、氧化镁、氧化钙和氧化镁、氧化铁、氧化银;碱金属和碱土金属氢化物如氢化锂、氢化钠、氢化钾和氢化钙,碱金属和碱土金属甲酸盐、乙酸盐和羧酸的其他金属盐,如甲酸钠、苯甲酸钠、乙酸锂、乙酸钠、乙酸钾、乙酸镁和乙酸钙;碱金属和碱土金属碳酸盐如碳酸锂、碳酸钠、碳酸钾、碳酸镁和碳酸钙,以及碱金属碳酸氢盐如碳酸氢锂、碳酸氢钠、碳酸氢钾;碱金属和碱土金属磷酸盐如磷酸钠、磷酸钾和磷酸钙;碱金属和碱土金属醇盐如甲醇钠、乙醇钠、乙醇钾、叔丁醇钾、叔戊醇钾。
优选的碱是如上所定义的碱金属和碱土金属醇盐。本文所用术语碱还包括两种或更多种,优选两种上述化合物的混合物。
碱可以等摩尔浓度或过量使用,优选基于式(III)的卤代三嗪类为1-10,尤其优选2-4当量,并且它们还可以用作溶剂。
合适酸的实例为无机酸如氢氟酸、盐酸、氢溴酸、氢碘酸、磷酸、硫酸;对甲苯磺酸;路易斯酸如三氟化硼、氯化铝、氯化铁III、氯化锡IV、氯化钛IV和氯化锌II,以及有机酸如甲酸、乙酸、丙酸、草酸、甲基苯磺酸、苯磺酸、樟脑磺酸、柠檬酸、三氟乙酸。
优选的酸为无机酸。
酸通常过量使用,或者合适的话,可以用作溶剂。
该反应的结束可以容易地由熟练技术人员借助常规方法确定。
反应混合物以常规方式后处理,例如通过与水混合,分离各相并且合适的话提纯粗产物。
制备式(I)化合物所要求的式(II)的苯胺类可市购或可以通过有机化学的标准方法,例如通过市购酚的硝化和随后硝基的还原来制备。
制备式(I)的二氨基三嗪类所要求的式(III)的卤代三嗪类由文献已知、可市购和/或可以类似于已知文献(例如J.K.Chakrabarti等,Tetrahedron1975,31,1879-1882)通过使式(IV)的硫代三嗪类与卤素源(例如Cl)或其他合适的卤化剂(例如SOCl2)反应来制备。
方法B)
式(I)的二氨基三嗪类可以通过在惰性有机溶剂中在碱性条件下相应的式(IV)的酚二氨基三嗪的烷基化来合成,如下面的方案所示:
变量R1、R2、R3和R4、R6、R7和R8具有如上面所述式(I)中的含义,尤其是优选含义;且
Hal为卤素;优选I或Br或Cl;
式(IV)的酚二氨基三嗪的烷基化反应可在室温至反应混合物的沸点下在有机溶剂中进行。
式(V)的烷基化剂和式(IV)化合物以等摩尔量使用,或者式(V)化合物相对于式(IV)的酚二氨基三嗪类过量使用。优选地,式(V)化合物与式(IV)的酚二氨基三嗪类的摩尔比为1.5:1-1:1,优选1.2:1。
式(III)的卤代三嗪类与式(II)化合物的反应在碱或酸的存在下进行。合适碱的实例包括含金属碱和含氮碱。
合适含金属碱的实例是碱金属和碱土金属氢化物,如氢化锂、氢化钠、氢化钾和氢化钙,碱金属和碱土金属碳酸盐,如碳酸锂、碳酸钠、碳酸钾、碳酸镁和碳酸钙,以及碱金属碳酸氢盐,如碳酸氢锂、碳酸氢钠、碳酸氢钾;碱金属和碱土金属磷酸盐,如磷酸钠、磷酸钾和磷酸钙;碱金属和碱土金属醇盐如叔丁醇钾、叔戊醇钾。
式(IV)的酚二氨基三嗪类可以按照用于合成式(I)的二氨基三嗪类所描述的程序:方法A来制备。
方法C)
变量R1、R2、R3和R4、R6、R7和R8具有如上面所述式(I)中的含义,尤其是优选含义,以及
L为可置换的离去基团如卤素、CN、C1-C6烷氧基、C1-C6烷氧基羰基、C1-C6烷基羰氧基或C1-C6烷氧基羰氧基;
优选卤素或C1-C6烷氧基;
特别优选Cl或C1-C6烷氧基,尤其优选Cl
式(VI)的双胍与式(VII)的羰基化合物的反应通常在50℃至反应混合物的沸点,优选50-200℃的温度下进行(例如R.Sathunuru等,J.Heterocycl.Chem.2008,45,1673-1678)。
该反应可以在大气压力下或在升高的压力下,合适的话在惰性气体下连续或分批进行。
在本发明方法的一个实施方案中,式(VI)的双胍和式(VII)的羰基化合物以等摩尔量使用。
在本发明方法的另一实施方案中,式(VII)的羰基化合物相对于式(VI)的双胍过量使用。
优选式(VII)的羰基化合物与式(VI)的双胍的摩尔比为1.5:1-1:1,优选1.2:1-1:1,特别优选1.2:1,还特别优选1:1。
式(VI)的双胍与式(VII)的羰基化合物的反应在有机溶剂中进行。
合适的溶剂原则上是所有能够在反应条件下至少部分和优选完全溶解式(VI)的双胍和式(VII)的羰基化合物的溶剂。
合适溶剂的实例为脂族烃类,如戊烷、己烷、环己烷、硝基甲烷和Cs-Cs链烷烃的混合物,芳族烃类,如苯、氯苯、甲苯,甲酚类、邻二甲苯、间二甲苯和对二甲苯,卤代烃类,如二氯甲烷、1,2-二氯乙烷、氯仿、四氯化碳和氯苯,醚类,如乙醚、二异丙醚、叔丁基甲基醚(TBME)、二烷、茴香醚和四氢呋喃(THF),腈类,如乙腈和丙腈,以及偶极非质子溶剂,如环丁砜、二甲亚砜、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAC)、1,3-二甲基-2-咪唑烷酮(DMI)、N,N′-二甲基亚丙基脲(DMPU)、二甲亚砜(DMSO)和1-甲基-2-吡咯烷酮(NMP)。
优选的溶剂为如上所定义的醚类和偶极非质子溶剂。更优选的溶剂为如上所定义的醚类。
本文所用术语溶剂还包括两种或更多种上述化合物的混合物。
式(VI)的双胍与式(VII)的羰基化合物的反应在碱存在下进行。
合适碱的实例包括含金属碱和含氮碱。
合适含金属碱的实例是无机化合物,如碱金属和碱土金属氧化物,以及其他金属氧化物,如氧化锂、氧化钠、氧化钾、氧化镁、氧化钙和氧化镁,氧化铁、氧化银;碱金属和碱土金属氢化物如氢化锂、氢化钠、氢化钾和氢化钙,碱金属氨基化物,如氨基锂、氨基钠和氨基钾;碱金属和碱土金属碳酸盐如碳酸锂、碳酸钠、碳酸钾、碳酸镁和碳酸钙,以及碱金属碳酸氢盐如碳酸氢锂、碳酸氢钠、碳酸氢钾;碱金属和碱土金属磷酸盐,如磷酸钠、磷酸钾和磷酸钙;以及此外还有有机碱,如叔胺如三-Ci-C6烷基胺,例如三乙胺、三甲胺、N-乙基二异丙基胺,以及N-甲基哌啶,吡啶,取代吡啶如可力丁、卢剔啶,N-甲基吗啉和4-二甲基氨基吡啶(DMAP),以及还有双环胺,如1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)或1,5-二氮杂双环[4.3.0]壬-5-烯(DBN)。
优选的碱是如上所定义的三C1-C6烷基胺。本文所用术语碱还包括两种或更多种,优选两种上述化合物的混合物。特别优选使用一种碱。碱通常过量使用;但它们还可以以等摩尔量使用或者合适的话可以用作溶剂。基于式(VII)的双胍使用优选1-5碱当量,特别优选3碱当量的碱。该反应的结束可以容易地由熟练技术人员借助常规方法确定。
反应混合物以常规方式后处理,例如通过与水混合,分离各相并且合适的话层析提纯粗产物。
一些中间体和终产物以粘稠油的形式得到,其可以在减压和适度升高的温度下提纯或除去挥发性组分。
如果中间体和终产物以固体形式得到,则提纯还可以通过重结晶或浸煮进行。
制备式(I)的二氨基三嗪类所要求的式(VII)的羰基化合物在文献中是已知的,和/或可以市购。
制备式(I)的二氨基三嗪类所要求的式(VI)的双胍可以通过使式(VIII)的氰基胍与式(II)的胺在酸存在下反应而制备:
式(VIII)的胍与式(II)的胺的反应通常在50℃至150℃,优选80℃至130℃下进行。合适的话,使用微波技术(例如C.O.Kappe,A.Stadler,Microwaves in Organic andMedicinal Chemistry,Weinheim 2012)。
该反应可以在大气压力下或在升高的压力下,合适的话在惰性气体下连续或分批进行。
在本发明方法的一个实施方案中,式(VIII)的胍与式(II)的苯胺以等摩尔量使用。
在本发明方法的另一实施方案中,式(II)的苯胺相对于式(VIII)的胍过量使用。
优选式(II)的苯胺与式(VIII)的胍的摩尔比为2:1-1:1,优选1.5:1-1:1,特别优选1:1。
式(VIII)的胍与式(II)的胺的反应在有机溶剂中进行。
合适的原则上是所有能够在反应条件下至少部分和优选完全溶解式(VIII)的胍和式(II)的苯胺的溶剂。
合适溶剂的实例是脂族烃类,如戊烷、己烷、环己烷、硝基甲烷和C5-C8链烷烃的混合物,芳族烃类,如苯、氯苯、甲苯,甲酚类、邻二甲苯、间二甲苯和对二甲苯,卤代烃类,如二氯甲烷、1,2-二氯乙烷、氯仿、四氯化碳和氯苯,醚类,如乙醚、二异丙醚、叔丁基甲基醚(TBME)、二烷、茴香醚和四氢呋喃(THF),酯类,如乙酸乙酯和乙酸丁酯;腈类,如乙腈和丙腈,以及偶极非质子溶剂,如环丁砜、二甲亚砜、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAC)、1,3-二甲基-2-咪唑烷酮(DMI)、N,N′-二甲基亚丙基脲(DMPU)、二甲亚砜(DMSO)和1-甲基-2-吡咯烷酮(NMP)。本文所用的术语溶剂还包括两种或更多种溶剂的混合物。
优选的溶剂为如上所定义的醚类、腈类和偶极非质子溶剂。
更优选的溶剂为如上所定义的腈类。
式(IX)的胍与式(II)的胺的反应在酸存在下进行。
合适酸的实例为无机酸如氢氟酸、盐酸、氢溴酸、氢碘酸、磷酸、硫酸;对甲苯磺酸;路易斯酸如三氟化硼、氯化铝、氯化铁III、氯化锡IV、氯化钛IV和氯化锌II,以及有机酸如甲酸、乙酸、丙酸、草酸、甲基苯磺酸、苯磺酸、樟脑磺酸、柠檬酸、三氟乙酸。
酸通常过量使用,或者合适的话,可以用作溶剂。
后处理可以以已知方式进行。
制备式(VII)的双胍所要求的式(IX)的胍可市购或者可以根据文献程序制备(例如J.L.LaMattina等,J.Med.Chem.1990,33,543-552;A.Perez-Medrano等,J.Med.Chem.2009,52,3366-3376)。
制备式(VII)的双胍所要求的式(II)的胺可市购或可根据已知文献程序制备(例如Barnes等人,WO/2007/067612)。
式(I)化合物具有除草活性。因此,它们可以用于控制不想要或不希望的植物或植物生长。它们还可以用于控制不想要或不希望的植物或植物生长的方法中,该方法包括使至少一种式(I)化合物或其盐作用于植物、其环境或种子上。为了使式(I)化合物或其盐作用于植物、其环境或种子上,将本发明化合物施用于植物、其环境或所述植物的种子。
为了拓宽作用谱并实现协同增效效果,可以将式(I)的二氨基三嗪化合物与大量其他除草或生长调节活性成分组的代表混合并随后同时施用。
适合混合物的组分例如为选自如下类别的除草剂:乙酰胺类、酰胺类、芳氧基苯氧基丙酸酯类、苯甲酰胺类、苯并呋喃、苯甲酸类、苯并噻二嗪酮类、联吡啶氨基甲酸酯类、氯代乙酰胺类、氯代羧酸、环己烷二酮类、二硝基苯胺类、二硝基苯酚类、二苯基醚、甘氨酸类、咪唑啉酮类、异唑类、异唑烷酮类、腈类、N-苯基苯邻二甲酰亚胺类、二唑类、唑烷二酮类、羟乙酰胺类、苯氧基羧酸类、苯基氨基甲酸酯类、苯基吡唑类、苯基吡唑啉类、苯基哒嗪类、次膦酸类、氨基磷酸酯类、二硫代磷酸酯类、邻氨甲酰苯甲酸酯类、吡唑类、哒嗪酮类、吡啶类、吡啶羧酸类、吡啶羧酰胺类、嘧啶二酮类、嘧啶基(硫代)苯甲酸酯类、喹啉羧酸类、缩氨基脲类、磺酰氨基羰基三唑啉酮类、磺酰脲类、四唑啉酮类、噻二唑类、硫代氨基甲酸酯类、三嗪类、三嗪酮类、三唑类、三唑啉酮类、三唑并羧酰胺类、三唑并嘧啶类、三酮类、尿嘧啶类、脲类。
本发明还涉及式(I)的二氨基三嗪化合物与至少一种其他除草剂B和/或至少一种安全剂C)的组合。
其他除草化合物B(组分B)尤其选自b1)-b15)类除草剂:
b1)类脂生物合成抑制剂;
b2)乙酰乳酸合成酶抑制剂(ALS抑制剂);
b3)光合成抑制剂;
b4)原卟啉原-IX氧化酶抑制剂,
b5)漂白剂除草剂;
b6)烯醇丙酮酰莽草酸3-磷酸合成酶抑制剂(EPSP抑制剂);
b7)谷氨酰胺合成酶抑制剂;
b8)7,8-二氢蝶酸合成酶抑制剂(DHP抑制剂);
b9)有丝分裂抑制剂;
b10)非常长链脂肪酸合成抑制剂(VLCFA抑制剂);
b11)纤维素生物合成抑制剂;
b12)去偶剂除草剂;
b13)植物生长素除草剂;
b14)植物生长素输送抑制剂;以及
b15)选自如下的其他除草剂:溴丁酰草胺(bromobutide)、氯甲丹(chlorflurenol)、氯甲丹(chlorflurenol-methyl)、环庚草醚(cinmethylin)、苄草隆(cumyluron)、茅草枯(dalapon)、棉隆(dazomet)、苯敌快(difenzoquat)、苯敌快(difenzoquat-metilsulfate)、噻节因(dimethipin)、甲胂钠(DSMA)、香草隆(dymron)、敌草腈(endothal)及其盐、乙苯酰草(etobenzanid)、氟燕灵(flamprop)、氟燕灵(flamprop-isopropyl)、甲氟燕灵(flamprop-methyl)、强氟燕灵(flamprop-M-isopropyl)、麦草伏(flamprop-M-methyl)、抑草丁(flurenol)、抑草丁(flurenol-butyl)、调嘧醇(flurprimidol)、膦铵素(fosamine)、膦铵素(fosamine-ammonium)、茚草酮(indanofan)、茚嗪氟草胺(indaziflam)、抑芽丹(maleic hydrazide)、氟草磺(mefluidide)、威百亩(metam)、methiozolin(CAS 403640-27-7)、叠氮甲烷(methyl azide)、溴甲烷(methylbromide)、苯丙隆(methyl-dymron)、碘甲烷(methyl iodide)、甲胂一钠(MSMA)、油酸(oleic acid)、氯嗪草(oxaziclomefone)、壬酸(pelargonic acid)、稗草畏(pyributicarb)、灭藻醌(quinoclamine)、苯氧丙胺津(triaziflam)、灭草环(tridiphane)和6-氯-3-(2-环丙基-6-甲基苯氧基)-4-哒嗪醇(CAS 499223-49-3)及其盐和酯;
包括其可农用盐或衍生物如醚、酯或酰胺。
优选包含至少一种选自b1、b6、b9、b10和b11类除草剂的除草剂B的那些本发明组合物。
可以与本发明的式(I)化合物组合使用的除草剂B的实例为:
b1)选自如下的类脂生物合成抑制剂:ACC除草剂如枯杀达(alloxydim)、枯杀达(alloxydim-sodium)、丁氧环酮(butroxydim)、烯草酮(clethodim)、炔草酯(clodinafop)、炔草酯(clodinafop-propargyl)、噻草酮(cycloxydim)、氰氟草酯(cyhalofop)、氰氟草酯(cyhalofop-butyl)、氯甲草(diclofop)、禾草灵(diclofop-methyl)、唑禾草灵(fenoxaprop)、唑禾草灵(fenoxaprop-ethyl)、高唑禾草灵(fenoxaprop-P)、高唑禾草灵(fenoxaprop-P-ethyl)、吡氟禾草灵(fluazifop)、吡氟禾草灵(fluazifop-butyl)、精吡氟禾草灵(fluazifop-P)、精吡氟禾草灵(fluazifop-P-butyl)、吡氟氯禾灵(haloxyfop)、吡氟氯禾灵(haloxyfop-methyl)、精吡氟氯禾灵(haloxyfop-P)、精吡氟氯禾灵(haloxyfop-P-methyl)、唑酰草胺(metamifop)、唑啉草酯(pinoxaden)、环苯草酮(profoxydim)、喔草酯(propaquizafop)、喹禾灵(quizalofop)、喹禾灵(quizalofop-ethyl)、喹禾灵(四氢糠基酯)(quizalofop-tefuryl)、精喹禾灵(quizalofop-P)、精喹禾灵(quizalofop-P-ethyl)、精喹禾灵(四氢糠基酯)(quizalofop-P-tefuryl)、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim)、4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS1312337-72-6)、4-(2',4'-二氯-4-环丙基[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS1312337-45-3)、4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS1033757-93-5)、4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-2,2,6,6-四甲基-2H-吡喃-3,5(4H,6H)-二酮(CAS1312340-84-3)、5-乙酰氧基-4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS1312337-48-6)、5-乙酰氧基-4-(2',4'-二氯-4-环丙基-[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮、5-乙酰氧基-4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS1312340-82-1)、5-乙酰氧基-4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS1033760-55-2)、4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS1312337-51-1)、4-(2',4'-二氯-4-环丙基-[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯、4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS 1312340-83-2)、4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS1033760-58-5);以及非ACC除草剂如呋草黄(benfuresate)、苏达灭(butylate)、草灭特(cycloate)、茅草枯(dalapon)、哌草丹(dimepiperate)、扑草灭(EPTC)、禾草畏(esprocarb)、乙呋草黄(ethofumesate)、四氟丙酸(flupropanate)、草达灭(molinate)、坪草丹(orbencarb)、克草猛(pebulate)、苄草丹(prosulfocarb)、TCA、杀草丹(thiobencarb)、丁草威(tiocarbazil)、野麦畏(triallate)和灭草猛(vernolate);
