CA2312703A1 - Herbicides 3-(benzazol-4-yl)pyrimidine-dione-derivatives - Google Patents
Herbicides 3-(benzazol-4-yl)pyrimidine-dione-derivatives Download PDFInfo
- Publication number
- CA2312703A1 CA2312703A1 CA002312703A CA2312703A CA2312703A1 CA 2312703 A1 CA2312703 A1 CA 2312703A1 CA 002312703 A CA002312703 A CA 002312703A CA 2312703 A CA2312703 A CA 2312703A CA 2312703 A1 CA2312703 A1 CA 2312703A1
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- butyl
- carbonyl
- ethyl
- halogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000004009 herbicide Substances 0.000 title claims description 10
- -1 1,3-propylene- Chemical class 0.000 claims abstract description 915
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 47
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 46
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 40
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 33
- 150000002367 halogens Chemical class 0.000 claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims abstract description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 20
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 125000004739 (C1-C6) alkylsulfonyl group Chemical group 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims abstract description 5
- 125000004738 (C1-C6) alkyl sulfinyl group Chemical group 0.000 claims abstract description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims abstract description 3
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 77
- 239000000203 mixture Substances 0.000 claims description 76
- 150000001875 compounds Chemical class 0.000 claims description 55
- 230000008569 process Effects 0.000 claims description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims description 43
- 239000001257 hydrogen Substances 0.000 claims description 42
- BTRZCXUPKJCHIB-UHFFFAOYSA-N 3-(1h-indol-4-yl)-1h-pyrimidine-2,4-dione Chemical class O=C1C=CNC(=O)N1C1=CC=CC2=C1C=CN2 BTRZCXUPKJCHIB-UHFFFAOYSA-N 0.000 claims description 24
- 239000000460 chlorine Chemical group 0.000 claims description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 229910052801 chlorine Chemical group 0.000 claims description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 16
- 230000002363 herbicidal effect Effects 0.000 claims description 16
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 15
- 239000011737 fluorine Chemical group 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 13
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 12
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 11
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 11
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 5
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000011593 sulfur Chemical group 0.000 claims description 4
- 125000004769 (C1-C4) alkylsulfonyl group Chemical group 0.000 claims description 3
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 125000004737 (C1-C6) haloalkoxy group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- ORTFAQDWJHRMNX-UHFFFAOYSA-N hydroxidooxidocarbon(.) Chemical group O[C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Substances SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims 1
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 abstract description 3
- 125000004768 (C1-C4) alkylsulfinyl group Chemical group 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 162
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 83
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 62
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 58
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 58
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 57
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 49
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 43
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 41
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 34
- 239000011541 reaction mixture Substances 0.000 description 31
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- 239000002585 base Substances 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 238000005160 1H NMR spectroscopy Methods 0.000 description 26
- 101150041968 CDC13 gene Proteins 0.000 description 26
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 26
- 239000002904 solvent Substances 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 239000004480 active ingredient Substances 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 125000005499 phosphonyl group Chemical group 0.000 description 21
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 20
- 239000002253 acid Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 241000196324 Embryophyta Species 0.000 description 18
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 16
- 239000007858 starting material Substances 0.000 description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000003085 diluting agent Substances 0.000 description 15
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 14
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 14
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 13
- 229910052794 bromium Inorganic materials 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 125000001931 aliphatic group Chemical group 0.000 description 12
- 238000009835 boiling Methods 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 125000001153 fluoro group Chemical group F* 0.000 description 12
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 235000011167 hydrochloric acid Nutrition 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 11
- 239000002798 polar solvent Substances 0.000 description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 description 11
- 235000011152 sodium sulphate Nutrition 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 10
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 10
- 239000012043 crude product Substances 0.000 description 10
- 150000004292 cyclic ethers Chemical class 0.000 description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 239000003480 eluent Substances 0.000 description 10
- 150000002431 hydrogen Chemical group 0.000 description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000012312 sodium hydride Substances 0.000 description 10
- 229910000104 sodium hydride Inorganic materials 0.000 description 10
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 9
- 150000001298 alcohols Chemical class 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- 150000001448 anilines Chemical class 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 6
- 239000004359 castor oil Substances 0.000 description 6
- 235000019438 castor oil Nutrition 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 238000003379 elimination reaction Methods 0.000 description 6
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 6
- 150000008282 halocarbons Chemical class 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000007530 organic bases Chemical class 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 235000011181 potassium carbonates Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- CCPHAMSKHBDMDS-UHFFFAOYSA-N Chetoseminudin B Natural products C=1NC2=CC=CC=C2C=1CC1(SC)NC(=O)C(CO)(SC)N(C)C1=O CCPHAMSKHBDMDS-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 235000013877 carbamide Nutrition 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 230000008030 elimination Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 238000006396 nitration reaction Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 125000006238 prop-1-en-1-yl group Chemical group [H]\C(*)=C(/[H])C([H])([H])[H] 0.000 description 5
- 238000007363 ring formation reaction Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 235000011150 stannous chloride Nutrition 0.000 description 5
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- WLOOYFSUYWVINT-UHFFFAOYSA-N 3-(2-amino-4-chloro-6-fluoro-3-hydroxyphenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4-dione Chemical compound O=C1N(C)C(C(F)(F)F)=CC(=O)N1C1=C(N)C(O)=C(Cl)C=C1F WLOOYFSUYWVINT-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical class ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 101100054666 Streptomyces halstedii sch3 gene Proteins 0.000 description 4
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 4
- 150000008046 alkali metal hydrides Chemical class 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 244000038559 crop plants Species 0.000 description 4
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000003818 flash chromatography Methods 0.000 description 4
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- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 125000004194 piperazin-1-yl group Chemical group [H]N1C([H])([H])C([H])([H])N(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000004574 piperidin-2-yl group Chemical group N1C(CCCC1)* 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 238000001556 precipitation Methods 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000000177 propargylthio group Chemical group [H]C#CC([H])([H])S* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 125000004307 pyrazin-2-yl group Chemical group [H]C1=C([H])N=C(*)C([H])=N1 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002206 pyridazin-3-yl group Chemical group [H]C1=C([H])C([H])=C(*)N=N1 0.000 description 1
- 125000004940 pyridazin-4-yl group Chemical group N1=NC=C(C=C1)* 0.000 description 1
- 150000004892 pyridazines Chemical class 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000004527 pyrimidin-4-yl group Chemical group N1=CN=C(C=C1)* 0.000 description 1
- 125000004528 pyrimidin-5-yl group Chemical group N1=CN=CC(=C1)* 0.000 description 1
- 150000008512 pyrimidinediones Chemical class 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000013526 red clover Nutrition 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000004576 sand Substances 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
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- OKQKDCXVLPGWPO-UHFFFAOYSA-N sulfanylidenephosphane Chemical compound S=P OKQKDCXVLPGWPO-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 125000004192 tetrahydrofuran-2-yl group Chemical group [H]C1([H])OC([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004187 tetrahydropyran-2-yl group Chemical group [H]C1([H])OC([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- AHJWSRRHTXRLAQ-UHFFFAOYSA-N tetramethoxymethane Chemical compound COC(OC)(OC)OC AHJWSRRHTXRLAQ-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000004324 thiepan-2-yl group Chemical group [H]C1([H])SC([H])(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000004275 thietan-2-yl group Chemical group [H]C1([H])SC([H])(*)C1([H])[H] 0.000 description 1
- 125000006300 thietan-3-yl group Chemical group [H]C1([H])SC([H])([H])C1([H])* 0.000 description 1
- 125000001730 thiiranyl group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- WTVXIBRMWGUIMI-UHFFFAOYSA-N trifluoro($l^{1}-oxidanylsulfonyl)methane Chemical group [O]S(=O)(=O)C(F)(F)F WTVXIBRMWGUIMI-UHFFFAOYSA-N 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004562 water dispersible granule Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- 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
- A01N43/647—Triazoles; Hydrogenated triazoles
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
- C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom
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- Chemical & Material Sciences (AREA)
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- Plant Pathology (AREA)
- Zoology (AREA)
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- Plural Heterocyclic Compounds (AREA)
Abstract
The invention relates to 3-(benzazol-4-yl)pyrimidine-dione-derivatives of formula (I) and the salts thereof, whereby X = O, S; R1 = H, NH2, C1-C6-alkyl, C1-C6-alkyl halide; R2 = H, halogen, C1-C6-alkyl, C1-C6-alkyl halide, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl; R3 = H, halogen, C1-C6-alkyl; R4 = H, halogen; R5 = CN, halogen, C1-C6-alkyl, C1-C6-alkyl halide, C1-C6-alkoxyl, C1-C6-alkoxyl halide; =Y- = a group =N-N(R6)-, =C(ZR7)-N(R6)-, =C(ZR7)-O-, =C(ZR7)-S-; R6 = C1-C6-alkyl, C1-C4-alkyl halide, C3-C6-cycloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkyl-SO2, C1-C6-alkyl-CO, C1-C6-alkyl halide-CO, C1-C6-alkyl-CS, C1-C6-alkoxyl-CO, C1-C6-alkoxyl-CS or optionally substituted C1-C6-alkyl; Z = chemical bond, O, S, -S(O)-, -SO2-, -NH-, -N(R8)-; R7, R8 = C1-C6-alkyl, C1-C6-alkyl halide, hydroxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkoxyl-C1-C4-alkyl, C1-C4-alkoxyl halide-C1-C4-alkyl, C3-C4-alkenyloxyl-C1-C4-alkyl, C3-C4-alkynyloxyl-C1-C4-alkyl, C3-C8-cycloalkoxyl-C1-C4-alkyl, amino-C1-C4-alkyl, C1-C4-alkylamino-C1-C4-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkylthio halide-C1-C4-alkyl, C3-C4-alkenylthio-C1-C4-alkyl, C3-C4-alkynylthio-C1-C4-alkyl, C1-C4-alkylsulfinyl-C1-C4-alkyl, C1-C4-alkylsulfinyl halide-C1-C4-alkyl, C3-C4-alkenylsulfinyl-C1-C4-alkyl, C3-C4-alkynylsulfinyl-C1-C4-alkyl, C3-C6-alkenyl, cyano-C3-C6-alkenyl, C3-C6-alkenyl halide, C3-C6-alkynyl, cyano-C3-C6-alkynyl, C3-C6-alkynyl halide, HO-CO-C1-C4-alkyl, (C1-C4-alkoxyl)CO-C1-C4-alkyl, (C1-C4-alkyl)CS-C1-C4-alkyl, H2N-CO-C1-C4-alkyl, C1-C4-alkyl-NHCO-C1-C4-alkyl, di(C1-C4-alkyl)NCO-C1-C4-alkyl, di(C1-C4-alkyl)phosphonyl-C1-C4-alkyl, optionally substituted C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenyl-C1-C4-alkyl, 3- to 7-linked heterocyclyl or heterocyclyl-C1-C4-alkyl, whereby each heterocyclyl ring can contain a CO-ring link or CS-ring link, or provided that Z = chemical bond, R7 also H, OH, CN, SH, NH2, halogen, -CH(OH)-CH2-R9, -CH(halogen)-CH2-R9, -CH2-CH(halogen)-R9, -CH=CH-R9 or -CH=C(halogen)-R9, whereby R9 = COOH, (C1-C4-alkoxyl)carbonyl, (C1-C4-alkylthio)carbonyl, CONH2, C1-C4-alkyl-NHCO or di(C1-C4-alkyl)NCO, or R7 + R8 = an optionally substituted 1,3-propylene-, tetramethylene-, pentamethylene-or ethylene oxyethylene-chain.
Description
HERBICIDES 3-(BENZAZOL-4-YL)PYRIMIDINE-DIONE-DERIVATIVES
The present invention relates to novel 3-(benzazol-4-yl)pyrimidinedione derivatives of the formula I
R1~ O R4 N~ - ~ ~ 5 R2 ~ N R
Ir N- Y
where the variables have the following meanings:
X is oxygen or sulfur;
R1 is hydrogen, amino, C1-C6-alkyl or C1-C6-haloalkyl;
R2 is hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylthio, C1-C6-alkylsulfinyl or C1-C6-alkylsulfonyl;
R3 is hydrogen, halogen or C1-C6-alkyl;
R4 is hydrogen or halogen;
RS is cyano, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
=Y- is a group =N-N(R6)-, =C(ZR~)-N(R6)-, =C(ZR7)-O- or =C(ZR7)-S-;
R6 is C1-C6-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkylsulfonyl, (C1-C6-alkyl)carbonyl, (C1-C6-haloalkyl)carbonyl, (C1-C6-alkyl)thiocarbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6-alkoxy)thiocarbonyl or C1-C6-alkyl which can be substituted by cyano, C1-C6-alkoxy, C1-C6-alkylthio, (C1-C6-alkoxy)carbonyl, (C1-C6-alkylamino)carbonyl, di(C1-C6-alkyl)aminocarbonyl or (C1-C6-alkyl)carbonyloxy;
The present invention relates to novel 3-(benzazol-4-yl)pyrimidinedione derivatives of the formula I
R1~ O R4 N~ - ~ ~ 5 R2 ~ N R
Ir N- Y
where the variables have the following meanings:
X is oxygen or sulfur;
R1 is hydrogen, amino, C1-C6-alkyl or C1-C6-haloalkyl;
R2 is hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylthio, C1-C6-alkylsulfinyl or C1-C6-alkylsulfonyl;
R3 is hydrogen, halogen or C1-C6-alkyl;
R4 is hydrogen or halogen;
RS is cyano, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
=Y- is a group =N-N(R6)-, =C(ZR~)-N(R6)-, =C(ZR7)-O- or =C(ZR7)-S-;
R6 is C1-C6-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkylsulfonyl, (C1-C6-alkyl)carbonyl, (C1-C6-haloalkyl)carbonyl, (C1-C6-alkyl)thiocarbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6-alkoxy)thiocarbonyl or C1-C6-alkyl which can be substituted by cyano, C1-C6-alkoxy, C1-C6-alkylthio, (C1-C6-alkoxy)carbonyl, (C1-C6-alkylamino)carbonyl, di(C1-C6-alkyl)aminocarbonyl or (C1-C6-alkyl)carbonyloxy;
Z is a chemical bond, oxygen, sulfur, -S(O)-, -S(O)2-, -NH- or R~ and Re independently of one another are C1-C6-alkyl, C1-C6-haloalkyl, hydroxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C3-C4-alkenyloxy-C1-C4-alkyl, C3-CQ-alkynyloxy-C1-C4-alkyl, C3-C$-cycloalkoxy-C1-C4-alkyl, amino-C1-C4-alkyl, C1-C4-alkylamino-C1-C4-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkylthio-C1-C4-alkyl, C3-C4-alkenylthio-C1-C4-alkyl, C3-C4-alkynylthio-C1-C4-alkyl, C1-C4-alkylsulfinyl-C1-C4-alkyl, Ci-C4-haloalkylsulfinyl-Cl-C4-alkyl, C3-C4-alkenylsulfinyl-C1-C4-alkyl, C3-C4-alkynylsulfinyl-C1-C4-alkyl, C1-C4-alkylsulfonyl-C1-C4-alkyl, C1-C4-haloalkylsulfonyl-C1-C4-alkyl, C3-Ca-alkenylsulfonyl-C1-C4-alkyl, C3-C4-alkynylsulfonyl-C1-C4-alkyl, C3-C6-alkenyl, cyano-C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-alkynyl, cyano-C3-C6-alkynyl, C3-C6-haloalkynyl, hydroxycarbonyl-C1-C4-alkyl, (Ci-C4-alkoxy)carbonyl-C1-C4-alkyl, (C1-C4-alkylthio)carbonyl-C1-C4-alkyl, aminocarbonyl-C1-C4-alkyl, (C1-C4-alkylamino)carbonyl-C1-C4-alkyl, di(C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl, di(C1-C4-alkyl)phosphonyl-C1-C4-alkyl, C3-Ce-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenyl-C1-C4-alkyl, 3- to 7-membered heterocyclyl or heterocyclyl-C1-C4-alkyl, it being possible for each heterocyclyl ring to contain a carbonyl or thiocarbonyl ring member, and it being possible for each cycloalkyl, phenyl and heterocyclyl ring to be unsubstituted or to have attached to it one to four substituents, in each case selected from the group consisting of cyano, nitro, amino, hydroxyl, carboxyl, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkyl)carbonyl, (C1-C4-haloalkyl)carbonyl, (C1-C4-alkyl)carbonyloxy, (C1_C4-haloalkyl)carbonyloxy and di(C1-C4-alkyl)amino, ' CA 02312703 2000-06-OS
or, if z is a chemical bond, R7 is, if desired, also hydrogen, hydroxyl, cyano, mercapto, amino, halogen, -CH(OH)-CH2-R9 , -CH(halogen)-CHz-R9, -CH2-CH(halogen)-R9, -CH=CH-R9 or -CH=C(halogen)-R9, where R9 is hydroxycarbonyl, (C1-C4-alkoxy)carbonyl, (C1-CQ-alkylthio)carbonyl, aminocarbonyl, (C1-CQ-alkylamino)carbonyl or di(C1-C4-alkyl)aminocarbonyl, or R7 and R8 together are a 1,3-propylene, tetramethylene, pentamethylene or ethyleneoxyethylene chain which can in each case be unsubstituted or have attached to it one to four C1-C4-alkyl groups or one or two (C1-C4-alkoxy)carbonyl groups;
and to the agriculturally useful salts of the compounds I.