b2)选自如下的ALS抑制剂:磺酰脲类,如磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron)、苄嘧黄隆(bensulfuron-methyl)、氯嘧黄隆(chlorimuron)、氯嘧黄隆(chlorimuron-ethyl)、绿黄隆(chlorsulfuron)、醚黄隆(cinosulfuron)、环丙黄隆(cyclosulfamuron)、胺苯黄隆(ethametsulfuron)、胺苯黄隆(ethametsulfuron-methyl)、乙氧嘧黄隆(ethoxysulfuron)、啶嘧黄隆(flazasulfuron)、氟吡磺隆(flucetosulfuron)、氟定黄隆(flupyrsulfuron)、氟定黄隆(flupyrsulfuron-methyl-sodium)、甲酰氨磺隆(foramsulfuron)、吡氯黄隆(halosulfuron)、吡氯黄隆(halosulfuron-methyl)、啶咪黄隆(imazosulfuron)、碘黄隆(iodosulfuron)、碘甲黄隆钠(iodosulfuron-methyl-sodium)、iofensulfuron、iofensulfuron-sodium、甲基二磺隆(mesosulfuron)、metazosulfuron、甲黄隆(metsulfuron)、甲黄隆(metsulfuron-methyl)、烟嘧黄隆(nicosulfuron)、嘧苯胺磺隆(orthosulfamuron)、环丙氧黄隆(oxasulfuron)、氟嘧黄隆(primisulfuron)、氟嘧黄隆(primisulfuron-methyl)、propyrisulfuron、氟丙黄隆(prosulfuron)、吡嘧黄隆(pyrazosulfuron)、吡嘧黄隆(pyrazosulfuron-ethyl)、玉嘧黄隆(rimsulfuron)、嘧黄隆(sulfometuron)、嘧黄隆(sulfometuron-methyl)、乙黄黄隆(sulfosulfuron)、噻黄隆(thifensulfuron)、噻黄隆(thifensulfuron-methyl)、醚苯黄隆(triasulfuron)、苯黄隆(tribenuron)、苯黄隆(tribenuron-methyl)、三氟啶磺隆(trifloxysulfuron)、氟胺磺隆(triflusulfuron)、氟胺磺隆(triflusulfuron-methyl)和三氟甲磺隆(tritosulfuron),咪唑啉酮类如咪草酯(imazamethabenz)、咪草酯(imazamethabenz-methyl)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)和咪草烟(imazethapyr),三唑并嘧啶类除草剂和磺酰苯胺类如唑嘧磺胺酸(cloransulam)、唑嘧磺胺盐(cloransulam-methyl)、唑嘧磺胺(diclosulam)、氟唑啶草(flumetsulam)、双氟磺草胺(florasulam)、唑草磺胺(metosulam)、五氟磺草胺(penoxsulam)、pyrimisulfan和啶磺草胺(pyroxsulam),嘧啶基苯甲酸酯类如双嘧苯甲酸(bispyribac)、双嘧苯甲酸钠(bispyribac-sodium)、嘧啶肟草醚(pyribenzoxim)、环酯草醚(pyriftalid)、肟啶草(pyriminobac)、肟啶草(pyriminobac-methyl)、嘧硫苯甲酸(pyrithiobac)、嘧硫苯甲酸钠(pyrithiobac-sodium)、4-[[[2-[(4,6-二甲氧基-2-嘧啶基)氧基]苯基]甲基]氨基]苯甲酸1-甲基乙基酯(CAS 420138-41-6)、4-[[[2-[(4,6-二甲氧基-2-嘧啶基)氧基]苯基]甲基]氨基]苯甲酸丙基酯(CAS 420138-40-5)、N-(4-溴苯基)-2-[(4,6-二甲氧基-2-嘧啶基)氧基]苯甲胺(CAS 420138-01-8),磺酰氨基羰基三唑啉酮类除草剂如氟酮磺隆(flucarbazone)、氟酮磺隆钠(flucarbazone-sodium)、丙苯磺隆(propoxycarbazone)、丙苯磺隆(propoxycarbazone-sodium)、thiencarbazone和thiencarbazone-methyl,以及氟酮磺草胺(triafamone);其中本发明的一个优选实施方案涉及包含至少一种咪唑啉酮类除草剂的那些组合物;
b3)选自如下的光合成抑制剂:胺唑草酮(amicarbazone),光合系统II抑制剂,例如1-(6-叔丁基嘧啶-4-基)-2-羟基-4-甲氧基-3-甲基-2H-吡咯-5-酮(CAS1654744-66-7)、1-(5-叔丁基异唑-3-基)-2-羟基-4-甲氧基-3-甲基-2H-吡咯-5-酮(CAS1637455-12-9)、1-(5-叔丁基异唑-3-基)-4-氯-2-羟基-3-甲基-2H-吡咯-5-酮(CAS1637453-94-1)、1-(5-叔丁基-1-甲基吡唑-3-基)-4-氯-2-羟基-3-甲基-2H-吡咯-5-酮(CAS1654057-29-0)、1-(5-叔丁基-1-甲基吡唑-3-基)-3-氯-2-羟基-4-甲基-2H-吡咯-5-酮(CAS1654747-80-4)、4-羟基-1-甲氧基-5-甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS2023785-78-4)、4-羟基-1,5-二甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS2023785-79-5)、5-乙氧基-4-羟基-1-甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS 1701416-69-4)、4-羟基-1-甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS1708087-22-2)、4-羟基-1,5-二甲基-3-[1-甲基-5-三氟甲基吡唑-3-基]咪唑烷-2-酮(CAS2023785-80-8)、1-(5-叔丁基异唑-3-基)-4-乙氧基-5-羟基-3-甲基咪唑烷-2-酮(CAS1844836-64-1),三嗪类除草剂,包括氯代三嗪类、三嗪酮类、三嗪二酮类、甲硫基三嗪类和哒嗪酮类,如莠灭净(ametryn)、莠去津(atrazine)、杀草敏(chloridazone)、草净津(cyanazine)、敌草净(desmetryn)、戊草津(dimethametryn)、六嗪同(hexazinone)、赛克津(metribuzin)、扑灭通(prometon)、扑草净(prometryn)、扑灭津(propazine)、西玛津(simazine)、西草净(simetryn)、甲氧去草净(terbumeton)、特丁津(terbuthylazin)、去草净(terbutryn)和草达津(trietazin);芳基脲类如氯溴隆(chlorobromuron)、绿麦隆(chlorotoluron)、枯草隆(chloroxuron)、丁隆(dimefuron)、敌草隆(diuron)、伏草隆(fluometuron)、异丙隆(isoproturon)、异恶隆(isouron)、利谷隆(linuron)、苯嗪草(metamitron)、噻唑隆(methabenzthiazuron)、色满隆(metobenzuron)、甲氧隆(metoxuron)、绿谷隆(monolinuron)、草不隆(neburon)、环草隆(siduron)、丁唑隆(tebuthiuron)和赛二唑素(thidiazuron),苯基氨基甲酸酯类如异苯敌草(desmedipham)、卡草灵(karbutilat)、苯敌草(phenmedipham)、乙苯敌草(phenmedipham-ethyl),腈类除草剂如杀草全(bromofenoxim)、溴苯腈(bromoxynil)及其盐和酯、碘苯腈(ioxynil)及其盐和酯,尿嘧啶类如除草定(bromacil)、环草定(lenacil)和特草定(terbacil),以及噻草平(bentazon)和噻草平(bentazon-sodium),达草止(pyridate)、pyridafol、蔬草灭(pentanochlor)和敌稗(propanil)以及光合系统I抑制剂如敌草快阳离子(diquat)、敌草快(diquat-dibromide)、对草快阳离子(paraquat)、对草快(paraquat-dichloride)和对草快(paraquat-dimetilsulfate)。其中本发明的一个优选实施方案涉及包含至少一种芳基脲类除草剂的那些组合物。其中本发明的一个优选实施方案同样涉及包含至少一种三嗪类除草剂的那些组合物。其中本发明的一个优选实施方案同样涉及包含至少一种腈类除草剂的那些除草剂;
b4)选自如下的原卟啉原-IX氧化酶抑制剂:氟锁草醚(acifluorfen)、氟锁草醚(acifluorfen-sodium)、唑啶炔草(azafenidin)、bencarbazone、双苯嘧草酮(benzfendizone)、治草醚(bifenox)、氟丙嘧草酯(butafenacil)、氟酮唑草(carfentrazone)、氟酮唑草(carfentrazone-ethyl)、氯硝醚(chlomethoxyfen)、吲哚酮草酯(cinidon-ethyl)、异丙吡草酯(fluazolate)、氟哒嗪草酯(flufenpyr)、氟哒嗪草酯(flufenpyr-ethyl)、酰亚胺苯氧乙酸(flumiclorac)、酰亚胺苯氧乙酸戊酯(flumiclorac-pentyl)、氟嗪酮(flumioxazin)、乙羧氟草醚(fluoroglycofen)、乙羧氟草醚(fluoroglycofen-ethyl)、达草氟(fluthiacet)、达草氟(fluthiacet-methyl)、氟黄胺草醚(fomesafen)、氟硝磺酰胺(halosafen)、乳氟禾草灵(lactofen)、炔丙唑草(oxadiargyl)、恶草灵(oxadiazon)、乙氧氟草醚(oxyfluorfen)、戊唑草(pentoxazone)、氟唑草胺(profluazol)、双唑草腈(pyraclonil)、氟唑草酯(pyraflufen)、氟唑草酯(pyraflufen-ethyl)、苯嘧磺草胺(saflufenacil)、磺胺草唑(sulfentrazone)、噻二唑胺(thidiazimin)、tiafenacil、trifludimoxazin、epyrifenacil、N-乙基-3-(2,6-二氯-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS 452098-92-9)、N-四氢糠基-3-(2,6-二氯-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS 915396-43-9)、N-乙基-3-(2-氯-6-氟-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS 452099-05-7)、N-四氢糠基-3-(2-氯-6-氟-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS 452100-03-7)、3-[7-氟-3-氧代-4-(丙-2-炔基)-3,4-二氢-2H-苯并[1,4]嗪-6-基]-1,5-二甲基-6-硫代-[1,3,5]三嗪烷(triazinan)-2,4-二酮、1,5-二甲基-6-硫代-3-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[b][1,4]嗪-6-基)-[1,3,5]三嗪烷-2,4-二酮(CAS1258836-72-4)、2-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[b][1,4]嗪-6-基)-4,5,6,7-四氢异吲哚-1,3-二酮、1-甲基-6-三氟甲基-3-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[1,4]嗪-6-基)-1H-嘧啶-2,4-二酮、(E)-4-[2-氯-5-(4-氯-5-二氟甲氧基-1H-甲基吡唑-3-基)-4-氟苯氧基]-3-甲氧基丁-2-烯酸甲酯(CAS948893-00-3)和3-[7-氯-5-氟-2-三氟甲基-1H-苯并咪唑-4-基]-1-甲基-6-三氟甲基-1H-嘧啶-2,4-二酮(CAS212754-02-4);2-[2-氯-5-[3-氯-5-(三氟甲基)-2-吡啶基]-4-氟苯氧基]-2-甲氧基乙酸甲酯(CAS 1970221-16-9)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]-乙酸甲酯(CAS2158274-96-3)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]乙酸乙酯(CAS 158274-50-9)、2-[[3-[2-氯-5-[4-(二氟甲基)-3-甲基-5-氧代-1,2,4-三唑-1-基]-4-氟苯氧基]-2-吡啶基]氧基]乙酸甲酯(CAS2271389-22-9)、2-[[3-[2-氯-5-[4-(二氟甲基)-3-甲基-5-氧代-1,2,4-三唑-1-基]-4-氟苯氧基]-2-吡啶基]氧基]乙酸乙酯(CAS2230679-62-4)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]-乙酸甲酯(CAS2158275-73-9)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]乙酸乙酯(CAS2158274-56-5)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]-N-(甲基磺酰基)-乙酰胺(CAS2158274-53-2)、2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]-N-(甲基磺酰基)-乙酰胺(CAS2158276-22-1)、3-[2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-4-氟苯基]-4,5-二氢-5-甲基-5-异唑甲酸乙酯(CAS1949837-17-5);
b5)选自如下的漂白剂除草剂:PDS抑制剂:氟丁酰草胺(beflubutamid)、吡氟草胺(diflufenican)、氟草同(fluridone)、氟咯草酮(flurochloridone)、呋草酮(flurtamone)、达草灭(norflurazon)、氟吡酰草胺(picolinafen)和4-(3-三氟甲基苯氧基)-2-(4-三氟甲基苯基)嘧啶(CAS180608-33-7),HPPD抑制剂:苯并双环酮(benzobicyclon)、吡草酮(benzofenap)、氟吡草酮(bicyclopyrone)、异恶草酮(clomazone)、fenquintrione、异氟草(isoxaflutole)、甲基磺草酮(mesotrione)、oxotrione(CAS1486617-21-3)、pyrasulfotole、吡唑特(pyrazolynate)、苄草唑(pyrazoxyfen)、磺草酮(sulcotrione)、tefuryltrione、tembotrione、tolpyralate、托普拉威(topramezone),漂白剂,未知目标:苯草醚(aclonifen)、杀草强(amitrole)、伏草隆(flumeturon)、2-氯-3-甲硫基-N-(1-甲基四唑-5-基)-4-三氟甲基苯甲酰胺(CAS1361139-71-0)、二氯异草酮(bixlozone)和2-(2,5-二氯苯基)甲基-4,4-二甲基-3-异唑烷酮(CAS 81778-66-7)、3-氯-2-[-3-(二氟甲基)异唑-5-基]苯基-5-氯嘧啶-2-基-醚、双唑草酮(bipyrazone)、苯唑氟草酮(fenpyrazone)、环吡氟草酮(cypyrafluone)、三唑磺草酮(tripyrasulfone)、benquinotrione、2-(3,4-二甲氧基苯基)-4-[2-羟基-6-氧代环己-1-烯-1基)羰基]-6-甲基哒嗪-3(2H)-酮;
b6)选自如下的EPSP合成酶抑制剂:草甘膦(glyphosate)、草甘膦异丙胺盐(glyphosate-isopropylammonium)、草甘膦钾和草硫膦(glyphosate-trimesium)(sulfosate);
b7)选自如下的谷氨酰胺合成酶抑制剂:双丙氨酰膦(bilanaphos(bialaphos))、双丙氨酰膦(bilanaphos-sodium)、草铵膦(glufosinate)、草铵膦(glufosinate-P)和草铵膦铵盐(glufosinate-ammonium);
b8)选自如下的DHP合成酶抑制剂:黄草灵(asulam);
b9)选自如下的有丝分裂抑制剂:K1组化合物:二硝基苯胺类如氟草胺(benfluralin)、地乐胺(butralin)、敌乐胺(dinitramine)、丁氟消草(ethalfluralin)、氟消草(fluchloralin)、黄草消(oryzalin)、胺硝草(pendimethalin)、氨基丙氟灵(prodiamine)和氟乐灵(trifluralin),氨基磷酸酯类如胺草磷(amiprophos)、甲基胺草磷(amiprophos-methyl)和草胺磷(butamiphos),苯甲酸类除草剂如敌草索(chlorthal)、敌草索(chlorthal-dimethyl),吡啶类如氟硫草定(dithiopyr)和噻氟啶草(thiazopyr),苯甲酰胺类如拿草特(propyzamide)和丙戊草胺(tebutam),K2组化合物:氯苯胺灵(chlorpropham)、苯胺灵(propham)和长杀草(carbetamide);其中优选K1组化合物,尤其优选二硝基苯胺类;
b10)选自如下的VLCFA抑制剂:氯乙酰胺类如乙草胺(acetochlor)、甲草胺(alachlor)、丁草胺(butachlor)、克草胺(dimethachlor)、噻吩草胺(dimethanamid)、精噻吩草胺(dimethenamid-P)、吡草胺(metazachlor)、异丙甲草胺(metolachlor)、S-异丙甲草胺(metolachlor-S)、烯草胺(pethoxamid)、丙草胺(pretilachlor)、扑草胺(propachlor)、异丙草胺(propisochlor)和噻醚草胺(thenylchlor),羟基乙酰苯胺类(oxyacetanilide)如氟噻草胺(flufenacet)和苯噻草胺(mefenacet),乙酰苯胺类如草乃敌(diphenamid)、萘丙胺(naproanilide)、草萘胺(napropamide)和精草萘胺(napropamide-M),四唑啉酮类如四唑酰草胺(fentrazamide)以及其他除草剂如莎稗磷(anilofos)、唑草胺(cafenstrole)、fenoxasulfone、ipfencarbazone、哌草磷(piperophos)、派罗克杀草砜(pyroxasulfone)及II.1、II.2、II.3、II.4、II.5、II.6、II.7、II.8和II.9的异唑啉化合物:
式(II)的异唑啉化合物在本领域中是已知的,例如由WO 2006/024820、WO2006/037945、WO 2007/071900和WO 2007/096576已知;
在VLCFA抑制剂中,优选氯代乙酰胺类和羟基乙酰胺类;
b11)选自如下的纤维素生物合成抑制剂:草克乐(chlorthiamid)、敌草腈(dichlobenil)、胺草唑(flupoxam)、异恶草胺(isoxaben)和1-环己基-5-五氟苯氧基-14-[1,2,4,6]硫杂三嗪-3-基胺:
b12)选自如下的去偶剂除草剂:地乐酚(dinoseb)、地乐消酚(dinoterb)以及二硝甲酚(DNOC)及其盐;
b13)选自如下的植物生长素除草剂:2,4-D及其盐和酯,如氯酰草膦(clacyfos),2,4-DB及其盐和酯,环丙嘧啶酸(aminocyclopyrachlor)及其盐和酯,氨草啶(aminopyralid)及其盐如氨草啶二甲铵盐(aminopyralid-dimethylammonium)、氨草啶异丙醇铵盐(aminopyralid-tris(2-hydroxypropyl)ammonium)及其酯,草除灵(benazolin),草除灵(benazolin-ethyl),草灭平(chloramben)及其盐和酯,稗草胺(clomeprop),二氯皮考啉酸(clopyralid)及其盐和酯,麦草畏(dicamba)及其盐和酯,2,4-滴丙酸(dichlorprop)及其盐和酯,高2,4-滴丙酸(dichlorprop-P)及其盐和酯,氟草烟(fluroxypyr),氟草烟(fluroxypyr-butometyl),氟氯胺啶(fluroxypyr-meptyl),氟氯吡啶酯(halauxifen)及其盐和酯(CAS 943832-60-8),MCPA及其盐和酯,2甲4氯乙硫酯(MCPA-thioethyl),MCPB及其盐和酯,2甲4氯丙酸(mecoprop)及其盐和酯,高2甲4氯丙酸(mecoprop-P)及其盐和酯,毒莠定(picloram)及其盐和酯,二氯喹啉酸(quinclorac),喹草酸(quinmerac),TBA(2,3,6)及其盐和酯以及绿草定(triclopyr)及其盐和酯;绿草定及其盐和酯,氯氟吡啶酯(florpyrauxifen),氯氟吡啶酯(florpyrauxifen-benzyl)(CAS1390661-72-9)和4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶甲酸(CAS1629965-65-6)
b14)选自如下的植物生长素输送抑制剂:二氟吡隆(diflufenzopyr)、二氟
吡隆钠(diflufenzopyr-sodium)、抑草生(naptalam)和抑草生(naptalam-sodium);
b15)选自如下的其他除草剂:溴丁酰草胺(bromobutide)、氯甲丹(chlorflurenol)、氯甲丹(chlorflurenol-methyl)、环庚草醚(cinmethylin)、苄草隆(cumyluron)、6-氯-4-(2,7-二甲基-1-萘基)-5-羟基-2-甲基-哒嗪-3-酮(CAS2414510-21-5)、cyclopyrimorate(CAS
499223-49-3)及其盐和酯、茅草枯(dalapon)、棉隆(dazomet)、苯敌快(difenzoquat)、苯敌快(difenzoquat-metilsulfate)、噻节因(dimethipin)、甲胂钠(DSMA)、香草隆(dymron)、敌草腈(endothal)及其盐、乙苯酰草(etobenzanid)、氟燕灵(flamprop)、氟燕灵(flamprop-isopropyl)、甲氟燕灵(flamprop-methyl)、强氟燕灵(flamprop-M-isopropyl)、麦草伏(flamprop-M-methyl)、抑草丁(flurenol)、抑草丁(flurenol-butyl)、调嘧醇(flurprimidol)、膦铵素(fosamine)、膦铵素(fosamine-ammonium)、茚草酮(indanofan)、茚嗪氟草胺(indaziflam)、抑芽丹(maleic hydrazide)、氟草磺(mefluidide)、威百亩(metam)、methiozolin(CAS 403640-27-7)、叠氮甲烷(methylazide)、溴甲烷(methyl bromide)、苯丙隆(methyl-dymron)、碘甲烷(methyl iodide)、甲胂一钠(MSMA)、油酸(oleic acid)、氯嗪草(oxaziclomefone)、壬酸(pelargonic acid)、稗草畏(pyributicarb)、灭藻醌(quinoclamine)、苯氧丙胺津(triaziflam)和灭草环(tridiphane)。
可以与本发明化合物I组合使用的优选除草剂B为:
b1)选自如下的类脂生物合成抑制剂:烯草酮(clethodim)、炔草酯(clodinafop-propargyl)、噻草酮(cycloxydim)、氰氟草酯(cyhalofop-butyl)、禾草灵(diclofop-methyl)、高唑禾草灵(fenoxaprop-P-ethyl)、精吡氟禾草灵(fluazifop-P-butyl)、精吡氟氯禾灵(haloxyfop-P-methyl)、唑酰草胺(metamifop)、唑啉草酯(pinoxaden)、环苯草酮(profoxydim)、喔草酯(propaquizafop)、精喹禾灵(quizalofop-P-ethyl)、精喹禾灵(四氢糠基酯)(quizalofop-P-tefuryl)、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim)、4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS
1312337-72-6)、4-(2',4'-二氯-4-环丙基[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS1312337-45-3)、4-(4'-氯-4-乙基-2'-氟
[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS
1033757-93-5)、4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-2,2,6,6-四甲基-2H-吡喃-3,5(4H,6H)-二酮(CAS1312340-84-3)、5-乙酰氧基-4-(4'-氯
-4-环丙基-2'-氟[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS1312337-48-6)、5-乙酰氧基-4-(2',4'-二氯-4-环丙基-[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮、5-乙酰氧基-4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS1312340-82-1)、5-乙酰氧基-4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS1033760-55-2)、4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代
-2H-吡喃-3-基甲酸甲酯(CAS1312337-51-1)、4-(2',4'-二氯-4-环丙基
-[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯、4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS1312340-83-2)、4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS1033760-58-5)、呋草黄(benfuresate)、哌草丹(dimepiperate)、扑草灭(EPTC)、禾草畏(esprocarb)、乙呋草黄(ethofumesate)、草达灭(molinate)、坪草丹(orbencarb)、苄草丹(prosulfocarb)、杀草丹(thiobencarb)和野麦畏(triallate);
b2)选自如下的ALS抑制剂:磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron-methyl)、双嘧苯甲酸钠(bispyribac-sodium)、氯嘧黄隆(chlorimuron-ethyl)、绿黄隆(chlorsulfuron)、唑嘧磺胺盐(cloransulam-methyl)、环丙黄隆(cyclosulfamuron)、唑嘧磺胺(diclosulam)、胺苯黄隆(ethametsulfuron-methyl)、乙氧嘧黄隆(ethoxysulfuron)、啶嘧黄隆(flazasulfuron)、双氟磺草胺(florasulam)、氟酮磺隆钠(flucarbazone-sodium)、氟吡磺隆(flucetosulfuron)、氟唑啶草(flumetsulam)、氟定黄隆(flupyrsulfuron-methyl-sodium)、甲酰氨磺隆(foramsulfuron)、吡氯黄隆(halosulfuron-methyl)、咪草酯(imazamethabenz-methyl)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)、咪草烟(imazethapyr)、啶咪黄隆(imazosulfuron)、碘黄隆(iodosulfuron)、碘甲黄隆钠(iodosulfuron-methyl-sodium)、iofensulfuron、iofensulfuron-sodium、甲基二磺隆(mesosulfuron)、metazosulfuron、唑草磺胺(metosulam)、甲黄隆(metsulfuron-methyl)、烟嘧黄隆(nicosulfuron)、嘧苯胺磺隆(orthosulfamuron)、环丙氧黄隆(oxasulfuron)、五氟磺草胺(penoxsulam)、氟嘧黄隆(primisulfuron-methyl)、丙苯磺隆(propoxycarbazon-sodium)、propyrisulfuron、氟丙黄隆(prosulfuron)、吡嘧黄隆(pyrazosulfuron-ethyl)、嘧啶肟草醚(pyribenzoxim)、pyrimisulfan、环酯草醚(pyriftalid)、肟啶草(pyriminobac-methyl)、嘧硫苯甲酸钠(pyrithiobac-sodium)、啶磺草胺(pyroxsulam)、玉嘧黄隆(rimsulfuron)、嘧黄隆(sulfometuron-methyl)、乙黄黄隆(sulfosulfuron)、thiencarbazone-methyl、噻黄隆(thifensulfuron-methyl)、醚苯黄隆(triasulfuron)、苯黄隆(tribenuron-methyl)、三氟啶磺隆(trifloxysulfuron)、氟胺磺隆(triflusulfuron-methyl)、三氟甲磺隆(tritosulfuron)和氟酮磺草胺(triafamone);
b3)选自如下的光合成抑制剂:莠灭净(ametryn)、胺唑草酮(amicarbazone)、莠去津(atrazine)、噻草平(bentazone)、噻草平(bentazone-sodium)、溴苯腈(bromoxynil)及其盐和酯、杀草敏(chloridazone)、绿麦隆(chlorotoluron)、草净津(cyanazine)、异苯敌草(desmedipham)、敌草快(diquat-dibromide)、敌草隆(diuron)、伏草隆(fluometuron)、六嗪同(hexazinone)、碘苯腈(ioxynil)及其盐和酯、异丙隆(isoproturon)、环草定(lenacil)、利谷隆(linuron)、苯嗪草(metamitron)、噻唑隆(methabenzthiazuron)、赛克津(metribuzin)、对草快阳离子(paraquat)、对草快(paraquat-dichloride)、苯敌草(phenmedipham)、敌稗(propanil)、达草止(pyridate)、西玛津(simazine)、去草净(terbutryn)、特丁津(terbuthylazine)、赛二唑素(thidiazuron)、1-(6-叔丁基嘧啶-4-基)-2-羟基-4-甲氧基-3-甲基-2H-吡咯-5-酮(CAS1654744-66-7)、1-(5-叔丁基异唑-3-基)-2-羟基-4-甲氧基-3-甲基-2H-吡咯-5-酮(CAS 1637455-12-9)、1-(5-叔丁基异唑-3-基)-4-氯-2-羟基-3-甲基-2H-吡咯-5-酮(CAS1637453-94-1)、1-(5-叔丁基-1-甲基吡唑-3-基)-4-氯-2-羟基-3-甲基-2H-吡咯-5-酮(CAS1654057-29-0)、1-(5-叔丁基-1-甲基吡唑-3-基)-3-氯-2-羟基-4-甲基-2H-吡咯-5-酮(CAS1654747-80-4)、4-羟基-1-甲氧基-5-甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS 2023785-78-4)、4-羟基-1,5-二甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS 2023785-79-5)、5-乙氧基-4-羟基-1-甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS 1701416-69-4)、4-羟基-1-甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS 1708087-22-2)、4-羟基-1,5-二甲基-3-[1-甲基-5-三氟甲基吡唑-3-基]咪唑烷-2-酮(CAS 2023785-80-8)和1-(5-叔丁基异唑-3-基)-4-乙氧基-5-羟基-3-甲基咪唑烷-2-酮(CAS 1844836-64-1);
b4)选自如下的原卟啉原-IX氧化酶抑制剂:氟锁草醚(acifluorfen-sodium)、bencarbazone、双苯嘧草酮(benzfendizone)、氟丙嘧草酯(butafenacil)、氟酮唑草(carfentrazone-ethyl)、吲哚酮草酯(cinidon-ethyl)、cyclopyranil、氟哒嗪草酯(flufenpyr-ethyl)、酰亚胺苯氧乙酸戊酯(flumiclorac-pentyl)、氟嗪酮(flumioxazin)、乙羧氟草醚(fluoroglycofen-ethyl)、氟黄胺草醚(fomesafen)、乳氟禾草灵(lactofen)、炔丙唑草(oxadiargyl)、恶草灵(oxadiazon)、乙氧氟草醚(oxyfluorfen)、戊唑草(pentoxazone)、氟唑草酯(pyraflufen)、氟唑草酯(pyraflufen-ethyl)、苯嘧磺草胺(saflufenacil)、磺胺草唑(sulfentrazone)、tiafenacil、trifludimoxazin、[3-[2-氯-4-氟-5-(1-甲基-6-三氟甲基-2,4-二氧代-1,2,3,4-四氢嘧啶-3-基)苯氧基]-2-吡啶氧基]乙酸乙酯(CAS 353292-31-6;S-3100)、N-乙基-3-(2,6-二氯-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS 452098-92-9)、N-四氢糠基-3-(2,6-二氯-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS 915396-43-9)、N-乙基-3-(2-氯-6-氟-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS 452099-05-7)、N-四氢糠基-3-(2-氯-6-氟-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS452100-03-7)、3-[7-氟-3-氧代-4-(丙-2-炔基)-3,4-二氢-2H-苯并[1,4]嗪-6-基]-1,5-二甲基-6-硫代-[1,3,5]三嗪烷-2,4-二酮(CAS 451484-50-7)、2-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[b][1,4]嗪-6-基)-4,5,6,7-四氢异吲哚-1,3-二酮(CAS1300118-96-0)、1-甲基-6-三氟甲基-3-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[1,4]嗪-6-基)-1H-嘧啶-2,4-二酮(CAS1304113-05-0)和3-[7-氯-5-氟-2-(三氟甲基)-1H-苯并咪唑-4-基]-1-甲基-6-(三氟甲基)-1H-嘧啶-2,4-二酮(CAS212754-02-4)、2-[2-氯-5-[3-氯-5-(三氟甲基)-2-吡啶基]-4-氟苯氧基]-2-甲氧基乙酸甲酯(CAS1970221-16-9)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]-乙酸甲酯(CAS 2158274-96-3)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]乙酸乙酯(CAS 158274-50-9)、2-[[3-[2-氯-5-[4-(二氟甲基)-3-甲基-5-氧代-1,2,4-三唑-1-基]-4-氟苯氧基]-2-吡啶基]氧基]乙酸甲酯(CAS2271389-22-9)、2-[[3-[2-氯-5-[4-(二氟甲基)-3-甲基-5-氧代-1,2,4-三唑-1-基]-4-氟苯氧基]-2-吡啶基]氧基]乙酸乙酯(CAS2230679-62-4)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]-乙酸甲酯(CAS2158275-73-9)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]乙酸乙酯(CAS2158274-56-5)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]-N-(甲基磺酰基)-乙酰胺(CAS2158274-53-2)、2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]-N-(甲基磺酰基)-乙酰胺(CAS2158276-22-1);
b5)选自如下的漂白剂除草剂:苯草醚(aclonifen)、杀草强(amitrole)、氟丁酰草胺(beflubutamid)、苯并双环酮(benzobicyclon)、氟吡草酮(bicyclopyrone)、异恶草酮(clomazone)、吡氟草胺(diflufenican)、fenquinotrione、flumeturon、氟咯草酮(flurochloridone)、呋草酮(flurtamone)、异氟草(isoxaflutole)、甲基磺草酮(mesotrione)、oxotrione(CAS1486617-21-3)、达草灭(norflurazon)、氟吡酰草胺(picolinafen)、pyrasulfotole、吡唑特(pyrazolynate)、磺草酮(sulcotrione)、tefuryltrione、tembotrione、tolpyralate、topramezone、4-(3-三氟甲基苯氧基)-2-(4-三氟甲基苯基)嘧啶(CAS 180608-33-7)、2-氯-3-甲硫基-N-(1-甲基四唑-5-基)-4-三氟甲基苯甲酰胺(CAS1361139-71-0)、二氯异草酮(bixlozone)和2-(2,5-二氯苯基)甲基-4,4-二甲基-3-异唑烷酮(CAS 81778-66-7);