Moreover, the invention relates to _ the use of the compounds I as herbicides, - herbicidal compositions which comprise the compounds I as active substances, processes for the preparation of the compounds I and of herbicidal compositions using the compounds I, - methods of controlling undesirable vegetation with the compounds I, and - intermediates of the formulae III, IV and V for the preparation of the compounds I.
WO 97/08170 describes certain 3-(benzox/benzothiazol-7-yl)-6-(trifluoromethyl)uracils as herbicides. Other 3-(benzothiazol-7-yl)uracils and their use as herbicides and for the desiccation/defoliation of plants are taught in WO 97/08171.
gubject-matter of WO 97/12886 are, inter alia, certain 3-benzisoxazol-7-yl-2,4-(1H,3H)pyrimidinediones, which are said to have a herbicidal and desiccant action.
It is an object of the present invention to provide novel herbicidally active uracil compounds which allow better targeted control of undesirable plants than was possible with the known compounds.
We have found that this object is achieved by the present 3-(benzazol-4-yl)pyrimidinedione derivatives of the formula I.
and to the agriculturally useful salts of the compounds I.
Moreover, the invention relates to _ the use of the compounds I as herbicides, - herbicidal compositions which comprise the compounds I as active substances, processes for the preparation of the compounds I and of herbicidal compositions using the compounds I, - methods of controlling undesirable vegetation with the compounds I, and - intermediates of the formulae III, IV and V for the preparation of the compounds I.
WO 97/08170 describes certain 3-(benzox/benzothiazol-7-yl)-6-(trifluoromethyl)uracils as herbicides. Other 3-(benzothiazol-7-yl)uracils and their use as herbicides and for the desiccation/defoliation of plants are taught in WO 97/08171.
gubject-matter of WO 97/12886 are, inter alia, certain 3-benzisoxazol-7-yl-2,4-(1H,3H)pyrimidinediones, which are said to have a herbicidal and desiccant action.
It is an object of the present invention to provide novel herbicidally active uracil compounds which allow better targeted control of undesirable plants than was possible with the known compounds.
We have found that this object is achieved by the present 3-(benzazol-4-yl)pyrimidinedione derivatives of the formula I.
There have furthermore been found herbicidal compositions which comprise the compounds I and which have a very good herbicidal action. Moreover, there have been found processes for the preparation of these compositions and methods of controlling undesirable vegetation with the compounds I.
Depending on the substitution pattern, the compounds of the formula I can have one or more chiral centers, in which case they exist as enantiomer or diastereomer mixtures. In the case of compounds I having at least one olefinic radical, E/Z isomers may also be possible. The present invention relates to the pure enantiomers or diastereomers and also to mixtures of these.
The formula I only represents one of the possible versions for some compounds according to the invention. Thus, for example, those compounds I where R7 = hydroxyl may also be written as tautomers I' [ -N=C ( OH ) -<---~-NH-CO- ]
\ O R4 N R
I~
R3 X HN (O/S/N) O
Suitable amongst agriculturally useful salts are mainly the salts of those cations or the acid addition salts of those acids whose cations, or anions, respectively, do not adversely affect the herbicidal action of the compounds I. Thus, suitable cations are, in particular, the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, can have attached to it one to four C1-C4-alkyl substituents and/or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-CQ-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-CQ-alkyl)sulfoxonium.
Anions of useful acid addition salts are, mainly, chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate benzoate, and the anions of C1-CQ-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric 5 acid or nitric acid.
The organic moieties - like the meaning of halogen - which are mentioned in the definition of the substituents R1 to R3 and R5 to R9 or as radicals of cycloalkyl, phenyl or heterocyclic rings represent collective terms for individual enumerations of the individual group members. All carbon chains, ie. all alkyl, haloalkyl, cyanoalkyl, hydroxyalkyl, aminoalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, phenylalkyl, heterocyclylalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkenyl, haloalkenyl, cyanoalkenyl, alkenyloxy, alkenylthio, alkenylsulfinyl, alkenylsulfonyl, alkynyl, haloalkynyl, cyanoalkynyl, alkynyloxy, alkynylthio, alkynylsulfinyl and alkynylsulfonyl moieties, can be straight-chain or branched. Halogenated substituents preferably have attached to them one to five identical or different halogen atoms. The meaning of halogen is in each case fluorine, chlorine, bromine or iodine.
ether meanings are, for example:
- C1-C4-alkyl: CH3, CZHS, CHZ-CZHS, CH(CH3)Z, n-butyl, CH(CH3)-CZHS, CH2-CH(CH3)2 Or C(CH3)3i - C1-C4-haloalkyl: a C1-C4-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. CHZF, CHF2, CF3, CH2C1, CH(C1)Z, C(C1)3, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, C2F5, 2-fluoropropyl, 3-fluoropropyl, 2.2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CH2-CzFS, CFZ-C2F5, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;
Depending on the substitution pattern, the compounds of the formula I can have one or more chiral centers, in which case they exist as enantiomer or diastereomer mixtures. In the case of compounds I having at least one olefinic radical, E/Z isomers may also be possible. The present invention relates to the pure enantiomers or diastereomers and also to mixtures of these.
The formula I only represents one of the possible versions for some compounds according to the invention. Thus, for example, those compounds I where R7 = hydroxyl may also be written as tautomers I' [ -N=C ( OH ) -<---~-NH-CO- ]
\ O R4 N R
I~
R3 X HN (O/S/N) O
Suitable amongst agriculturally useful salts are mainly the salts of those cations or the acid addition salts of those acids whose cations, or anions, respectively, do not adversely affect the herbicidal action of the compounds I. Thus, suitable cations are, in particular, the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, can have attached to it one to four C1-C4-alkyl substituents and/or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-CQ-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-CQ-alkyl)sulfoxonium.
Anions of useful acid addition salts are, mainly, chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate benzoate, and the anions of C1-CQ-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric 5 acid or nitric acid.
The organic moieties - like the meaning of halogen - which are mentioned in the definition of the substituents R1 to R3 and R5 to R9 or as radicals of cycloalkyl, phenyl or heterocyclic rings represent collective terms for individual enumerations of the individual group members. All carbon chains, ie. all alkyl, haloalkyl, cyanoalkyl, hydroxyalkyl, aminoalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, phenylalkyl, heterocyclylalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkenyl, haloalkenyl, cyanoalkenyl, alkenyloxy, alkenylthio, alkenylsulfinyl, alkenylsulfonyl, alkynyl, haloalkynyl, cyanoalkynyl, alkynyloxy, alkynylthio, alkynylsulfinyl and alkynylsulfonyl moieties, can be straight-chain or branched. Halogenated substituents preferably have attached to them one to five identical or different halogen atoms. The meaning of halogen is in each case fluorine, chlorine, bromine or iodine.
ether meanings are, for example:
- C1-C4-alkyl: CH3, CZHS, CHZ-CZHS, CH(CH3)Z, n-butyl, CH(CH3)-CZHS, CH2-CH(CH3)2 Or C(CH3)3i - C1-C4-haloalkyl: a C1-C4-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. CHZF, CHF2, CF3, CH2C1, CH(C1)Z, C(C1)3, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, C2F5, 2-fluoropropyl, 3-fluoropropyl, 2.2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CH2-CzFS, CFZ-C2F5, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;
- C1-C6-alkyl: a Cf-C4-alkyl radical as mentioned above or, for example, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl, preferably CH3. C2H5. CH2-C2H5, CH(CH3)2, n-butyl, C(CH3)3.
n-pentyl or n-hexyl;
- C1-C6-haloalkyl: a C1-C6-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. one of the radicals mentioned under C1-C4-haloalkyl or 5-fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodo-1-pentyl, 5,5,5-trichloro-1-pentyl, undecafluoropentyl, 6-fluoro-1-hexyl, 6-chloro-1-hexyl, 6-bromo-1-hexyl, 6-iodo-1-hexyl, 6,6,6-trichloro-1-hexyl or dodecafluorohexyl;
- cyano-C1-C4-alkyl: CH2CN, 1-cyanoethyl, 2-cyanoethyl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyanoprop-1-yl, 1-cyanobut-1-yl, 2-cyanobut-1-yl, 3-cyanobut-1-yl, 4-cyanobut-1-yl, 1-cyanobut-2-yl, 2-cyanobut-2-yl, 3-cyanobut-2-yl, 4-cyanobut-2-yl, 1-(CHZCN)eth-1-yl, 1-(CHZCN)-1-(CH3)-eth-1-yl or 1-(CH2CN)prop-1-yl;
- hydroxy-C1-C9-alkyl: CH20H, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxyprop-1-yl, 2-hydroxyprop-1-yl, 3-hydroxyprop-1-yl, 1-hydroxybut-1-yl, 2-hydroxybut-1-yl, 3-hydroxybut-1-yl, 4-hydroxybut-1-yl, 1-hydroxybut-2-yl, 2-hydroxybut-2-yl, 3-hydroxybut-2-yl, 4-hydroxybut-2-yl, 1-(CHzOH)eth-1-yl, 1-(CH20H)-1-(CH3)-eth-1-yl or 1-(CHZOH)prop-1-yl;
- amino-C1-C4-alkyl: CH2NH2, 1-aminoethyl, 2-aminoethyl, 1-aminoprop-1-yl, 2-aminoprop-1-yl, 3-aminoprop-1-yl, 1-amino-but-1-yl, 2-aminobut-1-yl, 3-aminobut-1-yl, 4-aminobut-1-yl, 1-aminobut-2-yl, 2-aminobut-2-yl, 3-aminobut-2-yl, 4-aminobut-2-yl, 1-(CH2NH2)eth-1-yl, 1-(CH2NH2)-1-(CH3)-eth-1-yl or 1-(CH2NH2)prop-1-yl;
- hydroxycarbonyl-C1-C4-alkyl: CH2COOH, 1-(COOH)ethyl, 2-(COOH)ethyl, 1-(COOH)prop-1-yl, 2-(COOH)prop-1-yl, 3-(COOH)prop-1-yl, 1-(COOH)but-1-yl, 2-(COOH)but-1-yl, 3-(COOH)but-1-yl, 4-(COOH)but-1-yl, 1-(COOH)but-2-yl, 2-(COOH)but-2-yl, 3-(COOH)but-2-yl, 4-(COOH)but-2-yl, 1-(CH2COOH)eth-1-yl, 1-(CHZCOOH)-1-(CH3)-eth-1-yl or 1-(CHZCOOH)prop-1-yl;
- aminocarbonyl-C1-Cq-alkyl: CH2CONH2, 1-(CONHZ)ethyl, 2-(CONHZ)ethyl, 1-(CONH2)prop-1-yl, 2-(CONH2)prop-1-yl, 3-(CONH2)prop-1-yl, 1-(CONH2)but-1-yl, 2-(CONHZ)but-1-yl, 3-(CONH2)but-1-yl, 4-(CONHZ)but-1-yl, 1-(CONH2)but-2-yl, 2-(CONH2)but-2-yl, 3-(CONHZ)but-2-yl, 4-(CONHZ)but-2-yl, 1-(CH2CONH2)eth-1-yl, 1-(CH2CONHZ)-1-(CH3)-eth-1-yl or 1-(CH2CONH2)prop-1-yl;
- phenyl-C1-C4-alkyl: benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl, 1-phenylbut-1-yl, 2-phenylbut-1-yl, 3-phenylbut-1-yl, 4-phenylbut-1-yl, 1-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2-yl, 4-phenylbut-2-yl, 1-(benzyl)eth-1-yl, 1-(benzyl)-1-(methyl)eth-1-yl or 1-(benzyl)prop-1-yl, preferably benzyl or 2-phenylethyl;
- heterocyclyl-C1-C4-alkyl: heterocyclylmethyl, 1-heterocyclylethyl, 2-heterocyclylethyl, 1-heterocyclylprop-1-yl, 2-heterocyclylprop-1-yl, 3-heterocyclylprop-1-yl, 1-heterocyclylbut-1-yl, 2-heterocyclylbut-1-yl, 3-heterocyclylbut-1-yl, 4-heterocyclylbut-1-yl, 1-heterocyclylbut-2-yl, 2-heterocyclylbut-2-yl, 3-heterocyclylbut-2-yl, 3-heterocyclylbut-2-yl, 4-heterocyclylbut-2-yl, 1-(heterocyclylmethyl)eth-1-yl, 1-(heterocyclylmethyl)-1-(methyl)eth-1-yl or 1-(heterocyclylmethyl)prop-1-yl, preferably heterocyclylmethyl or 2-heterocyclylethyl;
- C1-C4-alkoxy: OCH3, OC2H5, OCH2-C2H5, OCH(CH3)2, n-butoxy, OCH(CH3)-C2H5, OCH2-CH(CH3)z or C(CH3)3, preferably OCH3, OCZHS
or OCH(CH3)2:
- C1-C9-haloalkoxy: a C1-CQ-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. OCHzF, OCHF2, OCF3, OCHZC1, OCH(C1)2, pC(C1)3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC2F5, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-CZFS, OCFZ-CZFS, 1-(CH2F)-2-fluoroethoxy, 1-(CHZC1)-2-chloroethoxy, 1-(CHZBr)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, preferably OCHF2, OCF3, dichlorofluoromethoxy, chlorodifluoromethoxy or 2,2,2-trifluoroethoxy;
- C1-C6-alkoxy: a C1-C4-alkoxy radical as mentioned above or, for example, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy, preferably OCH3, OC2H5, OCH2-CZHS.
OCH(CH3)2, n-butoxy, OC(CH3)3, n-pentoxy or n-hexoxy;
- C1-C6-haloalkoxy: a C1-C6-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. one of the radicals mentioned under C1-C4-haloalkoxy or 5-fluoro-1-pentoxy, 5-chloro-1-pentoxy, 5-bromo-1-pentoxy, 5-iodo-1-pentoxy, 5,5,5-trichloro-1-pentoxy, undecafluoropentoxy, 6-fluoro-1-hexoxy, 6-chloro-1-hexoxy, 6-bromo-1-hexoxy, 6-iodo-1-hexoxy, 6,6,6-trichloro-1-hexoxy or dodecafluorohexoxy;
- C1-C4-alkylthio: SCH3, SCZHS, SCH2-CZHS, SCH(CH3)2, n-butylthio, SCH(CH3)-CzHS, SCH2-CH(CH3)2 or SC(CH3)3, preferably SCH3 or SCyHS;
C1-C4-haloalkylthio: a C1-C4-alkylthio radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. SCHZF, SCHFz, SCF3, SCH2C1, SCH(C1)2, SC(C1)3, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, SC2F5, 2-fluoropropylthio, 3-fluoropropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2,3-dichloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, SCHZ-CzFs, SCF2-C2F5, 1-(CHZF)-2-fluoroethylthio, 1-(CH2C1)-2-chloroethylthio, 1-(CHZBr)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio or SCFZ-CF2-CZFS, preferably SCHF2, SCF3, dichlorofluoromethylthio, chlorodifluoromethylthio or 2,2,2-trifluoroethylthio;
- C1-C6-alkylthio: a C1-C4-alkylthio radial as mentioned above or, for example, n-pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, n-hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio or 1-ethyl-2-methylpropylthio, preferably SCH3, SCZHS, SCH2-CZHS, SCH(CH3)2. n-butylthio, SC(CH3)3, n-pentylthio or n-hexylthio;
- C1-C4-alkoxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkoxy - as mentioned above -, eg. CHz-OCH3, CH2-OC2H5, n-propoxymethyl, CH2-OCH(CH3)2, n-butoxymethyl, (1-methylpropoxy)methyl, (2-methylpropoxy)methyl, CH2-OC(CH3)3.
2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)ethyl, 2-(1-methylethoxy)ethyl, 2-(n-butoxy)ethyl, 2-(1-methylpropoxy)ethyl, 2-(2-methylpropoxy)ethyl, 2-(1,1-dimethylethoxy)ethyl, 2-(methoxy)propyl, 2-(ethoxy)propyl, 2-(n-propoxy)propyl, 2-(1-methylethoxy)propyl, 2-(n-butoxy)propyl, 2-(1-methylpropoxy)propyl, 2-(2-methylpropoxy)propyl, 2-(1,1-dimethylethoxy)propyl, 3-(methoxy)propyl, 3-(ethoxy)-propyl, 3-(n-propoxy)propyl, 3-(1-methylethoxy)propyl, 3-(n-butoxy)propyl, 3-(1-methylpropoxy)propyl, 3-(2-methylpropoxy)propyl, 3-(1,1-dimethylethoxy)propyl, 2-(methoxy)butyl, 2-(ethoxy)butyl, 2-(n-propoxy)butyl, 2-(1-methylethoxy)butyl, 2-(n-butoxy)butyl, 2-(1-methylpropoxy)butyl, 2-(2-methylpropoxy)butyl, 2-(1,1-dimethylethoxy)butyl, 3-(methoxy)butyl, 3-(ethoxy)butyl, 3-(n-propoxy)butyl, 3-(1-methylethoxy)butyl, 3-(n-butoxy)butyl, 3-(1-methylpropoxy)butyl, 3-(2-methylpropoxy)butyl, 3-(1,1-dimethylethoxy)butyl, 4-(methoxy)butyl, 4-(ethoxy)butyl, 4-(n-propoxy)butyl, 4-(1-methylethoxy)butyl, 4-(n-butoxy)butyl, 4-(1-methylpropoxy)butyl, 4-(2-methylpropoxy)butyl or 4-(1,1-dimethylethoxy)butyl, preferably CHz-OCH3, CH2-OCZHS, 2-(OCH3)ethyl or 2-(OC2H5)ethyl;
- C1-C4-haloalkoxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-haloalkoxy as mentioned above, eg. 2-(OCHF2)ethyl, 2-(OCF3)ethyl or 2-(OC2F5)ethyl;
5 - C1-C4-alkylthio-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C9-alkylthio - as mentioned above -, eg. CH2-SCH3, CH2-SC2H5, n-propylthiomethyl, CH2-SCH(CH3)2, n-butylthiomethyl, (1-methylpropylthio)methyl, (2-methylpropylthio)methyl, CH2-SC(CH3)3, 2-(methylthio)ethyl, 2-(ethylthio)ethyl, 10 2-(n-propylthio)ethyl, 2-(1-methylethylthio)ethyl, 2-(n-butylthio)ethyl, 2-(1-methylpropylthio)ethyl, 2-(2-methylpropylthio)ethyl, 2-(1,1-dimethylethylthio)ethyl, 2-(methylthio)propyl, 2-(ethylthio)propyl, 2-(n-propylthio)propyl, 2-(1-methylethylthio)propyl, 2-(n-butylthio)propyl, 2-(1-methylpropylthio)propyl, 2-(2-methylpropylthio)propyl, 2-(1,1-dimethylethylthio)propyl, 3-(methylthio)propyl, 3-(ethylthio)propyl, 3-(n-propylthio)propyl, 3-(1-methylethylthio)propyl, 3-(n-butylthio)propyl, 3-(1-methylpropylthio)propyl, 3-(2-methylpropylthio)propyl, 3-(1,1-dimethylethylthio)propyl, 2-(methylthio)butyl, 2-(ethylthio)butyl, 2-(n-propylthio)butyl, 2-(1-methylethylthio)butyl, 2-(n-butylthio)butyl, 2-(1-methylpropylthio)butyl, 2-(2-methylpropylthio)butyl, 2-(1,1-dimethylethylthio)butyl, 3-(methylthio)butyl, 3-(ethylthio)butyl, 3-(n-propylthio)butyl, 3-(1-methylethylthio)butyl, 3-(n-butylthio)butyl, 3-(1-methylpropylthio)butyl, 3-(2-methylpropylthio)butyl, 3-(1,1-dimethylethylthio)butyl, 4-(methylthio)butyl, 4-(ethylthio)butyl, 4-(n-propylthio)butyl, 4-(1-methylethylthio)butyl, 4-(n-butylthio)butyl, 4-(1-methylpropylthio)butyl, 4-(2-methylpropylthio)butyl or 4-(1,1-dimethylethylthio)butyl, preferably CH2-SCH3, CH2-SC2H5, 2-(SCH3)ethyl or 2-(SC2H5)ethyl;
- C1-Ca-haloalkylthio-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-haloalkylthio as mentioned above, eg.
2-(SCHF2)ethyl, 2-(SCF3)ethyl or 2-(SC2F5)ethyl;
- (C1-C4-alkyl)carbonyl: CO-CH3, CO-C2H5, CO-CH2-C2H5, CO-CH(CHg)2, n-butylcarbonyl, CO-CH(CH3)-C2H5, CO-CH2-CH(CH3)2 or CO-C(CH3)3.
preferably CO-CH3 or CO-C2H5;
- (C1-C4-haloalkyl)carbonyl: a (C1-C4-alkyl)carbonyl radical - as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. CO-CH2F, CO-CHF2, CO-CF3, CO-CH2C1, CO-CH(C1)2, CO-C(C1)3, chlorofluoromethylcarbonyl, dichlorofluoromethylcarbonyl, chlorodifluoromethylcarbonyl, 2-fluoroethylcarbonyl, 2-chloroethylcarbonyl, 2-bromoethylcarbonyl, 2-iodoethylcarbonyl, 2,2-difluoroethylcarbonyl, 2,2,2-trifluoroethylcarbonyl, 2-chloro-2-fluoroethylcarbonyl, 2-chloro-2,2-difluoroethylcarbonyl, 2,2-dichloro-2-fluoroethylcarbonyl, 2,2,2-trichloroethylcarbonyl, CO-CZFS, 2-fluoropropylcarbonyl, 3-fluoropropylcarbonyl, 2,2-difluoropropylcarbonyl, 2,3-difluoropropylcarbonyl, 2-chloropropylcarbonyl, 3-chloropropylcarbonyl, 2,3-dichloropropylcarbonyl, 2-bromopropylcarbonyl, 3-bromopropylcarbonyl, 3,3,3-trifluoropropylcarbonyl, 3,3,3-trichloropropylcarbonyl, CO-CH2-C2F5, CO-CFZ-C2F5, 1-(CH2F)-2-fluoroethylcarbonyl, 1-(CH2C1)-2-chloroethylcarbonyl, 1-(CH2Br)-2-bromoethylcarbonyl, 4-fluorobutylcarbonyl, 4-chlorobutylcarbonyl, 4-bromobutylcarbonyl or nonafluorobutylcarbonyl, preferably CO-CF3, CO-CH2C1 or 2,2,2-trifluoroethylcarbonyl;
- (Ci-Cs-alkyl)carbonyl: one of the abovementioned (C1-CQ-alkyl)carbonyl radicals or, for example, n-pentyl-CO, 1-methylbutyl-CO, 2-methylbutyl-CO, 3-methylbutyl-CO, 2,2-dimethylpropyl-C0, 1-ethylpropyl-CO, n-hexyl-C0, 1,1-dimethylpropyl-CO, 1,2-dimethylpropyl-CO, 1-methylpentyl-C0, 2-methylpentyl-CO, 3-methylpentyl-CO, 4-methylpentyl-CO, 1,1-dimethylbutyl-CO, 1,2-dimethylbutyl-CO, 1,3-dimethylbutyl-C0, 2,2-dimethylbutyl-CO, 2,3-dimethylbutyl-C0, 3,3-dimethylbutyl-CO, 1-ethylbutyl-CO, 2-ethylbutyl-CO, 1,1,2-trimethylpropyl-CO, 12.2-trimethylpropyl-CO, 1-ethyl-1-methylpropyl-CO or 1-ethyl-2-methylpropyl-C0, preferably CO-CH3, CO-C2H5, CO-CH2-CZHS, CO-CH(CH3)2, n-butyl-CO, CO-C(CH3)3, CO-(n-C5H11) or CO-(n-C6H13):
- (C1-Cs-haloalkyl)carbonyl: a (C1-CS-alkyl)carbonylrest - as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. CO-CHZF, CO-CHF2, CO-CF3, CO-CH2C1, CO-CH(C1)z, CO-C(C1)3, chlorofluoromethylcarbonyl, dichlorofluoromethylcarbonyl, chlorodifluoromethylcarbonyl, 2-fluoroethylcarbonyl, 2-chloroethylcarbonyl, 2-bromoethylcarbonyl, 2-iodoethylcarbonyl, 2,2-difluoroethylcarbonyl, 2,2,2-trifluoroethylcarbonyl, 2-chloro-2-fluoroethylcarbonyl, 2-chloro-2,2-difluoroethylcarbonyl, 2~2-dichloro-2-fluoroethylcarbonyl, 2,2,2-trichloroethylcarbonyl, CO-C2F5, 2-fluoropropylcarbonyl, 3-fluoropropylcarbonyl, 2,2-difluoropropylcarbonyl, 2,3-difluoropropylcarbonyl, 2-chloropropylcarbonyl, 3-chloropropylcarbonyl, 2,3-dichloropropylcarbonyl, 2-bromopropylcarbonyl, 3-bromopropylcarbonyl, 3,3,3-trifluoropropylcarbonyl, 3,3,3-trichloropropylcarbonyl, CO-CHZ-C2F5, CO-CFZ-C2F5, 1-(CHZF)-2-fluoroethylcarbonyl, 1-(CH2C1)-2-chloroethylcarbonyl, 1-(CH2Br)-2-bromoethylcarbonyl, 4-fluorobutylcarbonyl, 4-chlorobutylcarbonyl, 4-bromobutylcarbonyl or nonafluorobutylcarbonyl, preferably CO-CF3, CO-CHZC1 or 2,2,2-trifluoroethylcarbonyl;
- (C1-C4-alkyl)carbonyloxy: 0-CO-CH3, O-CO-C2H5, 0-CO-CH2-C2H5, 0-CO-CH(CH3)2, 0-CO-CHz-CHZ-C2H5, 0-CO-CH(CH3)-CZHS, 0-CO-CH2-CH(CH3)2 or 0-CO-C(CH3)3, preferably 0-CO-CH3 or O-CO-CzHS;
- (C1-C4-haloalkyl)carbonyloxy: a (C1-C4-alkyl)carbonyl radical -as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. O-CO-CH2F, O-CO-CHF2, O-CO-CF3, 0-CO-CHZCl, O-CO-CH(C1)z, O-CO-C(C1)3, chlorofluoromethylcarbonyloxy, dichlorofluoromethylcarbonyloxy, chlorodifluoromethylcarbonyloxy, 2-fluoroethylcarbonyloxy, 2-chloroethylcarbonyloxy, 2-bromoethylcarbonyloxy, 2-iodoethylcarbonyloxy, 2,2-difluoroethylcarbonyloxy, 2,2,2-trifluoroethylcarbonyloxy, 2-chloro-2-fluoroethylcarbonyloxy, 2-chloro-2,2-difluoroethylcarbonyloxy, 2,2-dichloro-2-fluoroethylcarbonyloxy, 2,2,2-trichloroethylcarbonyloxy, 0-CO-C2F5, 2-fluoropropylcarbonyloxy, 3-fluoropropylcarbonyloxy, 2,2-difluoropropylcarbonyloxy, 2.3-difluoropropylcarbonyloxy, 2-chloropropylcarbonyloxy, 3-chloropropylcarbonyloxy, 2,3-dichloropropylcarbonyloxy, 2-bromopropylcarbonyloxy, 3-bromopropylcarbonyloxy, 3,3,3-trifluoropropylcarbonyloxy, 3,3,3-trichloropropylcarbonyloxy, O-CO-CHy-CzFS, O-CO-CF2-C2F5, 1-(CH2F)-2-fluoroethylcarbonyloxy, 1-(CH2C1)-2-chloroethylcarbonyloxy, 1-(CHzBr)-2-bromoethylcarbonyloxy, 4-fluorobutylcarbonyloxy, 4-chlorobutylcarbonyloxy, 4-bromobutylcarbonyloxy or nonafluorobutylcarbonyloxy, preferably O-CO-CF3, O-CO-CH2C1 or 2~2.2-trifluoroethylcarbonyloxy;
- (C1-C6-alkyl)carbonyloxy: one of the abovementioned (C1-C4-alkyl)carbonyloxy radicals or, for example, n-pentyl-COO, 1-methylbutyl-COO, 2-methylbutyl-COO, 3-methylbutyl-COO, 2,2-dimethylpropyl-COO, 1-ethylpropyl-COO, n-hexyl-COO, 1,1-dimethylpropyl-COO, 1,2-dimethylpropyl-COO, 1-methylpentyl-COO, 2-methylpentyl-COO, 3-methylpentyl-COO, 4-methylpentyl-C00, 1,1-dimethylbutyl-C00, 1,2-dimethylbutyl-COO, 1,3-dimethylbutyl-COO, 2,2-dimethylbutyl-COO, 2,3-dimethylbutyl-C00, 3,3-dimethylbutyl-COO, 1-ethylbutyl-COO, 2-ethylbutyl-COO, 1,1,2-trimethylpropyl-COO, 1,2,2-trimethylpropyl-C00, 1-ethyl-1-methylpropyl-COO or 1-ethyl-2-methylpropyl-COO, preferably O-CO-CHg, O-CO-CZHS, O-CO-CHZ-CzHS, O-CO-CH(CH3)2.
n-butyl-COO, 0-CO-C(CH3)3, 0-CO-(n-C5H11) or 0-CO-(n-C6H13):
- (C1-C6-alkyl)thiocarbonyl: CS-CH3, CS-C2H5, CS-CH2-CZHS, CS-CH(CH3)2, CS-(n-C4Hg), CS-CH(CH3)-CzHS, CS-CH2-CH(CH3)2.
CS-C(CH3)3, CS-(n-C5H11). CS-CH(CH3)-CHZ-CZHS.