b6)选自如下的EPSP合成酶抑制剂:草甘膦、草甘膦异丙胺盐(glyphosate-isopropylammonium)、草甘膦钾和草硫膦(glyphosate-trimesium)(sulfosate);
b7)选自如下的谷氨酰胺合成酶抑制剂:草铵膦、草铵膦(glufosinate-P)和草铵膦铵盐(glufosinate-ammonium);
b8)选自如下的DHP合成酶抑制剂:黄草灵(asulam);
b9)选自如下的有丝分裂抑制剂:氟草胺(benfluralin)、氟硫草定(dithiopyr)、丁氟消草(ethalfluralin)、氟燕灵(flamprop)、氟燕灵(flamprop-isopropyl)、甲氟燕灵(flamprop-methyl)、强氟燕灵(flamprop-M-isopropyl)、麦草伏(flamprop-M-methyl)、黄草消(oryzalin)、胺硝草(pendimethalin)、噻氟啶草(thiazopyr)和氟乐灵(trifluralin);
b10)选自如下的VLCFA抑制剂:乙草胺(acetochlor)、甲草胺(alachlor)、amidochlor、莎稗磷(anilofos)、丁草胺(butachlor)、唑草胺(cafenstrole)、dimesulfazet、噻吩草胺(dimethanamid)、精噻吩草胺(dimethenamid-P)、四唑酰草胺(fentrazamide)、氟噻草胺(flufenacet)、苯噻草胺(mefenacet)、吡草胺(metazachlor)、异丙甲草胺(metolachlor)、S-异丙甲草胺(S-metolachlor)、萘丙胺(naproanilide)、草萘胺(napropamide)、精草萘胺(napropamide-M)、丙草胺(pretilachlor)、fenoxasulfone、ipfencarbazone、派罗克杀草砜(pyroxasulfone)、噻醚草胺(thenylchlor)以及如上所述式II.1、II.2、II.3、II.4、II.5、II.6、II.7、II.8和II.9的异唑啉化合物;
b11)选自如下的纤维素生物合成抑制剂:敌草腈(dichlobenil)、胺草唑(flupoxam)、茚嗪氟草胺(indaziflam)、异恶草胺(isoxaben)、苯氧丙胺津(triaziflam)和1-环己基-5-五氟苯氧基-14-[1,2,4,6]硫杂三嗪-3-基胺(CAS175899-01-1);
b13)选自如下的植物生长素除草剂:2,4-D及其盐和酯、环丙嘧啶酸及其盐和酯、氨草啶(aminopyralid)及其盐如氨草啶二甲铵盐(aminopyralid-dimethylammonium)、氨草啶异丙醇铵盐(aminopyralid-tris(2-hydroxypropyl)ammonium)和其酯、二氯皮考啉酸(clopyralid)及其盐和酯、麦草畏(dicamba)及其盐和酯、高2,4-滴丙酸(dichlorprop-P)及其盐和酯、flopyrauxifen、氟氯胺啶(fluroxypyr-meptyl)、氟氯吡啶酯(halauxifen)及其盐和酯(CAS 943832-60-8)、MCPA及其盐和酯、MCPB及其盐和酯、高2甲4氯丙酸(mecoprop-P)及其盐和酯、毒莠定(picloram)及其盐和酯、二氯喹啉酸(quinclorac)、喹草酸(quinmerac)、绿草定(triclopyr)及其盐和酯、氯氟吡啶酯(florpyrauxifen)、氯氟吡啶酯(florpyrauxifen-benzyl)(CAS1390661-72-9)和4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶甲酸(CAS1629965-65-6);
b14)选自如下的植物生长素输送抑制剂:二氟吡隆(diflufenzopyr)和二氟吡隆钠(diflufenzopyr-sodium);
b15)选自如下的其他除草剂:溴丁酰草胺(bromobutide)、环庚草醚(cinmethylin)、苄草隆(cumyluron)、6-氯-4-(2,7-二甲基-1-萘基)-5-羟基-2-甲基-哒嗪-3-酮(CAS2414510-21-5)、cyclopyrimorate(CAS 499223-49-3)及其盐和酯、茅草枯(dalapon)、苯敌快(difenzoquat)、苯敌快(difenzoquat-metilsulfate)、甲胂钠(DSMA)、香草隆(dymron)(=daimuron)、茚草酮(indanofan)、威百亩(metam)、溴甲烷(methylbromide)、甲胂一钠(MSMA)、氯嗪草(oxaziclomefone)、稗草畏(pyributicarb)、tetflupyrolimet和灭草环(tridiphane)。可以与本发明式I化合物组合使用的特别优选除草剂B为:
b1)选自如下的类脂生物合成抑制剂:炔草酯(clodinafop-propargyl)、噻草酮(cycloxydim)、氰氟草酯(cyhalofop-butyl)、高唑禾草灵(fenoxaprop-P-ethyl)、唑啉草酯(pinoxaden)、环苯草酮(profoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim)、4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS1312337-72-6)、4-(2',4'-二氯-4-环丙基[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS1312337-45-3)、4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS1033757-93-5)、4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-2,2,6,6-四甲基-2H-吡喃-3,5(4H,6H)-二酮(CAS1312340-84-3)、5-乙酰氧基-4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS1312337-48-6)、5-乙酰氧基-4-(2',4'-二氯-4-环丙基-[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮、5-乙酰氧基-4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS1312340-82-1)、5-乙酰氧基-4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS 1033760-55-2)、4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS1312337-51-1)、4-(2',4'-二氯-4-环丙基-[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯、4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS 1312340-83-2)、4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS1033760-58-5)、禾草畏(esprocarb)、苄草丹(prosulfocarb)、杀草丹(thiobencarb)和野麦畏(triallate);
b2)选自如下的ALS抑制剂:苄嘧黄隆(bensulfuron-methyl)、双嘧苯甲酸钠(bispyribac-sodium)、环丙黄隆(cyclosulfamuron)、唑嘧磺胺(diclosulam)、氟唑啶草(flumetsulam)、氟定黄隆(flupyrsulfuron-methyl-sodium)、甲酰氨磺隆(foramsulfuron)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)、咪草烟(imazethapyr)、啶咪黄隆(imazosulfuron)、碘黄隆(iodosulfuron)、碘甲黄隆钠(iodosulfuron-methyl-sodium)、iofensulfuron、iofensulfuron-sodium、甲基二磺隆(mesosulfuron)、metazosulfuron、烟嘧黄隆(nicosulfuron)、五氟磺草胺(penoxsulam)、丙苯磺隆(propoxycarbazon-sodium)、propyrisulfuron、吡嘧黄隆(pyrazosulfuron-ethyl)、啶磺草胺(pyroxsulam)、玉嘧黄隆(rimsulfuron)、乙黄黄隆(sulfosulfuron)、thiencarbazon-methyl、三氟甲磺隆(tritosulfuron)和氟酮磺草胺(triafamone);
b3)选自如下的光合成抑制剂:莠灭净(ametryn)、莠去津(atrazine)、敌草隆(diuron)、伏草隆(fluometuron)、六嗪同(hexazinone)、异丙隆(isoproturon)、利谷隆(linuron)、赛克津(metribuzin)、对草快阳离子(paraquat)、对草快(paraquat-dichloride)、敌稗(propanil)、去草净(terbutryn)、特丁津(terbuthylazine)、1-(5-叔丁基异唑-3-基)-2-羟基-4-甲氧基-3-甲基-2H-吡咯-5-酮(CAS1637455-12-9)、1-(5-叔丁基异唑-3-基)-4-氯-2-羟基-3-甲基-2H-吡咯-5-酮(CAS 1637453-94-1)、1-(5-叔丁基异唑-3-基)-4-乙氧基-5-羟基-3-甲基咪唑烷-2-酮(CAS1844836-64-1);
b4)选自如下的原卟啉原-IX氧化酶抑制剂:cyclopyranil、氟嗪酮(flumioxazin)、乙氧氟草醚(oxyfluorfen)、氟唑草酯(pyraflufen)、氟唑草酯(pyraflufen-ethyl)、嘧啶肟草醚(saflufenacil)、磺胺草唑(sulfentrazone)、trifludimoxazin、[3-[2-氯-4-氟-5-(1-甲基-6-三氟甲基-2,4-二氧代-1,2,3,4-四氢嘧啶-3-基)苯氧基]-2-吡啶氧基]乙酸乙酯(CAS 353292-31-6;S-3100)、3-[7-氟-3-氧代-4-(丙-2-炔基)-3,4-二氢-2H-苯并[1,4]嗪-6-基]-1,5-二甲基-6-硫代-[1,3,5]三嗪烷-2,4-二酮(CAS 451484-50-7)、2-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[b][1,4]嗪-6-基)-4,5,6,7-四氢异吲哚-1,3-二酮(CAS1300118-96-0)和1-甲基-6-三氟甲基-3-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[1,4]嗪-6-基)-1H-嘧啶-2,4-二酮(CAS1304113-05-0)、2-[2-氯-5-[3-氯-5-(三氟甲基)-2-吡啶基]-4-氟苯氧基]-2-甲氧基乙酸甲酯(CAS 1970221-16-9)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]-乙酸甲酯(CAS2158274-96-3)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]乙酸乙酯(CAS 158274-50-9)、2-[[3-[2-氯-5-[4-(二氟甲基)-3-甲基-5-氧代-1,2,4-三唑-1-基]-4-氟苯氧基]-2-吡啶基]氧基]乙酸甲酯(CAS2271389-22-9)、2-[[3-[2-氯-5-[4-(二氟甲基)-3-甲基-5-氧代-1,2,4-三唑-1-基]-4-氟苯氧基]-2-吡啶基]氧基]乙酸乙酯(CAS2230679-62-4)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]-乙酸甲酯(CAS2158275-73-9)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]乙酸乙酯(CAS2158274-56-5)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]-N-(甲基磺酰基)-乙酰胺(CAS2158274-53-2)、2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]-N-(甲基磺酰基)-乙酰胺(CAS2158276-22-1);
b5)选自如下的漂白剂除草剂:杀草强(amitrole)、氟吡草酮(bicyclopyrone)、异恶草酮(clomazone)、吡氟草胺(diflufenican)、fenquinotrione、flumeturon、氟咯草酮(flurochloridone)、异氟草(isoxaflutole)、甲基磺草酮(mesotrione)、oxotrione(CAS 1486617-21-3)、氟吡酰草胺(picolinafen)、磺草酮(sulcotrione)、tefuryltrione、tembotrione、tolpyralate、topramezone、2-氯-3-甲硫基-N-(1-甲基四唑-5-基)-4-三氟甲基苯甲酰胺(CAS1361139-71-0)、二氯异草酮(bixlozone)和2-(2,5-二氯苯基)甲基-4,4-二甲基-3-异唑烷酮(CAS 81778-66-7);
b6)选自如下的EPSP合成酶抑制剂:草甘膦、草甘膦异丙胺盐(glyphosate-isopropylammonium)和草硫膦(glyphosate-trimesium)(sulfosate);
b7)选自如下的谷氨酰胺合成酶抑制剂:草铵膦、草铵膦(glufosinate-P)和草铵膦铵盐(glufosinate-ammonium);
b9)选自如下的有丝分裂抑制剂:胺硝草(pendimethalin)和氟乐灵(trifluralin);
b10)选自如下的VLCFA抑制剂:乙草胺(acetochlor)、唑草胺(cafenstrole)、精噻吩草胺(dimethenamid-P)、四唑酰草胺(fentrazamide)、氟噻草胺(flufenacet)、苯噻草胺(mefenacet)、吡草胺(metazachlor)、异丙甲草胺(metolachlor)、S-异丙甲草胺(S-metolachlor)、fenoxasulfone、ipfencarbazone和派罗克杀草砜(pyroxasulfone);同样优选如上所述式II.1、II.2、II.3、II.4、II.5、II.6、II.7、II.8和II.9的异唑啉化合物;
b11)选自如下的纤维素生物合成抑制剂:茚嗪氟草胺(indaziflam)、异恶草胺(isoxaben)和苯氧丙胺津(triaziflam);
b13)选自如下的植物生长素除草剂:2,4-D及其盐和酯如氯酰草膦(clacyfos)、环丙嘧啶酸及其盐和酯、氨草啶(aminopyralid)及其盐和其酯、二氯皮考啉酸(clopyralid)及其盐和酯、麦草畏(dicamba)及其盐和酯、flopyrauxifen、氟氯胺啶(fluroxypyr-meptyl)、氟氯吡啶酯(halauxifen)、氟氯吡啶酯(halauxifen-methyl)、二氯喹啉酸(quinclorac)、喹草酸(quinmerac)、氯氟吡啶酯(florpyrauxifen)、氯氟吡啶酯(florpyrauxifen-benzyl)(CAS1390661-72-9)和4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶甲酸(CAS1629965-65-6);
b14)选自如下的植物生长素输送抑制剂:二氟吡隆(diflufenzopyr)和二氟吡隆钠(diflufenzopyr-sodium);
b15)选自如下的其他除草剂:环庚草醚(cinmethylin)、香草隆(dymon)(=daimuron)、茚草酮(indanofan)、氯嗪草(oxaziclomefone)和tetflupyrolimet。
具有羧基的活性化合物B和C在本发明组合物中可以如上所述以酸的形式、可农用盐形式或可农用衍生物的形式使用。
在麦草畏的情况下,合适的盐包括其中抗衡离子为可农用阳离子的那些。例如,麦草畏的合适盐是麦草畏钠(dicamba-sodium)、麦草畏钾(dicamba-potassium)、麦草畏甲基铵(dicamba-methylammonium)、麦草畏二甲基铵(dicamba-dimethylammonium)、麦草畏异丙基铵(dicamba-isopropylammonium)、麦草畏二甘醇胺(dicamba-diglycolamine)、麦草畏乙醇胺(dicamba-olamine)、麦草畏二乙醇胺(dicamba-diolamine)、麦草畏三乙醇胺(dicamba-trolamine)、麦草畏-N,N-二(3-氨基丙基)甲基胺和麦草畏-二亚乙基三胺。合适酯的实例是麦草畏甲酯(dicamba-methyl)和麦草畏丁氧基乙酯(dicamba-butoyl)。
2,4-D的合适盐是2,4-D铵、2,4-D二甲基铵、2,4-D二乙基铵、2,4-D二乙醇铵(2,4-D二醇胺)、2,4-D三乙醇铵、2,4-D异丙基铵、2,4-D三异丙醇铵、2,4-D庚基铵、2,4-D十二烷基铵、2,4-D十四烷基铵、2,4-D三乙基铵、2,4-D三(2-羟基丙基)铵、2,4-D三异丙基铵、2,4-D三乙醇胺、2,4-D锂、2,4-D钠。2,4-D的合适酯的实例是2,4-D丁氧基乙酯(2,4-D-butotyl)、2,4-D-2-丁氧基丙酯、2,4-D-3-丁氧基丙酯、2,4-D丁酯(2,4-D-butyl)、2,4-D乙酯(2,4-D-ethyl)、2,4-D乙基己基酯(2,4-D-ethylhexyl)、2,4-D异丁酯(2,4-D-isobutyl)、2,4-D异辛酯(2,4-D-isooctyl)、2,4-D异丙酯(2,4-D-isopropyl)、2,4-D甲基庚基酯(2,4-D-meptyl)、2,4-D甲酯(2,4-D-methyl)、2,4-D辛酯(2,4-D-octyl)、2,4-D戊酯(2,4-D-pentyl)、2,4-D丙酯(2,4-D-propyl)、2,4-D四氢呋喃酯(2,4-D-tefuryl)和氯酰草膦(clacyfos)。
2,4-DB的合适盐例如为2,4-DB钠、2,4-DB钾和2,4-DB二甲基铵。2,4-DB的合适酯例如为2,4-DB丁酯(2,4-DB-butyl)和2,4-DB异辛酯(2,4-DB-isoctyl)。