CS-CHZ-CH(CH3)-C2H5, CS-CH2CHy-CH(CH3)2, CS-C(CHg)2-CZHS, CS-CH(CH3)-CH(CH3)2, CS-CHZ-C(CH3)3, CS-CH(CZHS)-C2H5, CS-(n-C6H13), CS-CH(CH3)-(n-CqHg), CS-CH2-CH(CH3)-CH2-C2H5, CS-CHZCH2-CH(CH3)-CZHS, CS-CHZCHZCH2-CH(CH3)y, CS-C(CH3)2-CHZ-C2H5, CS-CH(CH3)-CH(CH3)-C2H5, CS-CH(CHg)-CH2-CH(CH3)Z, CS-CHZ-C(CH3)2-CZHS, CS-CH2-CH(CH3)-CH(CH3)y, CS-CHZCH2-C(CH3)3, CS-CH(C2H5)-CHZ-CZHS, CS-CHy-CH(C2H5)-C2H5, CS-C(CH3)2-CH(CH3)y, CS-CH(CH3)-C(CH3)3, CS-C(CH3)(C2H5)-CZHS Or CS-CH(CzHS)-CH(CH3)2, preferably CS-CH3, CS-CZHS, CS-CH2-C2H5, CS-CH(CH3)2 Or CS-(n-C4Hg);
- (C1-C4-alkoxy)carbonyl: CO-OCH3, CO-OC2H5, CO-OCH2-C2H5, CO-OCH(CH3)2, n-butoxycarbonyl, CO-OCH(CH3)-C2H5, CO-OCH2-CH(CH3)z or CO-OC(CH3)3, preferably CO-OCH3 or CO-OC2H5;
- (C1-C6-alkoxy)carbonyl: one of the abovementioned (C1-C4-alkoxy)carbonyl radicals or, for example, n-pentoxy-CO, 1-methylbutoxy-CO, 2-methylbutoxy-CO, 3-methylbutoxy-CO, 2,2-dimethylpropoxy-CO, 1-ethylpropoxy-CO, n-hexoxy-CO, 1,1-dimethylpropoxy-CO, 1,2-dimethylpropoxy-CO, 1-methylpentoxy-CO, 2-methylpentoxy-CO, 3-methylpentoxy-CO, 4-methylpentoxy-CO, 1,1-dimethylbutoxy-C0, 1,2-dimethylbutoxy-CO, 1,3-dimethylbutoxy-CO, 2,2-dimethylbutoxy-CO, 2,3-dimethylbutoxy-CO, 3,3-dimethylbutoxy-CO, 1-ethylbutoxy-CO, 2-ethylbutoxy-CO, 1,1,2-trimethylpropoxy-CO, 1,2,2-trimethylpropoxy-C0, 1-ethyl-1-methylpropoxy-CO or 1-ethyl-2-methylpropoxy-CO, preferably CO-OCH3, CO-OC2H5, CO-OCHZ-CZHS, CO-OCH(CH3)2, n-butoxy-CO, CO-OC(CH3)3, n-pentoxy-CO or n-hexoxy-CO;
- (C1-C4-alkoxy)carbonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by (C1-C4-alkoxy)carbonyl - as mentioned above -, eg. CH2-CO-OCH3, CH2-CO-OCZHS, CHz-CO-OCH2-CZHS, CHz-CO-OCH(CH3)2, n-butoxycarbonylmethyl, CH2-CO-OCH(CH3)-C2H5, CH2-CO-OCH2-CH(CH3)2, CH2-CO-OC(CH3)3r I-(CO-OCH3)ethyl, 1-(CO-OC2H5)ethyl, 1-(CO-OCHZ-C2H5)ethyl, I-[CH(CH3)2]ethyl, 1-(n-butoxycarbonyl)ethyl, 1-[1-methylpropoxycarbonyl]ethyl, 1-[2-methylpropoxycarbonyl]ethyl, 2-(CO-OCH3)ethyl, 2-(CO-OCZHS)ethyl, 2-(CO-OCH2-C2H5)ethyl, 2-[CO-OCH(CH3)Z]ethyl, 2-(n-butoxycarbonyl)ethyl, 2-[1-methylpropoxycarbonyl]ethyl, 2-[2-methylpropoxycarbonyl]ethyl, 2-[CO-OC(CH3)3]ethyl, 2-(CO-OCH3)propyl, 2-(CO-OC2H5)propyl, 2-(CO-OCH2-CZHS)propyl, 2-[CO-OCH(CH3)Z]propyl, 2-(n-butoxycarbonyl)propyl, 2-[1-methylpropoxycarbonyl]propyl, 2-[2-methylpropoxycarbonyl]propyl, 2-[CO-OC(CH3)3]propyl, 3-(CO-OCH3)propyl, 3-(CO-OCZHS)propyl, 3-(CO-OCH2-C2H5)propyl, 3-[CO-OCH(CH3)2]propyl, 3-(n-butoxycarbonyl)propyl, 3-[1-methylpropoxycarbonyl]propyl, 3-[2-methylpropoxycarbonyl]propyl, 3-[CO-OC(CH3)3]propyl, 2-(CO-OCHg)butyl, 2-(CO-OCZHS)butyl, 2-(CO-0CH2-C2H5)butyl, 2-[CO-OCH(CH3)Z]butyl, 2-(n-butoxycarbonyl)butyl, 2-[1-methylpropoxycarbonyl]butyl, 2-[2-methylpropoxycarbonyl]butyl, 2-[CO-OC(CH3)3]butyl, 3-(CO-OCH3)butyl, 3-(CO-OCzHS)butyl, 3-(CO-OCH2-C2H5)butyl, 3-[CO-OCH(CH3)2]butyl, 3-(n-butoxycarbonyl)butyl, 3-[1-methylpropoxycarbonyl]butyl, 3-[2-methylpropoxycarbonyl]butyl, 3-[CO-OC(CH3)3]butyl, 4-(CO-OCH3)butyl, 4-(CO-OC2H5)butyl, 4-(CO-OCHZ-C2Hg)butyl, 4-ICO-OCH(CH3)Z]butyl, 4-(n-butoxycarbonyl)butyl, 4-[1-methylpropoxycarbonyl]butyl, 4-[2-methylpropoxycarbonyl]butyl or 4-[CO-OC(CH3)3]butyl, preferably CH2-CO-OCH3, CH2-CO-OCZHS, 1-(CO-OCH3)ethyl or 1-(CO-OC2H5)ethyl;
- (C1-C6-alkoxy)thiocarbonyl: for example CS-OCH3, CS-OC2H5, CS-OCHZ-CZHS, CS-OCH(CH3)z, CS-O(n-C4H9), CS-OCH(CH3)-CZHS, CS-OCH2-CH(CHg)2, CS-OC(CH3)3, CS-O(n-CSHii).
CS-OCH(CH3)-CHZ-C2H5, CS-OCH2-CH(CH3)-CZHS, CS-OCH2CH2-CH(CH3)2, CO-OCH2-C(CH3)3, CS-OCH(CZHS)-C2H5, CS-O(n-C6H13).
CS-OC(CH3)2-CZHS, CS-OCH(CH3)-CH(CH3)2, CS-OCH(CH3)-(n-C4H9), CS-OCHz-CH(CH3)-CHy-C2H5, CS-OCH2CH2-CH(CH3)-C2H5, CS-OCH2CH2CH2-CH(CH3)Z, CS-OC(CH3)2-CH2-C2H5, CS-OCH(CH3)-CH(CH3)-C2H5, CS-OCH(CH3)-CH2-CH(CH3)z, CS-OCH2-C(CH3)2-C2H5, CS-OCH2-CH(CH3)-CH(CH3)2, CS-OCHyCHy-C(CH3)3, CS-OC(CyHS)-CHy-C2H5, CS-OCH2-CH(CZHS)-C2H5, CS-OC(CH3)Z-CH(CH3)2, CS-OCH(CH3)-C(CH3)3, CS-OC(CH3)(C2H5)-C2H5 or CS-OCH(C2H5)-CH(CH3)2, preferably CS-OCH3 or CS-OC2H5;
(Ci-C4-alkylthio)carbonyl: CO-SCH3, CO-SC2H5, CO-SCHZ-C2H5, CO-SCH(CH3)Z, CO-SCHyCH2-C2H5, CO-SCH(CH3)-CZHS, CO-SCH2-CH(CH3)2 or CO-SC(CH3)3, preferably CO-SCH3 or CO-SC2H5:
- (C1-CQ-alkylthio)carbonyl-Cl-C4-alkyl: C1-CQ-alkyl which is substituted by (C1-C4-alkylthio)carbonyl - as mentioned above -, ie. CHZ-CO-SCH3, CHZ-CO-SC2H5, CH2-CO-SCH2-C2H5, CH2-CO-SCH(CH3)2, CHy-CO-SCH2CHy-C2Hg, 5 CHZ-CO-SCH(CH3)-CZHS, CH2-CO-SCHy-CH(CH3)2, CH2-CO-SC(CH3)3.
1-(CO-SCH3)ethyl, 1-(CO-SC2H5)ethyl, 1-(CO-SCH2-C2H5)ethyl, 1-[CO-SCH(CH3)2]ethyl, 1-(CO-SCH2CH2-CzHS)ethyl, 1-[CO-SCH(CH3)-C2H5]ethyl, 1-[CO-SCHZ-CH(CH3)2]ethyl, 1-[CO-SC(CH3)3]ethyl, 2-(CO-SCH3)ethyl, 2-(CO-SC2H5)ethyl, 10 2-(CO-SCHZ-C2H5)ethyl, 2-[CO-SCH(CH3)Z]ethyl, 2-(CO-SCH2CH2-C2H5)ethyl, 2-[CO-SCH(CH3)-CzHS]ethyl, 2-[CO-SCHz-CH(CH3)2]ethyl, 2-[CO-SC(CHg)3]ethyl, 2-(CO-SCH3)propyl, 2-(CO-SCZHS)propyl, 2-(CO-SCHZ-C2H5)propyl, 2-[CO-SCH(CH3)2]propyl, 2-(CO-SCHZCH2-C2H5)propyl, 15 2-ICO-SCH(CH3)-C2H5]propyl, 2-[CO-SCHZ-CH(CH3)Z]propyl, 2-[CO-SC(CH3)3]propyl, 3-(CO-SCH3)propyl, 3-(CO-SC2H5)propyl, 3-(CO-SCH2-CZHS)propyl, 3-[CO-SCH(CH3)z]propyl, 3-(CO-SCH2CH2-C2H5)propyl, 3-[CO-SCH(CH3)-CZHS]propyl, 3-[CO-SCH2-CH(CH3)z]propyl, 3-[CO-SC(CH3)3]propyl, 2-(CO-SCH3)butyl, 2-(CO-SC2H5)butyl, 2-(CO-SCHZ-C2H5)butyl, 2-[CO-SCH(CH3)2]butyl, 2-(CO-SCH2CH2-C2H5)butyl, 2-[CO-SCH(CH3)-C2H5]butyl, 2-[CO-SCHZ-CH(CH3)2]butyl, 2-[CO-SC(CH3)3]butyl, 3-(CO-SCH3)butyl, 3-(CO-SC2H5)butyl, 3-(CO-SCH2-CZHS)butyl, 3-[CO-SCH(CH3)2]butyl, 3-(CO-SCH2CH2-C2H5)butyl, 3-[CO-SCH(CH3)-CZH5]butyl, 3-[CO-SCHZ-CH(CH3)2]butyl, 3-[CO-SC(CH3)3]butyl, 4-(CO-SCH3)butyl, 4-(CO-SC2H5)butyl, 4-(CO-SCH2-C2H5)butyl, 4-[CO-SCH(CH3)2]butyl, 4-(CO-SCHZCH2-C2H5)butyl, 4-[CO-SCH(CH3)-C2H5]butyl, 4-[CO-SCHZ-CH(CH3)2]butyl or 4-[CO-SC(CH3)3]butyl, preferably CH2-CO-SCH3, CH2-CO-SCzHS, 1-(CO-SCH3)ethyl or 1-(CO-SCZH5)ethyl;
- C1-C6-alkylsulfinyl: a C1-CQ-alkylsulfinyl radical such as SO-CH3, SO-CZHS, SO-CH2-CZHg, SO-CH(CH3)2, SO-(n-CqHg), SO-CH(CH3)-CZHS, SO-CHz-CH(CH3)2 or SO-C(CH3)3, or, for example, SO-(n-CSH11), 1-methylbutyl-SO, 2-methylbutyl-S0, 3-methylbutyl-S0, 2,2-dimethylpropyl-S0, 1-ethylpropyl-S0, n-hexyl-S0, 1,1-dimethylpropyl-SO, 1,2-dimethylpropyl-SO, 1-methylpentyl-SO, 2-methylpentyl-SO, 3-methylpentyl-SO, 4-methylpentyl-S0, 1,1-dimethylbutyl-S0, 1,2-dimethylbutyl-SO, 1,3-dimethylbutyl-S0, 2,2-dimethylbutyl-SO, 2,3-dimethylbutyl-S0, 3,3-dimethylbutyl-SO, 1-ethylbutyl-SO, 2-ethylbutyl-SO, 1,1,2-trimethylpropyl-S0, 1,2,2-trimethylpropyl-SO, 1-ethyl-1-methylpropyl-SO or 1-ethyl-2-methylpropyl-S0, preferably SO-CH3, SO-C2H5, SO-CH2-C2H5, SO-CH(CH3)y, SO-(n-C4Hg), SO-C(CH3)3, SO-(n-C5H11) or SO-(n-C6Hls):
n-pentyl or n-hexyl;
- C1-C6-haloalkyl: a C1-C6-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. one of the radicals mentioned under C1-C4-haloalkyl or 5-fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodo-1-pentyl, 5,5,5-trichloro-1-pentyl, undecafluoropentyl, 6-fluoro-1-hexyl, 6-chloro-1-hexyl, 6-bromo-1-hexyl, 6-iodo-1-hexyl, 6,6,6-trichloro-1-hexyl or dodecafluorohexyl;
- cyano-C1-C4-alkyl: CH2CN, 1-cyanoethyl, 2-cyanoethyl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyanoprop-1-yl, 1-cyanobut-1-yl, 2-cyanobut-1-yl, 3-cyanobut-1-yl, 4-cyanobut-1-yl, 1-cyanobut-2-yl, 2-cyanobut-2-yl, 3-cyanobut-2-yl, 4-cyanobut-2-yl, 1-(CHZCN)eth-1-yl, 1-(CHZCN)-1-(CH3)-eth-1-yl or 1-(CH2CN)prop-1-yl;
- hydroxy-C1-C9-alkyl: CH20H, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxyprop-1-yl, 2-hydroxyprop-1-yl, 3-hydroxyprop-1-yl, 1-hydroxybut-1-yl, 2-hydroxybut-1-yl, 3-hydroxybut-1-yl, 4-hydroxybut-1-yl, 1-hydroxybut-2-yl, 2-hydroxybut-2-yl, 3-hydroxybut-2-yl, 4-hydroxybut-2-yl, 1-(CHzOH)eth-1-yl, 1-(CH20H)-1-(CH3)-eth-1-yl or 1-(CHZOH)prop-1-yl;
- amino-C1-C4-alkyl: CH2NH2, 1-aminoethyl, 2-aminoethyl, 1-aminoprop-1-yl, 2-aminoprop-1-yl, 3-aminoprop-1-yl, 1-amino-but-1-yl, 2-aminobut-1-yl, 3-aminobut-1-yl, 4-aminobut-1-yl, 1-aminobut-2-yl, 2-aminobut-2-yl, 3-aminobut-2-yl, 4-aminobut-2-yl, 1-(CH2NH2)eth-1-yl, 1-(CH2NH2)-1-(CH3)-eth-1-yl or 1-(CH2NH2)prop-1-yl;
- hydroxycarbonyl-C1-C4-alkyl: CH2COOH, 1-(COOH)ethyl, 2-(COOH)ethyl, 1-(COOH)prop-1-yl, 2-(COOH)prop-1-yl, 3-(COOH)prop-1-yl, 1-(COOH)but-1-yl, 2-(COOH)but-1-yl, 3-(COOH)but-1-yl, 4-(COOH)but-1-yl, 1-(COOH)but-2-yl, 2-(COOH)but-2-yl, 3-(COOH)but-2-yl, 4-(COOH)but-2-yl, 1-(CH2COOH)eth-1-yl, 1-(CHZCOOH)-1-(CH3)-eth-1-yl or 1-(CHZCOOH)prop-1-yl;
- aminocarbonyl-C1-Cq-alkyl: CH2CONH2, 1-(CONHZ)ethyl, 2-(CONHZ)ethyl, 1-(CONH2)prop-1-yl, 2-(CONH2)prop-1-yl, 3-(CONH2)prop-1-yl, 1-(CONH2)but-1-yl, 2-(CONHZ)but-1-yl, 3-(CONH2)but-1-yl, 4-(CONHZ)but-1-yl, 1-(CONH2)but-2-yl, 2-(CONH2)but-2-yl, 3-(CONHZ)but-2-yl, 4-(CONHZ)but-2-yl, 1-(CH2CONH2)eth-1-yl, 1-(CH2CONHZ)-1-(CH3)-eth-1-yl or 1-(CH2CONH2)prop-1-yl;
- phenyl-C1-C4-alkyl: benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl, 1-phenylbut-1-yl, 2-phenylbut-1-yl, 3-phenylbut-1-yl, 4-phenylbut-1-yl, 1-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2-yl, 4-phenylbut-2-yl, 1-(benzyl)eth-1-yl, 1-(benzyl)-1-(methyl)eth-1-yl or 1-(benzyl)prop-1-yl, preferably benzyl or 2-phenylethyl;
- heterocyclyl-C1-C4-alkyl: heterocyclylmethyl, 1-heterocyclylethyl, 2-heterocyclylethyl, 1-heterocyclylprop-1-yl, 2-heterocyclylprop-1-yl, 3-heterocyclylprop-1-yl, 1-heterocyclylbut-1-yl, 2-heterocyclylbut-1-yl, 3-heterocyclylbut-1-yl, 4-heterocyclylbut-1-yl, 1-heterocyclylbut-2-yl, 2-heterocyclylbut-2-yl, 3-heterocyclylbut-2-yl, 3-heterocyclylbut-2-yl, 4-heterocyclylbut-2-yl, 1-(heterocyclylmethyl)eth-1-yl, 1-(heterocyclylmethyl)-1-(methyl)eth-1-yl or 1-(heterocyclylmethyl)prop-1-yl, preferably heterocyclylmethyl or 2-heterocyclylethyl;
- C1-C4-alkoxy: OCH3, OC2H5, OCH2-C2H5, OCH(CH3)2, n-butoxy, OCH(CH3)-C2H5, OCH2-CH(CH3)z or C(CH3)3, preferably OCH3, OCZHS
or OCH(CH3)2:
- C1-C9-haloalkoxy: a C1-CQ-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. OCHzF, OCHF2, OCF3, OCHZC1, OCH(C1)2, pC(C1)3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC2F5, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-CZFS, OCFZ-CZFS, 1-(CH2F)-2-fluoroethoxy, 1-(CHZC1)-2-chloroethoxy, 1-(CHZBr)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, preferably OCHF2, OCF3, dichlorofluoromethoxy, chlorodifluoromethoxy or 2,2,2-trifluoroethoxy;
- C1-C6-alkoxy: a C1-C4-alkoxy radical as mentioned above or, for example, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy, preferably OCH3, OC2H5, OCH2-CZHS.