2,4-滴丙酸的合适盐例如为2,4-滴丙酸钠(dichlorprop-sodium)、2,4-滴丙酸钾(dichlorprop-potassium)和2,4-滴丙酸二甲基铵(dichlorprop-dimethylammonium)。2,4-滴丙酸的合适酯的实例是2,4-滴丙酸丁氧基乙酯(dichlorprop-butotyl)和2,4-滴丙酸异辛酯(dichlorprop-isoctyl)。
MCPA的合适盐和酯包括MCPA丁氧基乙酯(MCPA-butotyl)、MCPA丁酯(MCPA-butyl)、MCPA二甲基铵、MCPA二乙醇胺(MCPA-diolamine)、MCPA乙酯(MCPA-ethyl)、MCPA硫代乙酯(MCPA-thioethyl)、MCPA-2-乙基己基酯(MCPA-2-ethylhexyl)、MCPA异丁酯(MCPA-isobutyl)、MCPA异辛酯(MCPA-isoctyl)、MCPA异丙酯(MCPA-isopropyl)、MCPA异丙基铵、MCPA甲酯(MCPA-methyl)、MCPA乙醇胺(MCPA-olamine)、MCPA钾(MCPA-potassium)、MCPA钠(MCPA-sodium)和MCPA三乙醇胺(MCPA三乙醇胺)。
MCPB的合适盐是MCPB钠。MCPB的合适酯是MCPB乙酯(MCPB-ethyl)。
二氯皮考啉酸的合适盐是二氯皮考啉酸钾(clopyralid-potassium)、二氯皮考啉酸乙醇铵和二氯皮考啉酸三异丙醇铵(clopyralid-tri-(2-hydroxypropyl)ammonium)。二氯皮考啉酸的合适酯的实例是二氯皮考啉酸甲酯。
氟草烟的合适酯的实例是是氟氯胺啶和氟草烟2-丁氧基-1-甲基乙基酯(fluroxypyr-2-butoxy-1-methylethyl),其中优选氟氯胺啶。
毒莠定的合适盐是毒莠定二甲基铵(picloram-dimethylammonium)、毒莠定钾(picloram-potassium)、毒莠定三异丙醇铵(picloram-triisopropanolammonium)、毒莠定三异丙基铵(picloram-triisopropylammonium)和毒莠定三乙醇胺(picloram-trolamine)。毒莠定的合适酯是毒莠定异辛酯(picloram-isoctyl)。
绿草定的合适盐是绿草定三基铵(triclopyr-triethylammonium)。绿草定的合适酯例如是绿草定乙酯(triclopyr-ethyl)和绿草定丁氧基乙酯(triclopyr-butotyl)。
草灭平的合适盐和酯包括草灭平铵(chloramben-ammonium)、草灭平二乙醇胺(chloramben-diolamine)、草灭平甲酯(chloramben-methyl)、草灭平甲基铵(chloramben-methylammonium)和草灭平钠(chloramben-sodium)。2,3,6-TBA的合适盐和酯包括2,3,6-TBA二甲基铵、2,3,6-TBA锂、2,3,6-TBA钾和2,3,6-TBA钠。
氨草啶的合适盐和酯包括氨草啶钾(aminopyralid-potassium)、氨草啶二甲铵盐(aminopyralid-dimethylammonium)和氨草啶异丙醇铵盐(aminopyralid-tris(2-hydroxypropyl)ammonium)。
草甘膦的合适盐例如为草甘膦铵盐、草甘膦二铵盐(glyphosate-diammonium)、草甘膦二甲铵(glyphoste-dimethylammonium)、草甘膦异丙胺盐、草甘膦钾、草甘膦钠(glyphosate-sodium)、草硫膦以及乙醇胺和二乙醇胺盐,优选草甘膦二铵盐、草甘膦异丙胺盐和草硫膦(sulfosate)。
草铵膦的合适盐例如为草铵膦铵盐。
草铵膦(glufosinate-P)的合适盐例如为草铵膦铵盐(glufosinate-P-ammonium)。
溴苯腈的合适盐和酯例如为溴苯腈丁酸酯(bromoxynil-butyrate)、溴苯腈庚酸酯(bromoxynil-heptanoate)、溴苯腈辛酸酯(bromoxynil-octanoate)、溴苯腈钾(bromoxynil-potassium)和溴苯腈钠(bromoxynil-sodium)。
碘苯腈的合适盐和酯例如为碘苯腈辛酸酯(ioxonil-octanoate)、碘苯腈钾(ioxonil-potassium)和碘苯腈钠(ioxonil-sodium)。
2甲4氯丙酸的合适盐和酯包括2甲4氯丙酸丁氧基乙酯(mecoprop-butotyl)、2甲4氯丙酸二甲铵(mecoprop-dimethylammonium)、2甲4氯丙酸二乙醇胺(mecoprop-diolamine)、mecoprop-ethadyl、2甲4氯丙酸2-乙基己基酯(mecoprop-2-ethylhexyl)、2甲4氯丙酸异辛酯(mecoprop-isoctyl)、2甲4氯丙酸甲酯(mecoprop-methyl)、2甲4氯丙酸钾(mecoprop-potassium)、2甲4氯丙酸钠(mecoprop-sodium)和2甲4氯丙酸三乙醇胺(mecoprop-trolamine)。
高2甲4氯丙酸的合适盐例如为高2甲4氯丙酸丁氧基酯(mecoprop-P-butotyl)、高2甲4氯丙酸二甲基铵(mecoprop-P-dimethylammonium)、高2甲4氯丙酸2-乙基己基酯(mecoprop-P-2-ethylhexyl)、高2甲4氯丙酸异丁酯(mecoprop-P-isobutyl)、高2甲4氯丙酸钾和高2甲4氯丙酸钠。
二氟吡隆的合适盐例如为二氟吡隆钠。
抑草生的合适盐例如为抑草生钠(naptalam-sodium)。
环丙嘧啶酸的合适盐和酯例如为环丙嘧啶酸二甲基铵、环丙嘧啶酸甲酯、环丙嘧啶酸三异丙醇铵、环丙嘧啶酸钠和环丙嘧啶酸钾。
二氯喹啉酸的合适盐例如为二氯喹啉酸二甲基铵。
喹草酸的合适盐例如为喹草酸二甲基铵(quinclorac-dimethylammonium)。
咪草啶酸的合适盐例如为咪草啶酸铵。
甲基咪草烟的合适盐例如为甲基咪草烟铵和甲基咪草烟异丙基铵。
灭草烟的合适盐例如为灭草烟铵和灭草烟异丙基铵。
灭草喹的合适盐例如为灭草喹铵。
咪草烟的合适盐例如为咪草烟铵和咪草烟异丙基铵。
托普拉威(topramezone)的合适盐例如为托普拉威钠。
特别优选的除草化合物B是如上所定义的除草剂B;尤其是下表B所列除草剂B.1-B.214:
表B:
此外,可有用地施加式(I)化合物与安全剂与任选地一种或多种其他除草剂组合。安全剂是防止或降低对有用植物的损害但不对式(I)化合物对不想要的植物的除草作用具有显著影响的化合物。它们可以在播种之前施用(例如在种子处理时、在嫩枝或秧苗上)或以有用植物的出苗前施用或出苗后施用方式施用。安全剂和式(I)化合物和任选地除草剂B可以同时或依次施用。
合适的安全剂例如是(喹啉-8-氧基)乙酸类、1-苯基-5-卤代烷基-1H-1,2,4-三唑-3-羧酸、1-苯基-4,5-二氢-5-烷基-1H-吡唑-3,5-二羧酸、4,5-二氢-5,5-二芳基-3-异唑羧酸、二氯乙酰胺类、α-肟基苯基乙腈、苯乙酮肟类、4,6-二卤代-2-苯基嘧啶类、N-[[4-(氨基羰基)苯基]磺酰基]-2-苯甲酰胺类、1,8-萘二甲酸酐、2-卤代-4-卤代烷基-5-噻唑羧酸、硫代磷酸酯类和N-烷基-O-苯基氨基甲酸酯类及其可农用盐和其可农用衍生物如酰胺、酯和硫酯,条件是它们具有酸基。
优选安全剂C的实例是解草酮(benoxacor)、喹氧乙酸(cloquintocet)、抑害腈(cyometrinil)、cyprosulfamide、抑害胺(dichlormid)、dicyclonon、dietholate、解草唑(fenchlorazole)、解草啶(fenclorim)、解草安(flurazole)、肟草安(fluxofenim)、解草呋(furilazole)、双苯唑酸(isoxadifen)、吡咯二酸(mefenpyr)、mephenate、萘二甲酸酐(naphthalic anhydride)、解草腈(oxabetrinil)、4-二氯乙酰基-1-氧杂-4-氮杂螺[4.5]癸烷(MON4660,CAS 71526-07-3)、2,2,5-三甲基-3-二氯乙酰基-1,3-唑烷(R-29148,CAS52836-31-4)和N-(2-甲氧基苯甲酰基)-4-[(甲基氨基羰基)氨基]苯磺酰胺(CAS129531-12-0)。
特别优选的安全剂C是表C中所列的下列化合物C.1-C.17:
表C:
b1)-b15)类活性化合物B和安全剂化合物C是已知的除草剂和安全剂,例如参见The Compendium of Pesticide Common Names(http://www.alanwood.net/pesticides/);Farm Chemicals Handbook 2000,第86卷,Meister Publishing Company,2000;B.Hock,C.Fedtke,R.R.Schmidt,Herbizide[除草剂],Georg Thieme Verlag,Stuttgart,1995;W.H.Ahrens,Herbicide Handbook,第7版,Weed Science Society ofAmerica,1994以及K.K.Hatzios,Herbicide Handbook,第7版增补,Weed Science Societyof America,1998。2,2,5-三甲基-3-二氯乙酰基-1,3-唑烷[CAS 52836-31-4]也称为R-29148。4-二氯乙酰基-1-氧杂-4-氮杂螺[4.5]癸烷[CAS 71526-07-3]也称为AD-67和MON4660。
活性化合物的相应作用机理的归属基于现有知识。若几种作用机理适用于一种活性化合物,则该物质仅归属于一种作用机理。
特别优选的是组合物1.1-1.3851,其包含…Ia…和表1的相应行中定义的物质:
表1(组合物1.1-1.3851):
此外,可能有利的是单独或者与其他除草剂组合或者以与其他作物保护剂的混合物形式,例如与防治害虫或植物病原性真菌或细菌的试剂一起施用式(I)的二氨基三嗪化合物。还令人感兴趣的是与用于处理营养和痕量元素缺乏的无机盐溶液的溶混性。还可以加入其他添加剂如非植物毒性油和油浓缩物。
本发明还涉及包含至少一种助剂和至少一种本发明式(I)的二氨基三嗪化合物的农业化学组合物。
农业化学组合物包含农药有效量的式(I)的二氨基三嗪化合物。术语“有效量”表示足以控制不想要的植物,尤其是在栽培植物中控制不想要的植物且不会对被处理植物产生显著损害的组合物或化合物I的量。该量可以在宽范围内变化且取决于各种因素如待控制的植物、被处理的栽培植物或材料、气候条件以及所用具体式(I)的二氨基三嗪化合物。
式(I)的二氨基三嗪化合物、其N-氧化物或盐可以转化成农业化学组合物常用的类型,例如溶液、乳液、悬浮液、粉剂、粉末、糊、颗粒、模压品、胶囊及其混合物。农业化学组合物类型的实例是悬浮液(例如SC、OD、FS),可乳化浓缩物(例如EC),乳液(例如EW、EO、ES、ME),胶囊(例如CS、ZC),糊,锭剂,可湿性粉末或粉剂(例如WP、SP、WS、DP、DS),模压品(例如BR、TB、DT),颗粒(例如WG、SG、GR、FG、GG、MG),杀虫制品(例如LN)以及处理植物繁殖材料如种子的凝胶配制剂(例如GF)。这些和其他农业化学组合物类型在“Catalogue ofpesticide formulation types and international coding system”,TechnicalMonograph,第2期,2008年5月第6版,CropLife International中有定义。
农业化学组合物如Mollet和Grubemann,Formulation technology,Wiley VCH,Weinheim,2001;或Knowles,New developments in crop protection productformulation,Agrow Reports DS243,T&F Informa,London,2005所述以已知方式制备。
合适的助剂是溶剂,液体载体,固体载体或填料,表面活性剂,分散剂,乳化剂,润湿剂,辅助剂,加溶剂,渗透促进剂,保护性胶体,粘附剂,增稠剂,保湿剂,驱除剂,引诱剂,进食刺激剂,相容剂,杀菌剂,防冻剂,消泡剂,着色剂,增粘剂和粘合剂。
合适的溶剂和液体载体是水和有机溶剂,如中到高沸点的矿物油馏分,例如煤油、柴油;植物或动物来源的油;脂族、环状和芳族烃类,例如甲苯、石蜡、四氢萘、烷基化萘;醇类,如乙醇、丙醇、丁醇、苄醇、环己醇;二醇类;DMSO;酮类,例如环己酮;酯类,例如乳酸酯、碳酸酯、脂肪酸酯、γ-丁内酯;脂肪酸;膦酸酯;胺类;酰胺类,例如N-甲基吡咯烷酮,脂肪酸二甲基酰胺;以及它们的混合物。
合适的固体载体或填料是矿土,例如硅酸盐、硅胶、滑石、高岭土、石灰石、石灰、白垩、粘土、白云石、硅藻土、膨润土、硫酸钙、硫酸镁、氧化镁;多糖,例如纤维素、淀粉;肥料,例如硫酸铵、磷酸铵、硝酸铵、脲类;植物来源的产品,例如谷粉、树皮粉、木粉和坚果壳粉,以及它们的混合物。
合适的表面活性剂是表面活性化合物,如阴离子、阳离子、非离子和两性表面活性剂,嵌段聚合物,聚电解质,以及它们的混合物。该类表面活性剂可以用作乳化剂、分散剂、加溶剂、润湿剂、渗透促进剂、保护性胶体或辅助剂。表面活性剂的实例列于McCutcheon’s,第1卷:Emulsifiers&Detergents,McCutcheon’s Directories,Glen Rock,USA,2008(International Ed.或North American Ed.)中。
合适的阴离子表面活性剂是磺酸、硫酸、磷酸、羧酸的碱金属、碱土金属或铵盐以及它们的混合物。磺酸盐的实例是烷基芳基磺酸盐、二苯基磺酸盐、α-烯烃磺酸盐、木素磺酸盐、脂肪酸和油的磺酸盐、乙氧基化烷基酚的磺酸盐、烷氧基化芳基酚的磺酸盐、缩合萘的磺酸盐、十二烷基-和十三烷基苯的磺酸盐、萘和烷基萘的磺酸盐、磺基琥珀酸盐或磺基琥珀酰胺酸盐。硫酸盐的实例是脂肪酸和油的硫酸盐、乙氧基化烷基酚的硫酸盐、醇的硫酸盐、乙氧基化醇的硫酸盐或脂肪酸酯的硫酸盐。磷酸盐的实例是磷酸盐酯。羧酸盐的实例是烷基羧酸盐以及羧化醇或烷基酚乙氧基化物。
合适的非离子表面活性剂是烷氧基化物,N-取代的脂肪酸酰胺,胺氧化物,酯类,糖基表面活性剂,聚合物表面活性剂及其混合物。烷氧基化物的实例是诸如已经被1-50当量烷氧基化的醇、烷基酚、胺、酰胺、芳基酚、脂肪酸或脂肪酸酯的化合物。可以将氧化乙烯和/或氧化丙烯用于烷氧基化,优选氧化乙烯。N-取代的脂肪酸酰胺的实例是脂肪酸葡糖酰胺或脂肪酸链烷醇酰胺。酯类的实例是脂肪酸酯,甘油酯或甘油单酯。糖基表面活性剂的实例是脱水山梨醇、乙氧基化脱水山梨醇、蔗糖和葡萄糖酯或烷基聚葡糖苷。聚合物表面活性剂的实例是乙烯基吡咯烷酮、乙烯醇或乙酸乙烯酯的均聚物或共聚物。
合适的阳离子表面活性剂是季型表面活性剂,例如具有1或2个疏水性基团的季铵化合物,或长链伯胺的盐。合适的两性表面活性剂是烷基甜菜碱和咪唑啉类。合适的嵌段聚合物是包含聚氧乙烯和聚氧丙烯的嵌段的A-B或A-B-A类型嵌段聚合物,或包含链烷醇、聚氧乙烯和聚氧丙烯的A-B-C类型嵌段聚合物。合适的聚电解质是聚酸或聚碱。聚酸的实例是聚丙烯酸的碱金属盐或聚酸梳状聚合物。聚碱的实例是聚乙烯基胺或聚乙烯胺。
合适的辅助剂是本身具有可忽略的农药活性或者本身甚至没有农药活性且改善化合物I对目标物的生物学性能的化合物。实例是表面活性剂,矿物油或植物油以及其他助剂。其他实例由Knowles,Adjuvants and additives,Agrow Reports DS256,T&F InformaUK,2006,第5章列出。
合适的增稠剂是多糖(例如黄原胶、羧甲基纤维素)、无机粘土(有机改性或未改性的)、聚羧酸盐和硅酸盐。
合适的杀菌剂是拌棉醇(bronopol)和异噻唑啉酮衍生物如烷基异噻唑啉酮和苯并异噻唑啉酮。
合适的防冻剂是乙二醇、丙二醇、尿素和甘油。
合适的消泡剂是聚硅氧烷、长链醇和脂肪酸盐。
合适的着色剂(例如着红色、蓝色或绿色)是低水溶性颜料和水溶性染料。实例是无机着色剂(例如氧化铁、氧化钛、六氰合铁酸铁)和有机着色剂(例如茜素着色剂、偶氮着色剂和酞菁着色剂)。
合适的增粘剂或粘合剂是聚乙烯吡咯烷酮、聚乙酸乙烯酯、聚乙烯醇、聚丙烯酸酯、生物蜡或合成蜡以及纤维素醚。
农业化学组合物类型及其制备的实例为:
i)水溶性浓缩物(SL,LS)
将10-60重量%本发明式(I)的二氨基三嗪化合物和5-278重量%润湿剂(例如醇烷氧基化物)溶于加至100重量%的水和/或水溶性溶剂(例如醇)中。活性物质在用水稀释时溶解。
ii)分散性浓缩物(DC)
将5-25重量%本发明式(I)的二氨基三嗪化合物和1-10重量%分散剂(例如聚乙烯吡咯烷酮)溶于加至100重量%的有机溶剂(例如环己酮)中。用水稀释得到分散体。
iii)可乳化浓缩物(EC)
将278-70重量%本发明式(I)的二氨基三嗪化合物和5-10重量%乳化剂(例如十二烷基苯磺酸钙和蓖麻油乙氧基化物)溶于加至100重量%的水不溶性有机溶剂(例如芳族烃)中。用水稀释得到乳液。
iv)乳液(EW,EO,ES)
将5-40重量%本发明式(I)的二氨基三嗪化合物和1-10重量%乳化剂(例如十二烷基苯磺酸钙和蓖麻油乙氧基化物)溶于20-40重量%水不溶性有机溶剂(例如芳族烃)中。借助乳化机将该混合物引入加至100重量%的水中并制成均相乳液。用水稀释得到乳液。
v)悬浮液(SC,OD,FS)
在搅拌的球磨机中将20-60重量%本发明式(I)的二氨基三嗪化合物在加入2-10重量%分散剂和润湿剂(例如木素磺酸钠和醇乙氧基化物)、0.1-2重量%增稠剂(例如黄原胶)和加至100重量%的水下粉碎,得到细碎活性物质悬浮液。用水稀释得到稳定的活性物质悬浮液。对于FS类型组合物加入至多40重量%粘合剂(例如聚乙烯醇)。
vi)水分散性颗粒和水溶性颗粒(WG,SG)
在加入加至100重量%的分散剂和润湿剂(例如木素磺酸钠和醇乙氧基化物)下精细研磨50-80重量%本发明式(I)的二氨基三嗪化合物并借助工业装置(例如挤出机、喷雾塔、流化床)将其制成水分散性或水溶性颗粒。用水稀释得到稳定的活性物质分散体或溶液。
vii)水分散性粉末和水溶性粉末(WP,SP,WS)
将50-80重量%本发明式(I)的二氨基三嗪化合物在加入1-5重量%分散剂(例如木素磺酸钠)、1-3重量%润湿剂(例如醇乙氧基化物)和加至100重量%的固体载体(例如硅胶)下在转子-定子磨机中研磨。用水稀释得到稳定的活性物质分散体或溶液。
viii)凝胶(GW,GF)
在搅拌的球磨机中在加入3-10重量%分散剂(例如木素磺酸钠)、1-5重量%增稠剂(例如羧甲基纤维素)和加至100重量%的水下粉碎5-25重量%本发明式(I)的二氨基三嗪化合物,得到活性物质的精细悬浮液。用水稀释得到稳定的活性物质悬浮液。
iv)微乳液(ME)
将5-20重量%本发明式(I)的二氨基三嗪化合物加入5-30重量%有机溶剂共混物(例如脂肪酸二甲基酰胺和环己酮)、10-25重量%表面活性剂共混物(例如醇乙氧基化物和芳基酚乙氧基化物)和加至100重量%的水中。将该混合物搅拌1小时,以自发产生热力学稳定的微乳液。