OCH(CH3)2, n-butoxy, OC(CH3)3, n-pentoxy or n-hexoxy;
- C1-C6-haloalkoxy: a C1-C6-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. one of the radicals mentioned under C1-C4-haloalkoxy or 5-fluoro-1-pentoxy, 5-chloro-1-pentoxy, 5-bromo-1-pentoxy, 5-iodo-1-pentoxy, 5,5,5-trichloro-1-pentoxy, undecafluoropentoxy, 6-fluoro-1-hexoxy, 6-chloro-1-hexoxy, 6-bromo-1-hexoxy, 6-iodo-1-hexoxy, 6,6,6-trichloro-1-hexoxy or dodecafluorohexoxy;
- C1-C4-alkylthio: SCH3, SCZHS, SCH2-CZHS, SCH(CH3)2, n-butylthio, SCH(CH3)-CzHS, SCH2-CH(CH3)2 or SC(CH3)3, preferably SCH3 or SCyHS;
C1-C4-haloalkylthio: a C1-C4-alkylthio radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. SCHZF, SCHFz, SCF3, SCH2C1, SCH(C1)2, SC(C1)3, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, SC2F5, 2-fluoropropylthio, 3-fluoropropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2,3-dichloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, SCHZ-CzFs, SCF2-C2F5, 1-(CHZF)-2-fluoroethylthio, 1-(CH2C1)-2-chloroethylthio, 1-(CHZBr)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio or SCFZ-CF2-CZFS, preferably SCHF2, SCF3, dichlorofluoromethylthio, chlorodifluoromethylthio or 2,2,2-trifluoroethylthio;
- C1-C6-alkylthio: a C1-C4-alkylthio radial as mentioned above or, for example, n-pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, n-hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio or 1-ethyl-2-methylpropylthio, preferably SCH3, SCZHS, SCH2-CZHS, SCH(CH3)2. n-butylthio, SC(CH3)3, n-pentylthio or n-hexylthio;
- C1-C4-alkoxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkoxy - as mentioned above -, eg. CHz-OCH3, CH2-OC2H5, n-propoxymethyl, CH2-OCH(CH3)2, n-butoxymethyl, (1-methylpropoxy)methyl, (2-methylpropoxy)methyl, CH2-OC(CH3)3.
2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)ethyl, 2-(1-methylethoxy)ethyl, 2-(n-butoxy)ethyl, 2-(1-methylpropoxy)ethyl, 2-(2-methylpropoxy)ethyl, 2-(1,1-dimethylethoxy)ethyl, 2-(methoxy)propyl, 2-(ethoxy)propyl, 2-(n-propoxy)propyl, 2-(1-methylethoxy)propyl, 2-(n-butoxy)propyl, 2-(1-methylpropoxy)propyl, 2-(2-methylpropoxy)propyl, 2-(1,1-dimethylethoxy)propyl, 3-(methoxy)propyl, 3-(ethoxy)-propyl, 3-(n-propoxy)propyl, 3-(1-methylethoxy)propyl, 3-(n-butoxy)propyl, 3-(1-methylpropoxy)propyl, 3-(2-methylpropoxy)propyl, 3-(1,1-dimethylethoxy)propyl, 2-(methoxy)butyl, 2-(ethoxy)butyl, 2-(n-propoxy)butyl, 2-(1-methylethoxy)butyl, 2-(n-butoxy)butyl, 2-(1-methylpropoxy)butyl, 2-(2-methylpropoxy)butyl, 2-(1,1-dimethylethoxy)butyl, 3-(methoxy)butyl, 3-(ethoxy)butyl, 3-(n-propoxy)butyl, 3-(1-methylethoxy)butyl, 3-(n-butoxy)butyl, 3-(1-methylpropoxy)butyl, 3-(2-methylpropoxy)butyl, 3-(1,1-dimethylethoxy)butyl, 4-(methoxy)butyl, 4-(ethoxy)butyl, 4-(n-propoxy)butyl, 4-(1-methylethoxy)butyl, 4-(n-butoxy)butyl, 4-(1-methylpropoxy)butyl, 4-(2-methylpropoxy)butyl or 4-(1,1-dimethylethoxy)butyl, preferably CHz-OCH3, CH2-OCZHS, 2-(OCH3)ethyl or 2-(OC2H5)ethyl;
- C1-C4-haloalkoxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-haloalkoxy as mentioned above, eg. 2-(OCHF2)ethyl, 2-(OCF3)ethyl or 2-(OC2F5)ethyl;
5 - C1-C4-alkylthio-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C9-alkylthio - as mentioned above -, eg. CH2-SCH3, CH2-SC2H5, n-propylthiomethyl, CH2-SCH(CH3)2, n-butylthiomethyl, (1-methylpropylthio)methyl, (2-methylpropylthio)methyl, CH2-SC(CH3)3, 2-(methylthio)ethyl, 2-(ethylthio)ethyl, 10 2-(n-propylthio)ethyl, 2-(1-methylethylthio)ethyl, 2-(n-butylthio)ethyl, 2-(1-methylpropylthio)ethyl, 2-(2-methylpropylthio)ethyl, 2-(1,1-dimethylethylthio)ethyl, 2-(methylthio)propyl, 2-(ethylthio)propyl, 2-(n-propylthio)propyl, 2-(1-methylethylthio)propyl, 2-(n-butylthio)propyl, 2-(1-methylpropylthio)propyl, 2-(2-methylpropylthio)propyl, 2-(1,1-dimethylethylthio)propyl, 3-(methylthio)propyl, 3-(ethylthio)propyl, 3-(n-propylthio)propyl, 3-(1-methylethylthio)propyl, 3-(n-butylthio)propyl, 3-(1-methylpropylthio)propyl, 3-(2-methylpropylthio)propyl, 3-(1,1-dimethylethylthio)propyl, 2-(methylthio)butyl, 2-(ethylthio)butyl, 2-(n-propylthio)butyl, 2-(1-methylethylthio)butyl, 2-(n-butylthio)butyl, 2-(1-methylpropylthio)butyl, 2-(2-methylpropylthio)butyl, 2-(1,1-dimethylethylthio)butyl, 3-(methylthio)butyl, 3-(ethylthio)butyl, 3-(n-propylthio)butyl, 3-(1-methylethylthio)butyl, 3-(n-butylthio)butyl, 3-(1-methylpropylthio)butyl, 3-(2-methylpropylthio)butyl, 3-(1,1-dimethylethylthio)butyl, 4-(methylthio)butyl, 4-(ethylthio)butyl, 4-(n-propylthio)butyl, 4-(1-methylethylthio)butyl, 4-(n-butylthio)butyl, 4-(1-methylpropylthio)butyl, 4-(2-methylpropylthio)butyl or 4-(1,1-dimethylethylthio)butyl, preferably CH2-SCH3, CH2-SC2H5, 2-(SCH3)ethyl or 2-(SC2H5)ethyl;
- C1-Ca-haloalkylthio-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-haloalkylthio as mentioned above, eg.
2-(SCHF2)ethyl, 2-(SCF3)ethyl or 2-(SC2F5)ethyl;
- (C1-C4-alkyl)carbonyl: CO-CH3, CO-C2H5, CO-CH2-C2H5, CO-CH(CHg)2, n-butylcarbonyl, CO-CH(CH3)-C2H5, CO-CH2-CH(CH3)2 or CO-C(CH3)3.
preferably CO-CH3 or CO-C2H5;
- (C1-C4-haloalkyl)carbonyl: a (C1-C4-alkyl)carbonyl radical - as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. CO-CH2F, CO-CHF2, CO-CF3, CO-CH2C1, CO-CH(C1)2, CO-C(C1)3, chlorofluoromethylcarbonyl, dichlorofluoromethylcarbonyl, chlorodifluoromethylcarbonyl, 2-fluoroethylcarbonyl, 2-chloroethylcarbonyl, 2-bromoethylcarbonyl, 2-iodoethylcarbonyl, 2,2-difluoroethylcarbonyl, 2,2,2-trifluoroethylcarbonyl, 2-chloro-2-fluoroethylcarbonyl, 2-chloro-2,2-difluoroethylcarbonyl, 2,2-dichloro-2-fluoroethylcarbonyl, 2,2,2-trichloroethylcarbonyl, CO-CZFS, 2-fluoropropylcarbonyl, 3-fluoropropylcarbonyl, 2,2-difluoropropylcarbonyl, 2,3-difluoropropylcarbonyl, 2-chloropropylcarbonyl, 3-chloropropylcarbonyl, 2,3-dichloropropylcarbonyl, 2-bromopropylcarbonyl, 3-bromopropylcarbonyl, 3,3,3-trifluoropropylcarbonyl, 3,3,3-trichloropropylcarbonyl, CO-CH2-C2F5, CO-CFZ-C2F5, 1-(CH2F)-2-fluoroethylcarbonyl, 1-(CH2C1)-2-chloroethylcarbonyl, 1-(CH2Br)-2-bromoethylcarbonyl, 4-fluorobutylcarbonyl, 4-chlorobutylcarbonyl, 4-bromobutylcarbonyl or nonafluorobutylcarbonyl, preferably CO-CF3, CO-CH2C1 or 2,2,2-trifluoroethylcarbonyl;
- (Ci-Cs-alkyl)carbonyl: one of the abovementioned (C1-CQ-alkyl)carbonyl radicals or, for example, n-pentyl-CO, 1-methylbutyl-CO, 2-methylbutyl-CO, 3-methylbutyl-CO, 2,2-dimethylpropyl-C0, 1-ethylpropyl-CO, n-hexyl-C0, 1,1-dimethylpropyl-CO, 1,2-dimethylpropyl-CO, 1-methylpentyl-C0, 2-methylpentyl-CO, 3-methylpentyl-CO, 4-methylpentyl-CO, 1,1-dimethylbutyl-CO, 1,2-dimethylbutyl-CO, 1,3-dimethylbutyl-C0, 2,2-dimethylbutyl-CO, 2,3-dimethylbutyl-C0, 3,3-dimethylbutyl-CO, 1-ethylbutyl-CO, 2-ethylbutyl-CO, 1,1,2-trimethylpropyl-CO, 12.2-trimethylpropyl-CO, 1-ethyl-1-methylpropyl-CO or 1-ethyl-2-methylpropyl-C0, preferably CO-CH3, CO-C2H5, CO-CH2-CZHS, CO-CH(CH3)2, n-butyl-CO, CO-C(CH3)3, CO-(n-C5H11) or CO-(n-C6H13):
- (C1-Cs-haloalkyl)carbonyl: a (C1-CS-alkyl)carbonylrest - as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. CO-CHZF, CO-CHF2, CO-CF3, CO-CH2C1, CO-CH(C1)z, CO-C(C1)3, chlorofluoromethylcarbonyl, dichlorofluoromethylcarbonyl, chlorodifluoromethylcarbonyl, 2-fluoroethylcarbonyl, 2-chloroethylcarbonyl, 2-bromoethylcarbonyl, 2-iodoethylcarbonyl, 2,2-difluoroethylcarbonyl, 2,2,2-trifluoroethylcarbonyl, 2-chloro-2-fluoroethylcarbonyl, 2-chloro-2,2-difluoroethylcarbonyl, 2~2-dichloro-2-fluoroethylcarbonyl, 2,2,2-trichloroethylcarbonyl, CO-C2F5, 2-fluoropropylcarbonyl, 3-fluoropropylcarbonyl, 2,2-difluoropropylcarbonyl, 2,3-difluoropropylcarbonyl, 2-chloropropylcarbonyl, 3-chloropropylcarbonyl, 2,3-dichloropropylcarbonyl, 2-bromopropylcarbonyl, 3-bromopropylcarbonyl, 3,3,3-trifluoropropylcarbonyl, 3,3,3-trichloropropylcarbonyl, CO-CHZ-C2F5, CO-CFZ-C2F5, 1-(CHZF)-2-fluoroethylcarbonyl, 1-(CH2C1)-2-chloroethylcarbonyl, 1-(CH2Br)-2-bromoethylcarbonyl, 4-fluorobutylcarbonyl, 4-chlorobutylcarbonyl, 4-bromobutylcarbonyl or nonafluorobutylcarbonyl, preferably CO-CF3, CO-CHZC1 or 2,2,2-trifluoroethylcarbonyl;
- (C1-C4-alkyl)carbonyloxy: 0-CO-CH3, O-CO-C2H5, 0-CO-CH2-C2H5, 0-CO-CH(CH3)2, 0-CO-CHz-CHZ-C2H5, 0-CO-CH(CH3)-CZHS, 0-CO-CH2-CH(CH3)2 or 0-CO-C(CH3)3, preferably 0-CO-CH3 or O-CO-CzHS;
- (C1-C4-haloalkyl)carbonyloxy: a (C1-C4-alkyl)carbonyl radical -as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. O-CO-CH2F, O-CO-CHF2, O-CO-CF3, 0-CO-CHZCl, O-CO-CH(C1)z, O-CO-C(C1)3, chlorofluoromethylcarbonyloxy, dichlorofluoromethylcarbonyloxy, chlorodifluoromethylcarbonyloxy, 2-fluoroethylcarbonyloxy, 2-chloroethylcarbonyloxy, 2-bromoethylcarbonyloxy, 2-iodoethylcarbonyloxy, 2,2-difluoroethylcarbonyloxy, 2,2,2-trifluoroethylcarbonyloxy, 2-chloro-2-fluoroethylcarbonyloxy, 2-chloro-2,2-difluoroethylcarbonyloxy, 2,2-dichloro-2-fluoroethylcarbonyloxy, 2,2,2-trichloroethylcarbonyloxy, 0-CO-C2F5, 2-fluoropropylcarbonyloxy, 3-fluoropropylcarbonyloxy, 2,2-difluoropropylcarbonyloxy, 2.3-difluoropropylcarbonyloxy, 2-chloropropylcarbonyloxy, 3-chloropropylcarbonyloxy, 2,3-dichloropropylcarbonyloxy, 2-bromopropylcarbonyloxy, 3-bromopropylcarbonyloxy, 3,3,3-trifluoropropylcarbonyloxy, 3,3,3-trichloropropylcarbonyloxy, O-CO-CHy-CzFS, O-CO-CF2-C2F5, 1-(CH2F)-2-fluoroethylcarbonyloxy, 1-(CH2C1)-2-chloroethylcarbonyloxy, 1-(CHzBr)-2-bromoethylcarbonyloxy, 4-fluorobutylcarbonyloxy, 4-chlorobutylcarbonyloxy, 4-bromobutylcarbonyloxy or nonafluorobutylcarbonyloxy, preferably O-CO-CF3, O-CO-CH2C1 or 2~2.2-trifluoroethylcarbonyloxy;
- (C1-C6-alkyl)carbonyloxy: one of the abovementioned (C1-C4-alkyl)carbonyloxy radicals or, for example, n-pentyl-COO, 1-methylbutyl-COO, 2-methylbutyl-COO, 3-methylbutyl-COO, 2,2-dimethylpropyl-COO, 1-ethylpropyl-COO, n-hexyl-COO, 1,1-dimethylpropyl-COO, 1,2-dimethylpropyl-COO, 1-methylpentyl-COO, 2-methylpentyl-COO, 3-methylpentyl-COO, 4-methylpentyl-C00, 1,1-dimethylbutyl-C00, 1,2-dimethylbutyl-COO, 1,3-dimethylbutyl-COO, 2,2-dimethylbutyl-COO, 2,3-dimethylbutyl-C00, 3,3-dimethylbutyl-COO, 1-ethylbutyl-COO, 2-ethylbutyl-COO, 1,1,2-trimethylpropyl-COO, 1,2,2-trimethylpropyl-C00, 1-ethyl-1-methylpropyl-COO or 1-ethyl-2-methylpropyl-COO, preferably O-CO-CHg, O-CO-CZHS, O-CO-CHZ-CzHS, O-CO-CH(CH3)2.
n-butyl-COO, 0-CO-C(CH3)3, 0-CO-(n-C5H11) or 0-CO-(n-C6H13):
- (C1-C6-alkyl)thiocarbonyl: CS-CH3, CS-C2H5, CS-CH2-CZHS, CS-CH(CH3)2, CS-(n-C4Hg), CS-CH(CH3)-CzHS, CS-CH2-CH(CH3)2.
CS-C(CH3)3, CS-(n-C5H11). CS-CH(CH3)-CHZ-CZHS.