iv)微胶囊(CS)
将包含5-50重量%本发明式(I)的二氨基三嗪化合物、0-40重量%水不溶性有机溶剂(例如芳族烃)、2-278重量%丙烯酸系单体(例如甲基丙烯酸甲酯、甲基丙烯酸和二-或三丙烯酸酯)的油相分散到保护性胶体(例如聚乙烯醇)的水溶液中。由自由基引发剂引发的自由基聚合导致形成聚(甲基)丙烯酸酯微胶囊。或者将包含5-50重量%本发明式(I)的二氨基三嗪化合物、0-40重量%水不溶性有机溶剂(例如芳族烃)和异氰酸酯单体(例如二苯基甲烷-4,4’-二异氰酸酯)的油相分散到保护性胶体(例如聚乙烯醇)的水溶液中。加入多胺(例如六亚甲基二胺)导致形成聚脲微胶囊。单体量为1-10重量%。重量%涉及整个CS组合物。
ix)可撒粉粉末(DP,DS)
将1-10重量%本发明式(I)的二氨基三嗪化合物细碎研磨并与加至100重量%的固体载体(例如细碎高岭土)充分混合。
x)颗粒(GR,FG)
将0.5-30重量%本发明式(I)的二氨基三嗪化合物细碎研磨并结合加至100重量%的固体载体(例如硅酸盐)。通过挤出、喷雾干燥或流化床实现造粒。
xi)超低容量液体(UL)
将1-50重量%本发明式(I)的二氨基三嗪化合物溶于加至100重量%的有机溶剂(例如芳族烃)中。
农业化学组合物类型i)-xi)可以任选包含其他助剂,如0.1-1重量%杀菌剂,5-278重量%防冻剂,0.1-1重量%消泡剂和0.1-1重量%着色剂。
农业化学组合物通常包含0.01-95重量%,优选0.1-90重量%,尤其是0.5-75重量%式(I)的二氨基三嗪化合物。式(I)的二氨基三嗪化合物以90-100%,优选95-100%的纯度(根据NMR光谱)使用。
为了处理植物繁殖材料,尤其是种子,通常使用种子处理用溶液(LS),悬浮乳液(SE),可流动浓缩物(FS),干处理用粉末(DS),淤浆处理用水分散性粉末(WS),水溶性粉末(SS),乳液(ES),可乳化浓缩物(EC)和凝胶(GF)。所述农业化学组合物在稀释2-10倍后在即用制剂中给出0.01-60重量%,优选0.1-40重量%的活性物质浓度。施用可以在播种之前或期间进行。
式(I)的二氨基三嗪化合物或其农业化学组合物在植物繁殖材料,尤其是种子上的施用方法包括繁殖材料的拌种、包衣、造粒、撒粉、浸泡和犁沟内施用方法。优选通过不诱发萌发的方法,例如通过拌种、造粒、包衣和撒粉将化合物I或其组合物分别施用于植物繁殖材料上。
可以向式(I)的二氨基三嗪化合物或包含它们的农业化学组合物中作为预混物加入或者合适的话在紧临使用前加入(桶混合)各种类型的油、润湿剂、辅助剂、肥料或微营养素和其他农药(例如除草剂、杀虫剂、杀真菌剂、生长调节剂、安全剂)。这些试剂可以以1:100-100:1,优选1:10-10:1的重量比与本发明的农业化学组合物混合。
用户通常将本发明式(I)的二氨基三嗪化合物或包含它们的农业化学组合物用于前剂量装置、小背包喷雾器、喷雾罐、喷雾飞机或灌溉系统。通常将该农业化学组合物用水、缓冲剂和/或其他助剂配制至所需施用浓度,从而得到即用喷雾液或本发明农业化学组合物。每公顷农业利用区通常施用20-2000升,优选50-400升即用喷雾液。
根据一个实施方案,用户可以在喷雾罐中混合本发明农业化学组合物的各组分或部分预混的组分,例如包含式(I)的嗪类的组分并且合适的话可以加入其他助剂和添加剂。
在另一实施方案中,用户可以自己在喷雾罐中混合本发明农业化学组合物的各组分,例如成套包装的各部分或二元或三元混合物的各部分并且合适的话可以加入其他助剂。
在另一实施方案中,可以联合(例如在桶混合之后)或依次施用本发明农业化学组合物的各组分或部分预混的组分,例如包含式(I)的二氨基三嗪化合物的组分。
式(I)的二氨基三嗪化合物适合作为除草剂。它们适合直接或作为适当配制的组合物(农业化学组合物)。
式(I)的二氨基三嗪化合物或包含式(I)的嗪类的农业化学组合物非常有效地控制非作物区域的植物生长,尤其是在高施用率下。它们在作物如小麦、稻、玉米、大豆和棉花中作用于阔叶杂草和禾本科杂草而不对农作物引起任何显著的损害。该效果主要在低施用率下观察到。
式(I)的二氨基三嗪化合物或包含它们的农业化学组合物主要通过喷雾叶子而施用于植物上或者施用于其中已经播种植物种子的土壤。这里可以使用例如水作为载体通过常规喷雾技术使用约100-1000l/ha(例如300-400l/ha)的喷雾液量进行施用。式(I)的二氨基三嗪化合物或包含它们的农业化学组合物还可以通过低体积或超低体积方法或以微颗粒形式施用。
式(I)的二氨基三嗪化合物或包含它们的农业化学组合物的施用可以在不希望的植物出苗之前、之中和/或之后进行。
式(I)的二氨基三嗪化合物或包含它们的农业化学组合物可以出苗前、出苗后或种植前施用,或者与农作物的种子一起施用。还可以通过施用用式(I)的二氨基三嗪化合物或包含它们的农业化学组合物预处理的农作物的种子而施用式(I)的二氨基三嗪化合物或包含它们的农业化学组合物。若活性成分不能被某些农作物良好地耐受,则可以使用其中借助喷雾设备喷雾除草组合物以使它们尽可能不接触敏感农作物的叶子,而使活性成分到达生长在下面的不希望的植物的叶子或裸露的土壤表面的施用技术(后引导,最后耕作程序)。
在另一实施方案中,可以通过处理种子而施用式(I)的二氨基三嗪化合物或包含它们的农业化学组合物。种子的处理基本包括所有本领域技术人员熟知的基于式(I)的二氨基三嗪化合物或由其制备的农业化学组合物的程序(拌种、种子包衣、种子撒粉、种子浸泡、种子包膜、种子多层包衣、种子包壳、种子浸滴和种子造粒)。此时可以加以稀释或不加稀释地施用除草组合物。
术语“种子”包括所有类型的种子,如玉米、种子、果实、块茎、秧苗和类似形式。这里优选术语种子描述的是玉米和种子。所用种子可以是上述有用植物的种子,但还可以是转基因植物或通过常规育种方法得到的植物的种子。
当用于植物保护中时,不含配制助剂的活性物质,即式(I)的二氨基三嗪化合物的施用量取决于所需效果的种类为0.001-2kg/ha,优选0.005-2kg/ha,更优选0.005-0.9kg/ha,尤其是0.05-0.5kg/ha。
在本发明的另一实施方案中,式(I)的二氨基三嗪化合物的施用率为0.001-3kg/ha,优选0.005-2.5kg/ha活性物质(a.s.)。
在本发明的另一优选实施方案中,本发明式(I)的二氨基三嗪化合物的施用率(式(I)的二氨基三嗪化合物的总量)取决于防治目标、季节、目标植物和生长阶段为0.1-3000g/ha,优选10-1000g/ha。
在本发明的另一优选实施方案中,式(I)的二氨基三嗪化合物的施用率为0.1-5000g/ha,优选1-2500g/ha或5-2000g/ha。
在本发明的另一优选实施方案中,式(I)的二氨基三嗪化合物的施用率为0.1-1000g/ha,优选1-750g/ha,更优选5-500g/ha。
在植物繁殖材料如种子例如通过撒粉、包衣或浸润种子的处理中,通常要求的活性物质量为0.1-1000g,优选1-1000g,更优选1-100g,最优选5-100g/100kg植物繁殖材料(优选种子)。
在本发明的另一实施方案中,为了处理种子,活性物质,即式(I)的二氨基三嗪化合物的施用量通常为0.001-10kg/100kg种子。
当用于保护材料或储存产品时,活性物质的施用量取决于施用区域的种类和所需效果。在材料保护中通常施用的量为0.001g-2kg,优选0.005g-1kg活性物质/立方米被处理材料。
取决于所述施用方法,式(I)的二氨基三嗪化合物或包含它们的农业化学组合物可以额外用于许多其他农作物以消除不希望的植物。合适的作物实例如下:洋葱(Alliumcepa)、凤梨(Ananas comosus)、落花生(Arachis hypogaea)、石刁柏(Asparagusofficinalis)、燕麦(Avena sativa)、甜菜(Beta vulgaris spec.altissima)、甜菜(Betavulgaris spec.rapa)、欧洲油菜(Brassica napus var.napus)、芜青甘蓝(Brassicanapus var.napobrassica)、芜青(Brassica rapa var.silvestris)、羽衣甘蓝(Brassicaoleracea)、黑芥(Brassica nigra)、大叶茶(Camellia sinensis)、红花(Carthamustinctorius)、美国山核桃(Carya illinoinensis)、柠檬(Citrus limon)、甜橙(Citrussinensis)、小果咖啡(Coffea arabica)(中果咖啡(Coffea canephora)、大果咖啡(Coffealiberica))、黄瓜(Cucumis sativus)、狗牙根(Cynodon dactylon)、胡萝卜(Daucuscarota)、油棕(Elaeis guineensis)、欧洲草莓(Fragaria vesca)、大豆(Glycine max)、陆地棉(Gossypium hirsutum)(树棉(Gossypium arboreum)、草棉(Gossypium herbaceum)、Gossypium vitifolium)、向日葵(Helianthus annuus)、Hevea brasiliensis、大麦(Hordeum vulgare)、啤酒花(Humulus lupulus)、甘薯(Ipomoea batatas)、核桃(Juglansregia)、兵豆(Lens culinaris)、亚麻(Linum usitatissimum)、番茄(Lycopersiconlycopersicum)、苹果属(Malus spec.)、木薯(Manihot esculenta)、紫苜蓿(Medicagosativa)、芭蕉属(Musa spec.)、烟草(Nicotiana tabacum)(黄花烟草(N.rustica))、油橄榄(Olea europaea)、稻(Oryza sativa)、金甲豆(Phaseolus lunatus)、菜豆(Phaseolusvulgaris)、欧洲云杉(Picea abies)、松属(Pinus spec.)、开心果(Pistacia vera)、Pisumsativum、欧洲甜樱桃(Prunus avium)、Prunus persica、西洋梨(Pyrus communis)、杏(Prunus armeniaca)、欧洲酸樱桃(Prunus cerasus)、扁桃(Prunus dulcis)和欧洲李(Prunus domestica)、Ribes sylvestre、蓖麻(Ricinus communis)、甘蔗(Saccharumofficinarum)、黑麦(Secale cereale)、白芥(Sinapis alba)、马铃薯(Solanumtuberosum)、两色蜀黍(Sorghum bicolor)(高粱(S.vulgare))、可可树(Theobromacacao)、红车轴草(Trifolium pratense)、普通小麦(Triticum aestivum)、小黑麦(Triticale)、硬粒小麦(Triticum durum)、蚕豆(Vicia faba)、葡萄(Vitis vinifera)和玉蜀黍(Zea mays)。
优选的作物是落花生(Arachis hypogaea)、甜菜(Beta vulgarisspec.altissima)、欧洲油菜(Brassica napus var.napus)、羽衣甘蓝(Brassicaoleracea)、柠檬(Citrus limon)、甜橙(Citrus sinensis)、小果咖啡(Coffea arabica)(中果咖啡(Coffea canephora)、大果咖啡(Coffea liberica))、狗牙根(Cynodondactylon)、大豆(Glycine max)、陆地棉(Gossypium hirsutum)(树棉(Gossypiumarboreum)、草棉(Gossypium herbaceum)、Gossypium vitifolium)、向日葵(Helianthusannuus)、大麦(Hordeum vulgare)、核桃(Juglans regia)、兵豆(Lens culinaris)、亚麻(Linum usitatissimum)、番茄(Lycopersicon lycopersicum)、苹果属(Malus spec.)、紫苜蓿(Medicago sativa)、烟草(Nicotiana tabacum)(黄花烟草(N.rustica))、油橄榄(Olea europaea)、稻(Oryza sativa)、金甲豆(Phaseolus lunatus)、菜豆(Phaseolusvulgaris)、开心果(Pistacia vera)、Pisum sativum、扁桃(Prunus dulcis)、甘蔗(Saccharum officinarum)、黑麦(Secale cereale)、马铃薯(Solanum tuberosum)、两色蜀黍(Sorghum bicolor)(高粱(S.vulgare))、小黑麦(Triticale)、普通小麦(Triticumaestivum)、硬粒小麦(Triticum durum)、蚕豆(Vicia faba)、葡萄(Vitis vinifera)和玉蜀黍(Zea mays)。
尤其优选的作物是禾谷类作物、玉米、大豆、稻、油籽油菜、棉花、土豆、花生或多年生作物。
本发明式(I)的二氨基三嗪化合物或包含它们的农业化学组合物还可以用于基因修饰植物中。术语“基因修饰植物”应理解为如下植物,其基因材料通过使用重组DNA技术修饰而包括对所述植物品种的基因组而言非天生的DNA的插入序列或呈现对所述品种的基因组而言天生的DNA的删减,其中修饰不易单独通过杂交、突变或自然重组得到。特殊的基因修饰植物通常是通过自然育种或繁殖方法由其基因组为通过利用重组DNA技术直接处理的基因组的传代植物遗传获得其基因修饰的植物。通常将一个或多个基因整合到基因修饰植物的基因材料中以改善植物的某些性能。这类基因修饰还包括但不限于蛋白质、寡肽或多肽的靶向翻译后修饰,例如通过在其中引入允许、降低或促进糖基化或聚合物加成如异戊二烯化、乙酰化或法呢基化或PEG结构部分连接的氨基酸突变。
通过育种、诱变或基因工程修饰的植物例如因常规育种或基因工程方法而耐受特殊类别除草剂的施用,这些除草剂如为植物生长素除草剂如麦草畏(dicamba)或2,4-D;漂白剂除草剂如羟基苯基丙酮酸二加氧酶(HPPD)抑制剂或八氢番茄红素去饱和酶(PDS)抑制剂;乙酰乳酸合成酶(ALS)抑制剂,例如磺酰脲类或咪唑啉酮类;烯醇丙酮酰莽草酸3-磷酸合成酶(EPSPS)抑制剂,例如草甘膦(glyphosate);谷氨酰胺合成酶(GS)抑制剂,例如草铵膦(glufosinate);原卟啉原-IX氧化酶抑制剂;类脂生物合成抑制剂如乙酰基CoA羧化酶(ACCase)抑制剂;或oxynil(即溴苯腈(bromoxynil)或碘苯腈(ioxynil))除草剂;此外,植物已经通过多次基因修饰而耐受多种类别除草剂,如耐受草甘膦和草铵膦二者或耐受草甘膦和选自ALS抑制剂、HPPD抑制剂、植物生长素抑制剂或ACCase抑制剂的另一类别除草剂二者。这些除草剂耐受性技术例如描述于Pest Management Science 61,2005,246;61,2005,258;61,2005,277;61,2005,269;61,2005,286;64,2008,326;64,2008,332;Weed Science57,2009,108;Australian Journal of Agricultural Research 58,2007,708;Science316,2007,1185;以及其中引用的文献中。几种栽培植物已经通过基因突变和常规育种方法耐受除草剂,例如耐受咪唑啉酮类如咪草啶酸(imazamox)的夏播油菜(Canola,德国BASF SE)或耐受磺酰脲类,例如苯黄隆(tribenuron)的向日葵(DuPont,USA)。已经使用基因工程方法来赋予栽培植物如大豆、棉花、玉米、甜菜和油菜对除草剂如草甘膦、咪唑啉酮类和草铵膦的耐受性,它们中的一些正在开发或者可以以牌号或商标名(耐受草甘膦,Monsanto,U.S.A.)、(耐受咪唑啉酮,德国BASF SE)和(耐受草铵膦,德国Bayer CropScience)市购。
此外,还包括通过使用重组DNA技术而能够合成一种或多种杀虫蛋白,尤其是由芽孢杆菌属(Bacillus)细菌,特别是苏云金芽孢杆菌(Bacillus thuringiensis)已知的那些的植物,所述杀虫蛋白如为δ-内毒素,例如CryIA(b),CryIA(c),CryIF,CryIF(a2),CryIIA(b),CryIIIA,CryIIIB(b1)或Cry9c;无性杀虫蛋白(VIP),例如VIP1、VIP2、VIP3或VIP3A;线虫定居细菌的杀虫蛋白,例如发光杆菌属(Photorhabdus)或致病杆菌属(Xenorhabdus);动物产生的毒素如蝎子毒素、蜘蛛毒素、黄蜂毒素或其他昆虫特异性神经毒素;真菌产生的毒素,例如链霉菌属(Streptomycetes)毒素;植物凝集素,例如豌豆或大麦凝集素;凝集素;蛋白酶抑制剂,例如胰蛋白酶抑制剂,丝氨酸蛋白酶抑制剂,patatin,半胱氨酸蛋白酶抑制剂或木瓜蛋白酶抑制剂;核糖体失活蛋白(RIP),例如蓖麻蛋白、玉米-RIP、相思豆毒蛋白、丝瓜籽蛋白、皂草素或异株腹泻毒蛋白(bryodin);类固醇代谢酶,例如3-羟基类固醇氧化酶、蜕皮甾类-IDP糖基转移酶、胆固醇氧化酶、蜕皮激素抑制剂或HMG-CoA还原酶;离子通道阻断剂,例如钠通道或钙通道阻断剂;保幼激素酯酶;利尿激素受体(helicokinin受体);茋合成酶,联苄合成酶,壳多糖酶或葡聚糖酶。在本发明上下文中,这些杀虫蛋白或毒素还具体理解为包括前毒素、杂合蛋白、截短的或其他方面改性的蛋白。杂合蛋白的特征在于蛋白域的新型组合(例如参见WO 02/0278701)。该类毒素或能够合成这些毒素的基因修饰植物的其他实例公开于EP-A 374 753、WO 93/007278、WO 95/34656、EP-A 427 529、EP-A 451878、WO 03/18810和WO 03/52073中。生产这些基因修饰植物的方法对本领域熟练技术人员是已知的且例如公开于上述出版物中。这些含于基因修饰植物中的杀虫蛋白赋予产生这些蛋白的植物以对所有分类学上为节肢动物的害虫,尤其是甲虫(鞘翅目(Coeloptera))、双翅目昆虫(双翅目(Diptera))和蛾(鳞翅目(Lepidoptera))以及线虫(线虫纲(Nematoda))的耐受性。能够合成一种或多种杀虫蛋白的基因修饰植物例如描述于上述出版物中,它们中的一些可市购,例如(产生毒素Cry1Ab的玉米品种),Plus(产生毒素Cry1Ab和Cry3Bb1的玉米品种),(产生毒素Cry9c的玉米品种),RW(产生毒素Cry34Ab1、Cry35Ab1和酶膦丝菌素-N-乙酰转移酶[PAT]的玉米品种);33B(产生毒素Cry1Ac的棉花品种),I(产生毒素Cry1Ac的棉花品种),II(产生毒素Cry1Ac和Cry2Ab2的棉花品种);(产生VIP毒素的棉花品种);(产生毒素Cry3A的土豆品种);Bt- Bt11(例如CB)和法国SyngentaSeeds SAS的Bt176(产生毒素Cry1Ab和PAT酶的玉米品种),法国Syngenta Seeds SAS的MIR604(产生毒素Cry3A的修饰译本的玉米品种,参见WO 03/018810),比利时MonsantoEurope S.A.的MON 863(产生毒素Cry3Bb1的玉米品种),比利时Monsanto Europe S.A.的IPC 531(产生毒素Cry1Ac的修饰译本的棉花品种)和比利时Pioneer OverseasCorporation的27807(产生毒素Cry1F和PAT酶的玉米品种)。
此外,还包括通过使用重组DNA技术能够合成一种或多种对细菌、病毒或真菌病原体的抗性或耐受性增强的蛋白质的植物。该类蛋白的实例是所谓的“与发病机理相关的蛋白”(PR蛋白,例如参见EP-A 392 225),植物病害抗性基因(例如表达针对来自墨西哥野生土豆Solanum bulbocastanum的致病疫霉(Phytophthora infestans)起作用的抗性基因的土豆品种)或T4溶菌酶(例如能够合成对细菌如Erwinia amylvora具有增强的抗性的这些蛋白的土豆品种)。生产这些基因修饰植物的方法对本领域熟练技术人员是已知的且例如公开于上述出版物中。
此外,还包括通过使用重组DNA技术能够合成一种或多种蛋白以提高产量(例如生物质产生、谷粒产量、淀粉含量、油含量或蛋白质含量),对干旱、盐或其他生长限制性环境因素的耐受性或对害虫以及真菌、细菌和病毒病原体的耐受性的植物。
此外,还包括通过使用重组DNA技术而含有改变量的成分含量或新成分含量以尤其改善人类或动物营养的植物,例如产生促进健康的长链ω-3脂肪酸或不饱和ω-9脂肪酸的油料作物(例如油菜,加拿大DOW Agro Sciences)。
此外,还包括通过使用重组DNA技术而含有改变量的成分含量或新成分含量以尤其改善原料生产的植物,例如产生增加量的支链淀粉的土豆(例如土豆,德国BASF SE)。
本发明的另一实施方案为一种控制不希望的植物生长的方法,包括使除草活性量的至少一种如上所定义的式(I)化合物作用于植物、其环境或种子上。
式(I)的二氨基三嗪化合物的制备由实施例说明;然而,本发明主题并不限于所给实施例。
下面所示产物通过HPLC-MS光谱法测定的质量([m/z])或保留时间(RT;[min.])表征。
HPLC-MS=高效液相色谱联用质谱法;HPLC柱:
RP-18柱(Kinetex XB),50*2.1mm;移动相:水中0.1%三氟乙酸(TFA)+乙腈在1.5分钟内在60℃下,使用5:95至100:0的梯度,流速为在1.5分钟内0.8ml/min至1.0ml/min。
MS方法:四极电喷雾离子化,80V(正模式)。
使用如下缩写:
TFA:三氟乙酸
EtOAc:乙酸乙酯
THF:四氢呋喃
DMF:二甲基甲酰胺
MeOH:甲醇
MTBE:甲基叔丁基醚
HPLC:高压色谱法
LC:液相色谱法
MS:质谱法
式(I)的二氨基三嗪化合物的制备通过以下实施例进行说明:然而,本发明的主题不限于给出的实施例。
实施例3:N4-(6-溴-3-氟-2-甲氧基苯基)-6-(1-氟-1-甲基乙基)-1,3,5-三嗪-2,4-二胺
步骤1. 1-溴-4-氟-3-甲氧基-2-硝基-苯
在室温下,将甲醇钠(578mg,3.15mmol)缓慢添加到1-溴-3,4-二氟-2-硝基苯(500mg,2.01mmol)在3mL DMF中的溶液中。将反应混合物在室温下搅拌过夜,然后再次添加甲醇钠(54mg,1mmol)并搅拌过夜。用水和EtOAc萃取后处理之后,将粗品通过自动柱色谱法(二氧化硅,环己烷/EtOAc)纯化,得到487mg所需产物(24%产率)。
LC/MS RT:1.098,m/z未观察到最终化合物的电离。
步骤2. 6-溴-3-氟-2-甲氧基-苯胺
在室温下,将1-溴-4-氟-3-甲氧基-2-硝基-苯(435mg,1.75mmol)在3mL EtOAc中的溶液逐渐添加到锌(572mg,8.76mmol)在5mL乙酸中的悬浮液中。将反应混合物在室温下搅拌40小时。在H2O/EtOAc萃取后处理之后,蒸发溶剂后得到所需的苯胺(340mg,产率88%)。
LC/MS RT:1.033,m/z 221.7[M+H]+
步骤3.N4-(6-溴-3-氟-2-甲氧基-苯基)-6-(1-氟-1-甲基乙基)-1,3,5-三嗪-2,4-二胺
将6-溴-3-氟-2-甲氧基-苯胺(170mg,0.773mmol)和4-氯-6-(1-氟-1-甲基乙基)-1,3,5-三嗪-2-胺(147mg,0.7730mmol)溶解在6mL二烷中。添加3当量的4M HCl的二烷溶液后,将反应混合物在90℃下搅拌4小时。在H2O/EtOAc萃取后处理之后,通过自动柱色谱法纯化粗产物,得到164mg化合物3(产率57%)。
LC/MS RT:0.885,m/z 375.7[M+H]+
1H-NMR(400MHz,DMSO-d6)δ1.5(d,6H),3.7(s,3H),7.0(s,2H),7.2(t,1H),7.4(m,1H),9.1(s,1H)。
实施例21:N4-(2-溴-6-丁-2-炔氧基-3-氟-5-甲基-苯基)-6-(1-氟-1-甲基乙基)-1,3,5-三嗪-2,4-二胺
步骤1. 6-溴-4-氟-3-甲基-2-硝基-苯酚
在-20℃下,将硝酸(3.2mL,74.9mmol)滴加到6-溴-4-氟-3-甲基苯酚(16g,62.4mmol)在DCM(150mL)中的溶液中。将反应混合物在-15℃下搅拌20分钟。在H2O/DCM萃取后处理之后,通过自动柱色谱法(硅胶,环己烷/EtOAc)纯化粗产物,得到14.6g所需的硝基苯酚(75%产率)。
1H-NMR(400MHz,CDCl3)δ2.4(s,3H),7.9(d,1H),11.1(s,1H)。
步骤2. 1-溴-2-丁-2-炔氧基-5-氟-4-甲基-3-硝基-苯
将K2CO3(2.57g,9.28mmol)添加到6-溴-4-氟-3-甲基-2-硝基-苯酚(2.9g,9.23mmol)在DMF(30mL)中的溶液中。在室温下搅拌10分钟后,滴加1-溴-2-丁炔(1.48g,11.1mmol)并将反应混合物在室温下搅拌6小时。用H2O/EtOAc和MTBE萃取后处理之后,分离所需产物并用于下一步而无需进一步纯化(1.9g,58%产率)。
1H-NMR(400MHz,CDCl3)δ1.8(s,3H),2.2(s,3H),7.7(s,2H),7.4(d,1H)。
步骤3. 3-溴-2-丁-2-炔氧基-5-氟-6-甲基-苯胺。
在室温下,将2-溴-4-丁-2-炔氧基-1-氟-5-甲基-3-硝基-苯(1.90g,5.34mmol)在50mL EtOAc中的溶液逐渐添加到锌(1.39g,21mmol)在25mL乙酸中的悬浮液中过夜。添加第二份锌(1.90g,5.34mmol)和20mL乙酸,并将反应混合物再次在室温下搅拌过夜。粗产物通过自动柱色谱法(二氧化硅,环己烷/EtOAc)纯化,得到所需苯胺(650mg,45%产率)。
LC/MS RT:1.207,m/z 271.8[M+H]+
步骤4.N4-(3-溴-2-丁-2-炔氧基-5-氟-6-甲基-苯基)-6-(1-氟-1-甲基-乙基)-1,3,5-三嗪-2,4-二胺。
将3-溴-2-丁-2-炔氧基-5-氟-6-甲基-苯胺(650mg,2.389mmol)和4-氯-6-(1-氟-1-甲基乙基)-1,3,5-三嗪-2-胺(479mg,2.389mmol)溶解在15mL二烷中。添加3当量的4MHCl的二烷溶液后,将反应混合物在90℃下搅拌6小时。在H2O/EtOAc萃取后处理之后,通过自动柱色谱法(二氧化硅,环己烷/EtOAc)纯化粗产物,得到400mg化合物21(产率35%)。
LC/MS RT:1.069,m/z 427.6[M+H]+
类似于上述实施例制备下表3中所列的化合物(实施例3-158):
B应用实施例
式(I)的嗪类的除草活性由下列温室试验证实:
所用培养容器为含有含约3.0%腐殖土的壤质砂作为底物的塑料花盆。对每一品种单独播种测试植物的种子。
对于出苗前处理,直接在播种之后借助细分布喷嘴施用悬浮或乳化于水中的活性成分。温和灌溉容器以促进发芽和生长,然后用透明塑料罩覆盖,直到植物生根。该覆盖导致测试植物均匀发芽,除非这被活性成分损坏。
对于出苗后处理,首先使测试植物生长到3-15cm的高度,这取决于植物习性,并仅在此时用悬浮或乳化于水中的活性成分处理。为此,将测试植物直接播种并在相同容器中生长,或者首先使它们作为秧苗单独生长并在处理之前几天移植到测试容器中。
取决于品种,将植物分别保持在10-25℃或20-35℃下。
测试期为2-4周。在此期间照料植物并评价它们对各处理的响应。
使用0-100的评分进行评价。100表示没有植物出苗,或者至少地面上部分完全受损,而0表示没有损害,或者生长过程正常。对中等除草活性给予至少60的分值,对良好的除草活性给予至少70的分值,而对非常好的除草活性给予至少85的分值。
用于温室试验中的植物具有下列品种:
通过出苗前方法以250g/ha的施用率施用的实施例2对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例3对反枝苋、苘麻和大狗尾草显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例4对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例5对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例6对苘麻、稗草和大狗尾草分别显示出100%、85%和100%的除草活性。
通过出苗前方法以32g/ha的施用率施用的实施例7对苘麻、反枝苋和马唐草显示出100%的除草活性。
通过出苗前方法以32g/ha的施用率施用的实施例8对苘麻、反枝苋和马唐草显示出100%的除草活性。
通过出苗前方法以32g/ha的施用率施用的实施例9对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以32g/ha的施用率施用的实施例10对苘麻、反枝苋和马唐草显示出100%的除草活性。
通过出苗前方法以32g/ha的施用率施用的实施例11对苘麻、反枝苋和马唐草显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例12对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例13对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例14对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例15对大狗尾草、大穗看麦娘和多花黑麦草分别显示出90%、95%和95%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例16对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例17对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例18对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例19对大狗尾草、大穗看麦娘和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例20对大狗尾草、大穗看麦娘和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例21对大狗尾草、大穗看麦娘和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例22对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例23对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例24对阿披拉草和反枝苋显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例25对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例26对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例27对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例28对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例29对大狗尾草、反枝苋和苘麻显示出100%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例30对阿披拉草和反枝苋显示出85%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例31对阿披拉草、大狗尾草和苘麻显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例32对大穗看麦娘、大狗尾草和苘麻显示出100%的除草活性。
通过出苗前方法以125g/ha的施用率施用的实施例33对大穗看麦娘、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以125g/ha的施用率施用的实施例35对阿披拉草、苘麻和反枝苋显示出100%、95%和100%的除草活性。
通过出苗前方法以125g/ha的施用率施用的实施例36对阿披拉草、稗草和大狗尾草显示出100%、85%和90%的除草活性。
通过出苗前方法以125g/ha的施用率施用的实施例37对阿披拉草、苘麻和大狗尾草显示出100%、85%和85%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例38对反枝苋、苘麻和大狗尾草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例39对反枝苋、苘麻和大狗尾草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例40对稗草、苘麻和大狗尾草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例41对稗草、苘麻和大狗尾草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例45对多花黑麦草、苘麻和大狗尾草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例46对多花黑麦草、反枝苋和大狗尾草分别显示出80%、100%、100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例47对多花黑麦草和大狗尾草分别显示出80%和90%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例48对多花黑麦草、大狗尾草和稗草分别显示出98%、80%和90%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例49对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例50对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例51对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例52对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例53对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例54对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例55对苘麻、大狗尾草和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例56对苘麻、大狗尾草和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例57对反枝苋、大狗尾草和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例58对反枝苋、大狗尾草和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例59对反枝苋、大狗尾草和大穗看麦娘显示出100%、100%和95%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例60对反枝苋、大狗尾草和苘麻显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例61对大穗看麦娘、大狗尾草和稗草显示出75%、85%和70%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例62对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例63对苘麻、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例64对多花黑麦草、大狗尾草和稗草分别显示出98%、100%和100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例65对苘麻、大狗尾草和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例66对苘麻、大狗尾草和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例67对苘麻、大狗尾草和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例68对苘麻、大狗尾草和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例69对苘麻、大狗尾草和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例70对苘麻、大狗尾草和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例71对苘麻、大狗尾草和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例72对反枝苋和大狗尾草(Setaria faber)显示出100%和80%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例2对苘麻、稗草和马唐草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例3对苘麻、稗草和马唐草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例4对苘麻、稗草和马唐草显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例5对苘麻、稗草和马唐草分别显示出90%、85%和100%的除草活性。