CS-CHZ-CH(CH3)-C2H5, CS-CH2CHy-CH(CH3)2, CS-C(CHg)2-CZHS, CS-CH(CH3)-CH(CH3)2, CS-CHZ-C(CH3)3, CS-CH(CZHS)-C2H5, CS-(n-C6H13), CS-CH(CH3)-(n-CqHg), CS-CH2-CH(CH3)-CH2-C2H5, CS-CHZCH2-CH(CH3)-CZHS, CS-CHZCHZCH2-CH(CH3)y, CS-C(CH3)2-CHZ-C2H5, CS-CH(CH3)-CH(CH3)-C2H5, CS-CH(CHg)-CH2-CH(CH3)Z, CS-CHZ-C(CH3)2-CZHS, CS-CH2-CH(CH3)-CH(CH3)y, CS-CHZCH2-C(CH3)3, CS-CH(C2H5)-CHZ-CZHS, CS-CHy-CH(C2H5)-C2H5, CS-C(CH3)2-CH(CH3)y, CS-CH(CH3)-C(CH3)3, CS-C(CH3)(C2H5)-CZHS Or CS-CH(CzHS)-CH(CH3)2, preferably CS-CH3, CS-CZHS, CS-CH2-C2H5, CS-CH(CH3)2 Or CS-(n-C4Hg);
- (C1-C4-alkoxy)carbonyl: CO-OCH3, CO-OC2H5, CO-OCH2-C2H5, CO-OCH(CH3)2, n-butoxycarbonyl, CO-OCH(CH3)-C2H5, CO-OCH2-CH(CH3)z or CO-OC(CH3)3, preferably CO-OCH3 or CO-OC2H5;
- (C1-C6-alkoxy)carbonyl: one of the abovementioned (C1-C4-alkoxy)carbonyl radicals or, for example, n-pentoxy-CO, 1-methylbutoxy-CO, 2-methylbutoxy-CO, 3-methylbutoxy-CO, 2,2-dimethylpropoxy-CO, 1-ethylpropoxy-CO, n-hexoxy-CO, 1,1-dimethylpropoxy-CO, 1,2-dimethylpropoxy-CO, 1-methylpentoxy-CO, 2-methylpentoxy-CO, 3-methylpentoxy-CO, 4-methylpentoxy-CO, 1,1-dimethylbutoxy-C0, 1,2-dimethylbutoxy-CO, 1,3-dimethylbutoxy-CO, 2,2-dimethylbutoxy-CO, 2,3-dimethylbutoxy-CO, 3,3-dimethylbutoxy-CO, 1-ethylbutoxy-CO, 2-ethylbutoxy-CO, 1,1,2-trimethylpropoxy-CO, 1,2,2-trimethylpropoxy-C0, 1-ethyl-1-methylpropoxy-CO or 1-ethyl-2-methylpropoxy-CO, preferably CO-OCH3, CO-OC2H5, CO-OCHZ-CZHS, CO-OCH(CH3)2, n-butoxy-CO, CO-OC(CH3)3, n-pentoxy-CO or n-hexoxy-CO;
- (C1-C4-alkoxy)carbonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by (C1-C4-alkoxy)carbonyl - as mentioned above -, eg. CH2-CO-OCH3, CH2-CO-OCZHS, CHz-CO-OCH2-CZHS, CHz-CO-OCH(CH3)2, n-butoxycarbonylmethyl, CH2-CO-OCH(CH3)-C2H5, CH2-CO-OCH2-CH(CH3)2, CH2-CO-OC(CH3)3r I-(CO-OCH3)ethyl, 1-(CO-OC2H5)ethyl, 1-(CO-OCHZ-C2H5)ethyl, I-[CH(CH3)2]ethyl, 1-(n-butoxycarbonyl)ethyl, 1-[1-methylpropoxycarbonyl]ethyl, 1-[2-methylpropoxycarbonyl]ethyl, 2-(CO-OCH3)ethyl, 2-(CO-OCZHS)ethyl, 2-(CO-OCH2-C2H5)ethyl, 2-[CO-OCH(CH3)Z]ethyl, 2-(n-butoxycarbonyl)ethyl, 2-[1-methylpropoxycarbonyl]ethyl, 2-[2-methylpropoxycarbonyl]ethyl, 2-[CO-OC(CH3)3]ethyl, 2-(CO-OCH3)propyl, 2-(CO-OC2H5)propyl, 2-(CO-OCH2-CZHS)propyl, 2-[CO-OCH(CH3)Z]propyl, 2-(n-butoxycarbonyl)propyl, 2-[1-methylpropoxycarbonyl]propyl, 2-[2-methylpropoxycarbonyl]propyl, 2-[CO-OC(CH3)3]propyl, 3-(CO-OCH3)propyl, 3-(CO-OCZHS)propyl, 3-(CO-OCH2-C2H5)propyl, 3-[CO-OCH(CH3)2]propyl, 3-(n-butoxycarbonyl)propyl, 3-[1-methylpropoxycarbonyl]propyl, 3-[2-methylpropoxycarbonyl]propyl, 3-[CO-OC(CH3)3]propyl, 2-(CO-OCHg)butyl, 2-(CO-OCZHS)butyl, 2-(CO-0CH2-C2H5)butyl, 2-[CO-OCH(CH3)Z]butyl, 2-(n-butoxycarbonyl)butyl, 2-[1-methylpropoxycarbonyl]butyl, 2-[2-methylpropoxycarbonyl]butyl, 2-[CO-OC(CH3)3]butyl, 3-(CO-OCH3)butyl, 3-(CO-OCzHS)butyl, 3-(CO-OCH2-C2H5)butyl, 3-[CO-OCH(CH3)2]butyl, 3-(n-butoxycarbonyl)butyl, 3-[1-methylpropoxycarbonyl]butyl, 3-[2-methylpropoxycarbonyl]butyl, 3-[CO-OC(CH3)3]butyl, 4-(CO-OCH3)butyl, 4-(CO-OC2H5)butyl, 4-(CO-OCHZ-C2Hg)butyl, 4-ICO-OCH(CH3)Z]butyl, 4-(n-butoxycarbonyl)butyl, 4-[1-methylpropoxycarbonyl]butyl, 4-[2-methylpropoxycarbonyl]butyl or 4-[CO-OC(CH3)3]butyl, preferably CH2-CO-OCH3, CH2-CO-OCZHS, 1-(CO-OCH3)ethyl or 1-(CO-OC2H5)ethyl;
- (C1-C6-alkoxy)thiocarbonyl: for example CS-OCH3, CS-OC2H5, CS-OCHZ-CZHS, CS-OCH(CH3)z, CS-O(n-C4H9), CS-OCH(CH3)-CZHS, CS-OCH2-CH(CHg)2, CS-OC(CH3)3, CS-O(n-CSHii).
CS-OCH(CH3)-CHZ-C2H5, CS-OCH2-CH(CH3)-CZHS, CS-OCH2CH2-CH(CH3)2, CO-OCH2-C(CH3)3, CS-OCH(CZHS)-C2H5, CS-O(n-C6H13).
CS-OC(CH3)2-CZHS, CS-OCH(CH3)-CH(CH3)2, CS-OCH(CH3)-(n-C4H9), CS-OCHz-CH(CH3)-CHy-C2H5, CS-OCH2CH2-CH(CH3)-C2H5, CS-OCH2CH2CH2-CH(CH3)Z, CS-OC(CH3)2-CH2-C2H5, CS-OCH(CH3)-CH(CH3)-C2H5, CS-OCH(CH3)-CH2-CH(CH3)z, CS-OCH2-C(CH3)2-C2H5, CS-OCH2-CH(CH3)-CH(CH3)2, CS-OCHyCHy-C(CH3)3, CS-OC(CyHS)-CHy-C2H5, CS-OCH2-CH(CZHS)-C2H5, CS-OC(CH3)Z-CH(CH3)2, CS-OCH(CH3)-C(CH3)3, CS-OC(CH3)(C2H5)-C2H5 or CS-OCH(C2H5)-CH(CH3)2, preferably CS-OCH3 or CS-OC2H5;
(Ci-C4-alkylthio)carbonyl: CO-SCH3, CO-SC2H5, CO-SCHZ-C2H5, CO-SCH(CH3)Z, CO-SCHyCH2-C2H5, CO-SCH(CH3)-CZHS, CO-SCH2-CH(CH3)2 or CO-SC(CH3)3, preferably CO-SCH3 or CO-SC2H5:
- (C1-CQ-alkylthio)carbonyl-Cl-C4-alkyl: C1-CQ-alkyl which is substituted by (C1-C4-alkylthio)carbonyl - as mentioned above -, ie. CHZ-CO-SCH3, CHZ-CO-SC2H5, CH2-CO-SCH2-C2H5, CH2-CO-SCH(CH3)2, CHy-CO-SCH2CHy-C2Hg, 5 CHZ-CO-SCH(CH3)-CZHS, CH2-CO-SCHy-CH(CH3)2, CH2-CO-SC(CH3)3.
1-(CO-SCH3)ethyl, 1-(CO-SC2H5)ethyl, 1-(CO-SCH2-C2H5)ethyl, 1-[CO-SCH(CH3)2]ethyl, 1-(CO-SCH2CH2-CzHS)ethyl, 1-[CO-SCH(CH3)-C2H5]ethyl, 1-[CO-SCHZ-CH(CH3)2]ethyl, 1-[CO-SC(CH3)3]ethyl, 2-(CO-SCH3)ethyl, 2-(CO-SC2H5)ethyl, 10 2-(CO-SCHZ-C2H5)ethyl, 2-[CO-SCH(CH3)Z]ethyl, 2-(CO-SCH2CH2-C2H5)ethyl, 2-[CO-SCH(CH3)-CzHS]ethyl, 2-[CO-SCHz-CH(CH3)2]ethyl, 2-[CO-SC(CHg)3]ethyl, 2-(CO-SCH3)propyl, 2-(CO-SCZHS)propyl, 2-(CO-SCHZ-C2H5)propyl, 2-[CO-SCH(CH3)2]propyl, 2-(CO-SCHZCH2-C2H5)propyl, 15 2-ICO-SCH(CH3)-C2H5]propyl, 2-[CO-SCHZ-CH(CH3)Z]propyl, 2-[CO-SC(CH3)3]propyl, 3-(CO-SCH3)propyl, 3-(CO-SC2H5)propyl, 3-(CO-SCH2-CZHS)propyl, 3-[CO-SCH(CH3)z]propyl, 3-(CO-SCH2CH2-C2H5)propyl, 3-[CO-SCH(CH3)-CZHS]propyl, 3-[CO-SCH2-CH(CH3)z]propyl, 3-[CO-SC(CH3)3]propyl, 2-(CO-SCH3)butyl, 2-(CO-SC2H5)butyl, 2-(CO-SCHZ-C2H5)butyl, 2-[CO-SCH(CH3)2]butyl, 2-(CO-SCH2CH2-C2H5)butyl, 2-[CO-SCH(CH3)-C2H5]butyl, 2-[CO-SCHZ-CH(CH3)2]butyl, 2-[CO-SC(CH3)3]butyl, 3-(CO-SCH3)butyl, 3-(CO-SC2H5)butyl, 3-(CO-SCH2-CZHS)butyl, 3-[CO-SCH(CH3)2]butyl, 3-(CO-SCH2CH2-C2H5)butyl, 3-[CO-SCH(CH3)-CZH5]butyl, 3-[CO-SCHZ-CH(CH3)2]butyl, 3-[CO-SC(CH3)3]butyl, 4-(CO-SCH3)butyl, 4-(CO-SC2H5)butyl, 4-(CO-SCH2-C2H5)butyl, 4-[CO-SCH(CH3)2]butyl, 4-(CO-SCHZCH2-C2H5)butyl, 4-[CO-SCH(CH3)-C2H5]butyl, 4-[CO-SCHZ-CH(CH3)2]butyl or 4-[CO-SC(CH3)3]butyl, preferably CH2-CO-SCH3, CH2-CO-SCzHS, 1-(CO-SCH3)ethyl or 1-(CO-SCZH5)ethyl;
- C1-C6-alkylsulfinyl: a C1-CQ-alkylsulfinyl radical such as SO-CH3, SO-CZHS, SO-CH2-CZHg, SO-CH(CH3)2, SO-(n-CqHg), SO-CH(CH3)-CZHS, SO-CHz-CH(CH3)2 or SO-C(CH3)3, or, for example, SO-(n-CSH11), 1-methylbutyl-SO, 2-methylbutyl-S0, 3-methylbutyl-S0, 2,2-dimethylpropyl-S0, 1-ethylpropyl-S0, n-hexyl-S0, 1,1-dimethylpropyl-SO, 1,2-dimethylpropyl-SO, 1-methylpentyl-SO, 2-methylpentyl-SO, 3-methylpentyl-SO, 4-methylpentyl-S0, 1,1-dimethylbutyl-S0, 1,2-dimethylbutyl-SO, 1,3-dimethylbutyl-S0, 2,2-dimethylbutyl-SO, 2,3-dimethylbutyl-S0, 3,3-dimethylbutyl-SO, 1-ethylbutyl-SO, 2-ethylbutyl-SO, 1,1,2-trimethylpropyl-S0, 1,2,2-trimethylpropyl-SO, 1-ethyl-1-methylpropyl-SO or 1-ethyl-2-methylpropyl-S0, preferably SO-CH3, SO-C2H5, SO-CH2-C2H5, SO-CH(CH3)y, SO-(n-C4Hg), SO-C(CH3)3, SO-(n-C5H11) or SO-(n-C6Hls):
- C1-C4-alkylsulfinyl-C1-C4-alkyl: C1-CQ-alkyl which is substituted by C1-C4-alkylsulfinyl as mentioned above, eg.
CHZSOCH3, CHySOC2H5, n-propylsulfinylmethyl, CHZSOCH(CH3)2, n-butylsulfinylmethyl, (1-methylpropylsulfinyl)methyl, (2-methylpropylsulfinyl)methyl, (1,1-dimethylethylsulfinyl)-methyl, 2-methylsulfinylethyl, 2-ethylsulfinylethyl, 2-(n-propylsulfinyl)ethyl, 2-(1-methylethylsulfinyl)ethyl, 2-(n-butylsulfinyl)ethyl, 2-(1-methylpropylsulfinyl)ethyl, 2-(2-methylpropylsulfinyl)ethyl, 2-(1.1-dimethylethylsulfinyl)ethyl, 2-(SOCH3)propyl, 3-(SOCH3)propyl, 2-(SOC2H5)propyl, 3-(SOCZHS)propyl, 3-(propylsulfinyl)propyl, 3-(butylsulfinyl)propyl, 4-(SOCH3)butyl, 4-(SOCZHS)butyl, 4-(n-propylsulfinyl)butyl or 4-(n-butylsulfinyl)butyl, in particular 2-(SOCH3)ethyl;
- Cl-CQ-haloalkylsulfinyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-haloalkylsulfinyl as mentioned above, eg.
2-(2,2,2-trifluoroethylsulfinyl)ethyl;
- C1-C4-alkylsulfonyl: SOZ-CH3, S02-C2H5, SOZ-CHZ-CZHS, S02-CH(CH3)2, n-butylsulfonyl, S02-CH(CH3)-CZHS, S02-CHz-CH(CH3)2 or SOZ-C(CH3)3, preferably S02-CH3 or S02-CZHS;
- C1-C4-haloalkylsulfonyl: a C1-C4-alkylsulfonyl radical - as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. S02-CH2F, SOZ-CHFy, S02-CF3, SOZ-CHyCl, S02-CH(C1)2, SOz-C(C1)3, chlorofluoromethylsulfonyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl, S02-C2F5, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2,3-dichloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3-trichloropropylsulfonyl, S02-CH2-CZFS. S02-CF2-C2F5.
1-(fluoromethyl)-2-fluoroethylsulfonyl, 1-(chloromethyl)-2-chloroethylsulfonyl, 1-(bromomethyl)-2-bromoethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl or nonafluorobutylsulfonyl, preferably S02-CH2C1, S02-CF3 or 2,2,2-trifluoroethylsulfonyl;
- C1-C6-alkylsulfonyl: a C1-C4-alkylsulfonyl radical as mentioned above or, for example, S02-(n-CSH11), 1-methylbutyl-S02, 2-methylbutyl-502, 3-methylbutyl-S02, 2,2-dimethylpropyl-S02, 1-ethylpropyl-SOz, n-hexyl-502, 1,1-dimethylpropyl-S02, 1,2-dimethylpropyl-502, 1-methylpentyl-S02, 2-methylpentyl-S02, 3-methylpentyl-S02, 4-methylpentyl-S02, 1,1-dimethylbutyl-S02, 1,2-dimethylbutyl-S02, 1,3-dimethylbutyl-S02, 2,2-dimethylbutyl-S02, 2,3-dimethylbutyl-S02, 3,3-dimethylbutyl-S02, 1-ethylbutyl-S02, 2-ethylbutyl-502, 1,1,2-trimethylpropyl-S02, 1,2,2-trimethylpropyl-502, 1-ethyl-1-methylpropyl-S02 or 1-ethyl-2-methylpropyl-S02, preferably S02-CH3, S02-C2H5, S02-CH2-C2H5, S02-CH(CH3)2.
S02-(n-CqHg), S02-C(CH3)3, S02-(n-C5H11) Or S02-(n-C6H13)1 - C1-C4-alkylsulfonyl-C1-CQ-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkylsulfonyl as mentioned above, eg.
CH2S02-CH3, CH2S02-C2H5, CH2S02-CH2-C2H5, CH2S02-CH(CH3)2, CH2S02-CH2CH2-C2H5, (1-methylpropylsulfonyl)methyl, (2-methylpropylsulfonyl)methyl, CH2S02-C(CH3)3, CH(CH3)S02-CH3, CH(CH3)SOz-C2H5, CH2CH2S02-CH3, CH2CH2S02-C2H5, CH2CHzS02-CH2-C2H5.
CH2CH2S02-CH(CH3)2, CH2CH2S02-CHyCH2-C2H5, 2-(1-methylpropylsulfonyl)ethyl, 2-(2-methylpropylsulfonyl)ethyl, CH2CH2S02-C(CH3)3.
2-(S02-CH3)propyl, 2-(S02-C2H5)propyl, 2-(S02-CH2-C2H5)propyl, 2-[S02-CH(CH3)2]propyl, 2-(S02-CH2CH2-C2H5)propyl, 2-(1-methylpropylsulfonyl)propyl, 2-(2-methylpropylsulfonyl)propyl, 2-[S02-C(CH3)3]propyl, 3-(S02-CH3)propyl, 3-(S02-C2H5)propyl, 3-(S02-CH2-C2H5)propyl, 3-[S02-CH(CH3)2]propyl, 3-(S02-CH2CH2-C2H5)propyl, 3-(1-methylpropylsulfonyl)propyl, 3-(2-methylpropylsulfonyl)propyl, 3-[S02-C(CH3)3]propyl, 2-(S02-CH3)butyl, 2-(S02-C2H5)butyl, 2-(S02-CH2-C2H5)butyl, 2-[S02-CH(CH3)2]butyl, 2-(S02-CH2CH2-C2Hg)butyl, 2-(1-methylpropylsulfonyl)butyl, 2-(2-methylpropylsulfonyl)butyl, 2-[S02-C(CH3)3]butyl, 3-(S02-CH3)butyl, 3-(S02-C2H5)butyl, 3-(S02-CHZ-C2Hg)butyl, 3-[S02-CH(CH3)2]butyl, 3-(S02-CH2CH2-C2H5)butyl, 3-(1-methylpropylsulfonyl)butyl, 3-(2-methylpropylsulfonyl)butyl, 3-[S02-C(CH3)3]butyl, 4-(S02-CH3)butyl, 4-(S02-C2H5)butyl, 4-(S02-CH2-C2H5)butyl, 4-[S02-CH(CH3)2]butyl, 4-(S02-CHZCH2-C2H5)butyl, 4-(1-methylpropylsulfonyl)butyl, 4-(2-methylpropylsulfonyl)butyl or 4-[S02-C(CH3)3]butyl, in particular CH2CH2S02-CH3 or CH2CH2S02-C2H5;
CHZSOCH3, CHySOC2H5, n-propylsulfinylmethyl, CHZSOCH(CH3)2, n-butylsulfinylmethyl, (1-methylpropylsulfinyl)methyl, (2-methylpropylsulfinyl)methyl, (1,1-dimethylethylsulfinyl)-methyl, 2-methylsulfinylethyl, 2-ethylsulfinylethyl, 2-(n-propylsulfinyl)ethyl, 2-(1-methylethylsulfinyl)ethyl, 2-(n-butylsulfinyl)ethyl, 2-(1-methylpropylsulfinyl)ethyl, 2-(2-methylpropylsulfinyl)ethyl, 2-(1.1-dimethylethylsulfinyl)ethyl, 2-(SOCH3)propyl, 3-(SOCH3)propyl, 2-(SOC2H5)propyl, 3-(SOCZHS)propyl, 3-(propylsulfinyl)propyl, 3-(butylsulfinyl)propyl, 4-(SOCH3)butyl, 4-(SOCZHS)butyl, 4-(n-propylsulfinyl)butyl or 4-(n-butylsulfinyl)butyl, in particular 2-(SOCH3)ethyl;
- Cl-CQ-haloalkylsulfinyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-haloalkylsulfinyl as mentioned above, eg.
2-(2,2,2-trifluoroethylsulfinyl)ethyl;
- C1-C4-alkylsulfonyl: SOZ-CH3, S02-C2H5, SOZ-CHZ-CZHS, S02-CH(CH3)2, n-butylsulfonyl, S02-CH(CH3)-CZHS, S02-CHz-CH(CH3)2 or SOZ-C(CH3)3, preferably S02-CH3 or S02-CZHS;
- C1-C4-haloalkylsulfonyl: a C1-C4-alkylsulfonyl radical - as mentioned above - which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. S02-CH2F, SOZ-CHFy, S02-CF3, SOZ-CHyCl, S02-CH(C1)2, SOz-C(C1)3, chlorofluoromethylsulfonyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl, S02-C2F5, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2,3-dichloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3-trichloropropylsulfonyl, S02-CH2-CZFS. S02-CF2-C2F5.
1-(fluoromethyl)-2-fluoroethylsulfonyl, 1-(chloromethyl)-2-chloroethylsulfonyl, 1-(bromomethyl)-2-bromoethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl or nonafluorobutylsulfonyl, preferably S02-CH2C1, S02-CF3 or 2,2,2-trifluoroethylsulfonyl;
- C1-C6-alkylsulfonyl: a C1-C4-alkylsulfonyl radical as mentioned above or, for example, S02-(n-CSH11), 1-methylbutyl-S02, 2-methylbutyl-502, 3-methylbutyl-S02, 2,2-dimethylpropyl-S02, 1-ethylpropyl-SOz, n-hexyl-502, 1,1-dimethylpropyl-S02, 1,2-dimethylpropyl-502, 1-methylpentyl-S02, 2-methylpentyl-S02, 3-methylpentyl-S02, 4-methylpentyl-S02, 1,1-dimethylbutyl-S02, 1,2-dimethylbutyl-S02, 1,3-dimethylbutyl-S02, 2,2-dimethylbutyl-S02, 2,3-dimethylbutyl-S02, 3,3-dimethylbutyl-S02, 1-ethylbutyl-S02, 2-ethylbutyl-502, 1,1,2-trimethylpropyl-S02, 1,2,2-trimethylpropyl-502, 1-ethyl-1-methylpropyl-S02 or 1-ethyl-2-methylpropyl-S02, preferably S02-CH3, S02-C2H5, S02-CH2-C2H5, S02-CH(CH3)2.
S02-(n-CqHg), S02-C(CH3)3, S02-(n-C5H11) Or S02-(n-C6H13)1 - C1-C4-alkylsulfonyl-C1-CQ-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkylsulfonyl as mentioned above, eg.
CH2S02-CH3, CH2S02-C2H5, CH2S02-CH2-C2H5, CH2S02-CH(CH3)2, CH2S02-CH2CH2-C2H5, (1-methylpropylsulfonyl)methyl, (2-methylpropylsulfonyl)methyl, CH2S02-C(CH3)3, CH(CH3)S02-CH3, CH(CH3)SOz-C2H5, CH2CH2S02-CH3, CH2CH2S02-C2H5, CH2CHzS02-CH2-C2H5.
CH2CH2S02-CH(CH3)2, CH2CH2S02-CHyCH2-C2H5, 2-(1-methylpropylsulfonyl)ethyl, 2-(2-methylpropylsulfonyl)ethyl, CH2CH2S02-C(CH3)3.
2-(S02-CH3)propyl, 2-(S02-C2H5)propyl, 2-(S02-CH2-C2H5)propyl, 2-[S02-CH(CH3)2]propyl, 2-(S02-CH2CH2-C2H5)propyl, 2-(1-methylpropylsulfonyl)propyl, 2-(2-methylpropylsulfonyl)propyl, 2-[S02-C(CH3)3]propyl, 3-(S02-CH3)propyl, 3-(S02-C2H5)propyl, 3-(S02-CH2-C2H5)propyl, 3-[S02-CH(CH3)2]propyl, 3-(S02-CH2CH2-C2H5)propyl, 3-(1-methylpropylsulfonyl)propyl, 3-(2-methylpropylsulfonyl)propyl, 3-[S02-C(CH3)3]propyl, 2-(S02-CH3)butyl, 2-(S02-C2H5)butyl, 2-(S02-CH2-C2H5)butyl, 2-[S02-CH(CH3)2]butyl, 2-(S02-CH2CH2-C2Hg)butyl, 2-(1-methylpropylsulfonyl)butyl, 2-(2-methylpropylsulfonyl)butyl, 2-[S02-C(CH3)3]butyl, 3-(S02-CH3)butyl, 3-(S02-C2H5)butyl, 3-(S02-CHZ-C2Hg)butyl, 3-[S02-CH(CH3)2]butyl, 3-(S02-CH2CH2-C2H5)butyl, 3-(1-methylpropylsulfonyl)butyl, 3-(2-methylpropylsulfonyl)butyl, 3-[S02-C(CH3)3]butyl, 4-(S02-CH3)butyl, 4-(S02-C2H5)butyl, 4-(S02-CH2-C2H5)butyl, 4-[S02-CH(CH3)2]butyl, 4-(S02-CHZCH2-C2H5)butyl, 4-(1-methylpropylsulfonyl)butyl, 4-(2-methylpropylsulfonyl)butyl or 4-[S02-C(CH3)3]butyl, in particular CH2CH2S02-CH3 or CH2CH2S02-C2H5;
- C1-C4-haloalk~ylsulfonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-haloalkylsulfonyl as mentioned above, eg.
2-(2,2,2-trifluoroethylsulfonyl)ethyl;
- C1-C4-alkylamino-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-Cq-alkylamino such as H3C-NH-, H5C2-NH-, n-propyl-NH-, 1-methylethyl-NH-, n-butyl-NH-, 1-methylpropyl-NH-, 2-methylpropyl-NH- and 1,1-dimethylethyl-NH-, preferably H3C-NH- or H5C2-NH-, ie., for example, CHZCHZ-NH-CH3, CH2CH2-N(CH3)2, CH2CHy-NH-CyHS or CHZCH2-N(CZHS)2;
- (C1-CQ-alkylamino)carbonyl: CO-NH-CH3, CO-NH-CZHS, n-propylamino, CO-NH-CH(CH3)Z, CO-NH-CH2CHy-CZHS, CO-NH-CH(CH3)-CzHS, CO-NH-CH2-CH(CH3)z or CO-NH-C(CH3)3.
preferably CO-NH-CH3 or CO-NH-CZHS;
- (C1-C6-alkylamino)carbonyl: one of the (C1-C4-alkylamino)carbonyl radicals mentioned above or, for example, CO-NH-(n-CSH11), 1-methylbutyl-NHCO-, 2-methylbutyl-NHCO-, 3-methylbutyl-NHCO-, 2,2-dimethylpropyl-NHCO-, 1-ethylpropyl-NHCO-, CO-NH-(n-C6H13).
1,1-dimethylpropyl-NHCO-; 1,2-dimethylpropyl-NHCO-, 1-methylpentyl-NHCO-, 2-methylpentyl-NHCO-, 3-methylpentyl-NHCO-, 4-methylpentyl-NHCO-, 1,1-dimethylbutyl-NHCO-, 1,2-dimethylbutyl-NHCO-, 1,3-dimethylbutyl-NHCO-, 2,2-dimethylbutyl-NHCO-, 2,3-dimethylbutyl-NHCO-, 3,3-dimethylbutyl-NHCO-, 1-ethylbutyl-NHCO-, 2-ethylbutyl-NHCO-, 1,1,2-trimethylpropyl-NHCO-, 1,2,2-trimethylpropyl-NHCO-, 1-ethyl-1-methylpropyl-NHCO- or 1-ethyl-2-methylpropyl-NHCO-, preferably CO-NH-CH3, CO-NH-CZHS, CO-NH-CHZ-CZHS, CO-NH-CH(CH3)Z, CO-NH-(n-C4H9), CO-NH-C(CH3)3, CO-NH-(n-C5H11) or CO-NH-(n-C6H13)f - (C1-C4-alkylamino)carbonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted [lacuna] (C1-C4-alkylamino)carbonyl as mentioned above, preferably by CO-NH-CH3 or CO-NH-CZHS, as [sic] eg.
CHZ-CO-NH-CH3, CH2-CO-NH-C2H5, CH2-CO-NH-CHy-CzHS, CH2-CO-NH-CH(CH3)2, CHZ-CO-NH-CH2CHz-CzHS, CHZ-CO-NH-CH(CH3)-C2H5, CH2-CO-NH-CHZ-CH(CH3)p, CHy-CO-NH-C(CH3)3, CH(CH3)-CO-NH-CH3, CH(CH3)-CO-NH-CzHS, 2-(CO-NH-CH3)ethyl, 2-(CO-NH-CZHS)ethyl, 2-(CO-NH-CHZ-C2H5)ethyl, 2-[CH2-CO-NH-CH(CH3)2]ethyl, 2-(CO-NH-CHZCHZ-CzHS)ethyl, 2-[CO-NH-CH(CH3)-CZHS]ethyl, 2-[CO-NH-CHZ-CH(CHg)2Jethyl, 2-[CO-NH-C(CH3)3]ethyl, 2-(CO-NH-CH3)propyl, 2-(CO-NH-C2H5)propyl, 2-(CO-NH-CHZ-C2H5)propyl, 2-[CHZ-CO-NH-CH(CH3)z]propyl, 2-(CO-NH-CH2CH2-CzHS)propyl, 2-[CO-NH-CH(CH3)-C2H5]propyl, 2-[CO-NH-CHZ-CH(CH3)2]propyl, 2-[CO-NH-C(CH3)3]propyl, 3-(CO-NH-CHg)propyl, 3-(CO-NH-CZHS)propyl, 3-(CO-NH-CHZ-CZHS)propyl, 3-[CHy-CO-NH-CH(CH3)z]propyl, 3-(CO-NH-CHyCH2-C2H5)propyl, 3-[CO-NH-CH(CH3)-C2Hg]propyl, 3-[CO-NH-CH2-CH(CH3)y]propyl, 3-(CO-NH-C(CH3)3]propyl, 2~(CO-NH-CH3)butyl, 2-(CO-NH-C2H5)butyl, 2-(CO-NH-CHZ-CZHS)butyl, 2-[CH2-CO-NH-CH(CH3)2]butyl, 2-(CO-NH-CHZCH2-CyHS)butyl, 2-[CO-NH-CH(CH3)-C2H5]butyl, 2-[CO-NH-CH2-CH(CH3)2]butyl, 2-[CO-NH-C(CH3)3]butyl, 3-(CO-NH-CH3)butyl, 3-(CO-NH-C2H5)butyl, 3-(CO-NH-CH2-C2H5)butyl, 3-[CHz-CO-NH-CH(CH3)y]butyl, 3-(CO-NH-CHZCHZ-CZHS)butyl, 3-[CO-NH-CH(CH3)-CZHS]butyl, 3-[CO-NH-CHZ-CH(CH3)2]butyl, 3-[CO-NH-C(CH3)3]butyl, 4-(CO-NH-CH3)butyl, 4-(CO-NH-CZHS)butyl, 4-(CO-NH-CH2-C2H5)butyl, 4-[CH2-CO-NH-CH(CH3)2]butyl, 4-(CO-NH-CH2CH2-C2H5)butyl, 4-[CO-NH-CH(CH3)-CZHS]butyl, 4-[CO-NH-CH2-CH(CH3)2]butyl or 4-[CO-NH-C(CH3)3]butyl, preferably CHZ-CO-NH-CH3, CHZ-CO-NH-C2H5, CH(CH3)-CO-NH-CH3 or CH(CHg)-CO-NH-C2H5;
- di(C1-C4-alkyl)amino: N(CH3)Z, N(C2H5)2, N,N-dipropylamino, N,N-di(1-methylethyl)amino, N,N-dibutylamino, N,N-di(1-methylpropyl)amino, N,N-di(2-methylpropyl)amino, N.N-di(1,1-dimethylethyl)amino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-methyl-N-(1-methylethyl)amino, N-butyl-N-methylamino, N-methyl-N-(1-methylpropyl)amino, N-methyl-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-methylamino, N-ethyl-N-propylamino, N-ethyl-N-(1-methylethyl)amino, N-butyl-N-ethylamino, N-ethyl-N-(1-methylpropyl)amino, N-ethyl-N-(2-methylpropyl)amino, N-ethyl-N-(1,1-dimethylethyl)amino, N-(1-methylethyl)-N-propylamino, N-butyl-N-propylamino, N-(1-methylpropyl)-N-propylamino, N-(2-methylpropyl)-N-propylamino, N-(1,1-dimethylethyl)-N-propylamino, N-butyl-N-(1-methylethyl)amino, N-(1-methylethyl)-N-(1-methylpropyl)amino, N-(1-methylethyl)-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-(1-methylethyl)amino, N-butyl-N-(1-methylpropyl)amino, N-butyl-N-(2-methylpropyl)amino, N-butyl-N-(1,1-dimethylethyl)amino, N-(1-methylpropyl)-N-(2-methylpropyl)amino, N_(1,1-dimethylethyl)-N-(1-methylpropyl)amino or N-(1,1-dimethylethyl)-N-(2-methylpropyl)amino, preferably N(CH3)2 or N(CzHS)27 - di(C1-C4-alkyl)amino-C1-C4-alkyl: C1-C4-alkyl which is 5 substituted by di(C1-C4-alkyl)amino as mentioned above, eg.