通过出苗前方法以125g/ha的施用率施用的实施例6对苘麻、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以125g/ha的施用率施用的实施例7对苘麻、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以125g/ha的施用率施用的实施例8对苘麻、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例9对反枝苋、苘麻和大狗尾草分别显示出100%、90%和95%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例10对反枝苋、苘麻和大狗尾草显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例11对大穗看麦娘、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例12对大穗看麦娘、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例13对大穗看麦娘、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以125g/ha的施用率施用的实施例14对大穗看麦娘、稗草和大狗尾草分别显示出98%、98%和100%的除草活性。
通过出苗前方法以125g/ha的施用率施用的实施例15对大穗看麦娘、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例16对反枝苋、稗草和苘麻显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例17对反枝苋、稗草和苘麻显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例18对反枝苋、稗草和苘麻显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例19对反枝苋、稗草和苘麻显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例20对反枝苋、稗草和苘麻显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例21对反枝苋、稗草和大狗尾草分别显示出95%、100%和100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例22对反枝苋、稗草和大狗尾草分别显示出85%、85%和100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例23对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例24对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例25对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例26对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例27对反枝苋和大狗尾草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例28对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例29对反枝苋、大狗尾草和苘麻显示出100%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例30对大狗尾草、大穗看麦娘和苘麻显示出100%的除草活性。
通过出苗前方法以250g/ha的施用率施用的实施例31对反枝苋、稗草和苘麻显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例32对反枝苋、稗草和苘麻显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例33对反枝苋、稗草和苘麻分别显示出100%、98%和100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例34对反枝苋、稗草和苘麻显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例35对反枝苋、稗草和苘麻显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例36对反枝苋、稗草和苘麻显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例37对反枝苋、稗草和苘麻分别显示出100%、100%和98%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例38对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例39对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例40对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例41对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例42对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例43对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例44对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例45对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例46对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例47对反枝苋、稗草和大狗尾草显示出100%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例48对反枝苋、稗草和大狗尾草分别显示出100%、70%和100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例49对反枝苋、稗草和苘麻显示出100%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例50对反枝苋、大狗尾草和苘麻分别显示出100%、100%和80%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例51对反枝苋、大狗尾草和苘麻显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例52对稗草、大狗尾草和阿披拉草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例53对稗草、大狗尾草和大穗看麦娘分别显示出98%、100%和90%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例54对大穗看麦娘、苘麻和稗草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例55对反枝苋、苘麻和稗草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例56对大狗尾草、苘麻和稗草分别显示出100%、90%和90%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例57对大狗尾草、苘麻和稗草分别显示出100%、98%和100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例58对大狗尾草、苘麻和稗草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例59对大狗尾草、苘麻和稗草分别显示出100%、100%和95%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例60对大狗尾草、反枝苋和阿披拉草分别显示出98%、100%和95%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例61对苘麻、反枝苋和稗草分别显示出100%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例62对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以31g/ha的施用率施用的实施例63对大狗尾草、反枝苋和大穗看麦娘分别显示出100%、80%和80%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例64对大狗尾草、苘麻和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例65对大狗尾草、苘麻和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例66对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例67对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例68对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例69对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例70对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例71对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例72对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例73对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例74对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例75对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例76对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例77对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例78对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例79对大狗尾草、反枝苋和苘麻显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例80对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例81对大狗尾草、苘麻和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例82对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例83对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例84对大狗尾草、苘麻和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例85对大狗尾草、苘麻和稗草分别显示出98%、85%和100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例86对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例87对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例88对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例89对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例90对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例91对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例92对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例92对苘麻、大穗看麦娘和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例93对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例93对苘麻、反枝苋和大狗尾草分别显示出80%、100%和70%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例94对大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例95对苘麻、大狗尾草、反枝苋和稗草显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例96对大狗尾草和稗草分别显示出75%和70%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例97对大狗尾草、反枝苋和大穗看麦娘分别显示出85%、85%和70%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例98对大狗尾草、反枝苋和大穗看麦娘显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例99对大狗尾草、反枝苋和苘麻显示出100%的除草活性。
通过出苗前方法以62g/ha的施用率施用的实施例100对大狗尾草、稗草和大穗看麦娘分别显示出100%、100%和98%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例102对大穗看麦娘、大狗尾草和多花黑麦草分别显示出85%、80%和90%的除草活性。
通过出苗前方法以62,5g/ha的施用率施用的实施例104对大穗看麦娘、大狗尾草和多花黑麦草分别显示出90%、85%和100%的除草活性。
Claims (12)
1.式(I)的二氨基三嗪化合物:
其中
R1为Cl、Br、I、CR1A;
其中R1A为H或卤素;
R2选自H、卤素、CR2A;
其中R2A为H或卤素;
R3为H、卤素;
R4选自卤素、CR4A;
其中R4A为H或卤素;
R5选自H、卤素、CN、C1-C6烷基、(C1-C6烷氧基)-C1-C6烷基、C3-C6环烷基、(C3-C6环烷基)-C1-C4烷基、C1-C6烷氧基、C2-C6链烯氧基、C2-C6炔氧基、C3-C6环烷氧基、(C3-C6环烷基)-C1-C4烷氧基,其中所述基团的脂族和环脂族部分未被取代、部分或完全被卤化;
R6选自H、卤素、CN、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基和C1-C6卤代烷氧基;
R7选自卤素、CN、C1-C6烷基、C2-C6链烯基、C3-C6炔基、C3-C6环烷基、(C3-C6环烷基)-C1-C4烷基、C3-C6环烯基和C1-C6烷氧基-C1-C6烷基,其中所述基团的脂族和环脂族部分未被取代、部分或完全被卤化;
R6和R7与其所连接的碳原子一起形成选自羰基、C3-C6环烷基、C3-C6环烯基、3-6员饱和或部分不饱和的杂环基的结构部分,和结构部分>C=CRxRy,其中Rx和Ry为氢、C1-C4烷基、C1-C4卤代烷基、C3-C6环烷基或者CRxRy形成3-6员环烷基;
R8选自C1-C6烷基、C2-C6链烯基、C2-C6炔基、(C1-C6烷氧基)-C1-C6烷基、(C1-C6烷氧基)-C2-C6链烯基、(C1-C6烷氧基)-C2-C6炔基、(C1-C6环烷基)-C2-C6炔基、(C3-C6环烷基)-C1-C4烷基、(C3-C6环烷氧基)-C1-C4烷基,其中上述基团未被取代、部分或完全被卤化,并且其中后提到的6个基团的环脂族部分可以带有1、2、3、4、5或6个甲基,
包括其可农用盐。
2.根据权利要求1的化合物,其中R2选自Cl、Br、CH3。
3.根据权利要求1或2的化合物,其中R4选自H、F、CH3。
4.根据权利要求1-3中任一项的化合物,其中R3为H。
5.根据权利要求1-4中任一项的化合物,其中R4选自F、Cl、Br、CH3。
6.根据权利要求1-5中任一项的化合物,其中
R5选自氢、氟、C1-C4烷基和C1-C4烷氧基;
R6选自氢、氟、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基和C1-C6卤代烷氧基;
R7选自C1-C6烷基、C1-C6卤代烷基、C2-C6链烯基、C3-C6炔基、C3-C6环烷基、C3-C6环烯基和C1-C6烷氧基-C1-C6烷基;或者
R6和R7与其所连接的碳原子一起形成选自C3-C6环烷基、C3-C6环烯基和3-6员饱和或部分不饱和的杂环基的结构部分。
7.根据权利要求1-6中任一项的化合物,其中
R5选自氢、氟;
R6选自氢、氟、C1-C4烷基;
R7选自C1-C6烷基;或者
R6和R7与其所连接的碳原子一起形成选自C3-C6环烷基的结构部分。
8.根据权利要求1-7中任一项的化合物,其中
R8选自C1-C6烷基、C2-C6链烯基、C2-C6炔基、(C1-C6烷氧基)-C1-C6烷基。
9.根据权利要求1-8中任一项的化合物,其中
R8选自CH3、CH2CC、CH2CCCH3、CH2OCH3。
10.一种农业化学组合物,包含除草活性量的至少一种如权利要求1-9中任一项所要求保护的化合物和至少一种惰性液体和/或固体载体以及合适的话,至少一种表面活性物质。
11.一种控制不希望的植物生长的方法,包括使除草活性量的至少一种如权利要求1-10中任一项所要求保护的化合物作用于植物、其环境或种子上。
12.如权利要求1-11中任一项所要求保护的化合物作为除草剂或使植物干燥/脱叶的用途。
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