CH2N(CH3)2, CH2N(CZHS)Z, N,N-dipropylaminomethyl, N,N-di[CH(CH3)Z]aminomethyl, N,N-dibutylaminomethyl, N,N-di-(1-methylpropyl)aminomethyl, N,N-di(2-methylpropyl)aminomethyl, N,N-di[C(CH3)3]aminomethyl, N-ethyl-N-methylaminomethyl, 10 N-methyl-N-propylaminomethyl, N-methyl-N-[CH(CH3)2]aminomethyl, N-butyl-N-methylaminomethyl, N-methyl-N-(1-methylpropyl)aminomethyl, N-methyl-N-(2-methylpropyl)aminomethyl, N-[C(CH3)3]-N-methylaminomethyl, N-ethyl-N-propylaminomethyl, 15 N-ethyl-N-[CH(CH3)2]aminomethyl, N-butyl-N-ethylaminomethyl, N-ethyl-N-(1-methylpropyl)aminomethyl, N-ethyl-N-(2-methylpropyl)aminomethyl, N-ethyl-N-[C(CH3)3]aminomethyl, N-[CH(CH3)Z]-N-propylaminomethyl, N-butyl-N-propylaminomethyl, 20 N-(1-methylpropyl)-N-propylaminomethyl, N-(2-methylpropyl)-N-propylaminomethyl, N-[C(CH3)3]-N-propylaminomethyl, N-butyl-N-(1-methylethyl)-aminomethyl, N-[CH(CH3)2]-N-(1-methylpropyl)aminomethyl, N-[CH(CH3)2]-N-(2-methylpropyl)aminomethyl, N-[C(CH3)3]-N-[CH(CH3)Z]aminomethyl, N-butyl-N-(1-methylpropyl)aminomethyl, N-butyl-N-(2-methylpropyl)aminomethyl, N-butyl-N-[C(CH3)3]-aminomethyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminomethyl, N-[C(CH3)3]-N-(1-methylpropyl)aminomethyl, N-[C(CH3)a]-N-(2-methylpropyl)aminomethyl, N,N-dimethylaminoethyl, N~N-diethylaminoethyl, N,N-di(n-propyl)aminoethyl, N,N-di[CH(CH3)2]aminoethyl, N,N-dibutylaminoethyl, N,N-di(1-methylpropyl)aminoethyl, N,N-di(2-methylpropyl)aminoethyl, N,N-di[C(CH3)3]aminoethyl, N-ethyl-N-methylaminoethyl, N-methyl-N-propylaminoethyl, N-methyl-N-[CH(CH3)Z]aminoethyl, N-butyl-N-methylaminoethyl, N-methyl-N-(1-methylpropyl)aminoethyl, N-methyl-N-(2-methylpropyl)aminoethyl, N-[C(CH3)3]-N-methylaminoethyl, N-ethyl-N-propylaminoethyl, N-ethyl-N-[CH(CH3)2]aminoethyl, N-butyl-N-ethylaminoethyl, N-ethyl-N-(1-methylpropyl)aminoethyl, N_ethyl-N-(2-methylpropyl)aminoethyl, N-ethyl-N-[C(CH3)3]aminoethyl, N-[CH(CH3)2]-N-propylaminoethyl, N-butyl-N-propylaminoethyl, N-(1-methylpropyl)-N-propylaminoethyl, N-(2-methylpropyl)-N-propylaminoethyl, N-[C(CH3)3]-N-propylaminoethyl, N-butyl-N-[CH(CH3)2]aminoethyl, N-[CH(CH3)Z]-N-(1-methylpropyl)aminoethyl, N-[CH(CH3)Z]-N-(2-methylpropyl)aminoethyl, N-[C(CH3)3]-N-[CH(CH3)z]aminoethyl, N-butyl-N-(1-methylpropyl)aminoethyl, N-butyl-N-(2-methylpropyl)aminoethyl, N-butyl-N-[C(CH3)3]aminoethyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminoethyl, N-[C(CH3)3]-N-(1-methylpropyl)aminoethyl or N-[C(CH3)3]-N-(2-methylpropyl)aminoethyl, in particular N,N-dimethylaminoethyl or N,N-diethylaminoethyl;
- di(C1-C9-alkyl)aminocarbonyl: CO-N(CH3)z, CO-N(CzHs), CO-N(CHZ-CZHS)z, CO-N[CH(CH3)zlz. N,N-dibutylaminocarbonyl, CO-N[CH(CH3)-C2H5]z, CO-N[CHz-CH(CH3)z]z, CO-N[C(CH3)3]2.
N-ethyl-N-methylaminocarbonyl, N-methyl-N-propylaminocarbonyl, N-methyl-N-[CH(CH3)2]aminocarbonyl, N-butyl-N-methylaminocarbonyl, N-methyl-N-(1-methylpropyl)aminocarbonyl, N-methyl-N-(2-methylpropyl)aminocarbonyl, N-[C(CH3)3]-N-methylaminocarbonyl, N-ethyl-N-propylaminocarbonyl, N-ethyl-N-[CH(CH3)z]aminocarbonyl, N-butyl-N-ethylaminocarbonyl, N-ethyl-N-(1-methylpropyl)aminocarbonyl, N-ethyl-N-(2-methylpropyl)aminocarbonyl, N-ethyl-N-[C(CH3)3]aminocarbonyl, N-[CH(CH3)z]-N-propylaminocarbonyl, N-butyl-N-propylaminocarbonyl, N-(1-methylpropyl)-N-propylaminocarbonyl, N-(2-methylpropyl)-N-propylaminocarbonyl, N-[C(CH3)3]-N-propylaminocarbonyl, N-butyl-N-[CH(CH3)z]aminocarbonyl, N-[CH(CH3)Z]-N-(1-methylpropyl)aminocarbonyl, N-[CH(CH3)z]-N-(2-methylpropyl)aminocarbonyl, N-[C(CH3)3]-N-[CH(CH3)z]aminocarbonyl, N-butyl-N-(1-methylpropyl)aminocarbonyl, N-butyl-N-(2-methylpropyl)aminocarbonyl, N-butyl-N-[C(CH3)3]aminocarbonyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminocarbonyl, N-[C(CH3)3)-N-(1-methylpropyl)aminocarbonyl or N-[C(CH3)3]-N-(2-methylpropyl)aminocarbonyl, preferably CO-N(CH3)z or CO-N(CZHS)2i - di(CI-C6-alkyl)aminocarbonyl: one of the abovementioned di(C1-C4-alkyl)aminocarbonyl radicals or, for example, N(CH3)-(n-C5H11)r N(C2H5)-(n-C5H11)r N(CH2-C2H5)-(n-C5H11)r N(n C4H9) (n C5H11)r N(n-C5H11)-(n-C5H11)r N(n-C6H13)-(n-C5H11)r N(CH3)-(n-C6H13)r N(C2H5)-(n-C6H13). N(CHz-CzHS)-(n-C6H13).
N(n-C4H9)-(n-C6H13)r N(n-C5H11)-(n-C6H13) Or N(n-C6H13)2i - di(C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl: Ci-C9-alkyl which is substituted by di(C1-C4-alkyl)aminocarbonyl as mentioned above, preferably by CO-N(CH3)2 or CO-N(C2H5)2, eg. CHZ-CO-N(CHg)2, CH2-CO-N(C2H5)Z, CH(CH3)-CO-N(CH3)Z or CH(CH3)-CO-N(CzHS)2.
preferably CHZ-CO-N(CH3)2 or CH(CH3)-CO-N(CH3)27 - di(C1-C4-alkyl)phosphonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by di(C1-C4-alkyl)phosphonyl such as -PO(OCH3)2, -PO(OCZHS)2, N,N-dipropylphosphonyl, N,N-di(1-methylethyl)phosphonyl, N,N-dibutylphosphonyl, N,N-di(1-methylpropyl)phosphonyl, N,N-di(2-methylpropyl)phosphonyl, N,N-di(l,l-dimethylethyl)phosphonyl, N-ethyl-N-methylphosphonyl, N-methyl-N-propylphosphonyl, N-methyl-N-(1-methylethyl)phosphonyl, N-butyl-N-methylphosphonyl, N-methyl-N-(1-methylpropyl)-phosphonyl, N-methyl-N-(2-methylpropyl)phosphonyl, N-(1,1-dimethylethyl)-N-methylphosphonyl, N-ethyl-N-propylphosphonyl, N-ethyl-N-(1-methylethyl)phosphonyl, N-butyl-N-ethylphosphonyl, N-ethyl-N-(1-methylpropyl)phosphonyl, N-ethyl-N-(2-methylpropyl)phosphonyl, N-ethyl-N-(1,1-dimethylethyl)phosphonyl, N-(1-methylethyl)-N-propylphosphonyl, N-butyl-N-propylphosphonyl, N-(1-methylpropyl)-N-propylphosphonyl, N-(2-methylpropyl)-N-propylphosphonyl, N-(1,1-dimethylethyl)-N-propylphosphonyl, N-butyl-N-(1-methylethyl)phosphonyl, N-(1-methylethyl)-N-(1-methylpropyl)phosphonyl, N-(1-methylethyl)-N-(2-methylpropyl)phosphonyl, N-(1,1-dimethylethyl)-N-(1-methylethyl)phosphonyl, N-butyl-N-(1-methylpropyl)phosphonyl, N-butyl-N-(2-methylpropyl)phosphonyl, N-butyl-N-(1,1-dimethylethyl)phosphonyl, N-(1-methylpropyl)-N-(2-methylpropyl)phosphonyl, N-(1,1-dimethylethyl)-N-(1-methylpropyl)phosphonyl or N-(1,1-dimethylethyl)-N-(2-methylpropyl)phosphonyl, preferably by -PO(OCH3)2 or -PO(OC2H5)2, eg. CH2-PO(OCH3)Z, CH2-PO(OC2H5)2, CH(CH3)-PO(OCH3)2 or CH(CH3)-PO(OCZHS)2:
- C3-C6-alkenyl: prop-1-en-1-yl, allyl, 1-methylethenyl, 1-buten-1-yl, 1-buten-2-yl, 1-buten-3-yl, 2-buten-1-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1-ethylprop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl, n-hex-3-en-1-yl, n-hex-4-en-1-yl, n-hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, I.3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl or 1-ethyl-2-methylprop-2-en-1-yl;
- C3-C6-haloalkenyl: C3-C6-alkenyl as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. 2-chloroallyl, 3-chloroallyl, 2,3-dichloroallyl, 3,3-dichloroallyl, 2,3,3-trichloroallyl, 2,3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2~3-dibromoallyl, 3,3-dibromoallyl, 2,3,3-tribromoallyl or 2,3-dibromobut-2-enyl;
- cyano-C3-C6-alkenyl: for example 2-cyanoallyl, 3-cyanoallyl, 4-cyanobut-2-enyl, 4-cyanobut-3-enyl or 5-cyanopent-4-enyl;
- C3-C6-alkynyl: prop-1-yn-1-yl, prop-2-yn-1-yl, n-but-1-yn-1-yl, n-but-1-yn-3-yl, n-but-1-yn-4-yl, n-but-2-yn-1-yl, n-pent-1-yn-1-yl, n-pent-1-yn-3-yl, n-pent-1-yn-4-yl, n-pent-1-yn-5-yl, n-pent-2-yn-1-yl, n-pent-2-yn-4-yl, n-pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, n-hex-1-yn-I-yl, n-hex-1-yn-3-yl, n-hex-1-yn-4-yl, n-hex-1-yn-5-yl, n-hex-1-yn-6-yl, n-hex-2-yn-1-yl, n-hex-2-yn-4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yI, n-hex-3-yn-1-yl, n-hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl and 4-methylpent-2-yn-5-yl, preferably prop-2-yn-1-yl;
- C3-C6-haloalkynyl: C3-C6-alkynyl as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. 1,1-difluoroprop-2-yn-1-yl, 4-fluorobut-2-yn-1-yI, 4-chlorobut-2-yn-1-yl, 1,1-difluorobut-2-yn-1-yl, 5-fluoropent-3-yn-1-yl or 6-fluorohex-4-yn-1-yl;
- cyano-C3-C6-alkynyl: for example 3-cyanopropargyl, 4-cyanobut-2-yn-1-yl, 5-cyanopent-3-yn-1-yl and 6-cyanohex-4-yn-1-yl;
- C3-Cq-alkenyloxy-C1-Cq-alkyl: C1-Cq-alkyl which is substituted by C3-Cq-alkenyloxy such as allyloxy, but-I-en-3-yloxy, but-1-en-4-yloxy, but-2-en-1-yloxy, 1-methylprop-2-enyloxy or 2-methylprop-2-enyloxy, ie., for example, allyloxymethyl, 2-allyloxyethyl or but-1-en-4-yloxymethyl, in particular 2-allyloxyethyl;
- C3-Cq-alkynyloxy-C1-Cq-alkyl: C1-Cq-alkyl which is substituted by C3-Cq-alkynyloxy such as propargyloxy, but-1-yn-3-yloxy, but-1-yn-4-yloxy, but-2-yn-1-yloxy, 1-methylprop-2-ynyloxy or 2-methylprop-2-ynyloxy, preferably propargyloxy, ie., for example, propargyloxymethyl or 2-propargyloxyethyl, in particuar 2-propargyloxyethyl;
- C3-Cq-alkenylthio-C1-Cq-alkyl: C1-Cq-alkyl which is substituted by C3-Cq-alkenylthio such as allylthio, but-1-en-3-ylthio, but-1-en-4-ylthio, but-2-en-1-ylthio, 1-methylprop-2-enylthio or 2-methylprop-2-enylthio, ie., for example, allylthiomethyl, 2-allylthioethyl or but-1-en-4-ylthiomethyl, in particular 2-(allylthio)ethyl;
- C3-Cq-alkynylthio-C1-Cq-alkyl: C1-Cq-alkyl which is substituted by C3-Cq-alkynylthio, such as propargylthio, but-1-yn-3-ylthio, but-1-yn-4-ylthio, but-2-yn-1-ylthio, 1-methylprop-2-ynylthio or 2-methylprop-2-ynylthio, preferably propargylthio, ie., for example, propargylthiomethyl or 2-propargylthioethyl, in particular 2-(propargylthio)ethyl;
- C3-C4-alkenylsulfinyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by C3-C4-alkenylsulfinyl, such as allylsulfinyl, but-1-en-3-ylsulfinyl, but-1-en-4-ylsulfinyl, but-2-en-1-ylsulfinyl, 1-methylprop-2-enylsulfinyl or 5 2-methylprop-2-enylsulfinyl, ie., for example, allylsulfinylmethyl, 2-allylsulfinylethyl or but-1-en-4-ylsulfinylmethyl, in particular 2-(allylsulfinyl)ethyl;
10 - C3-CQ-alkynylsulfinyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by C3-C4-alkynylsulfinyl, such as propargylsulfinyl, but-1-yn-3-ylsulfinyl, but-1-yn-4-ylsulfinyl, but-2-yn-1-ylsulfinyl, 1-methylprop-2-ynylsulfinyl or 2-methylprop-2-ynylsulfinyl, 15 preferably propargylsulfinyl, ie., for example, propargylsulfinylmethyl or 2-propargylsulfinylethyl, in particular 2-(propargylsulfinyl)ethyl;
- C3-C4-alkenylsulfonyl-C1-C4-alkyl: C1-C4-alkyl which is 20 substituted by C3-C4-alkenylsulfonyl, such as allylsulfonyl, but-1-en-3-ylsulfonyl, but-1-en-4-ylsulfonyl, but-2-en-1-ylsulfonyl, 1-methylprop-2-enylsulfonyl or 2-methylprop-2-enylsulfonyl, ie., for example, allylsulfonylmethyl, 2-allylsulfonylethyl or 25 but-1-en-4-ylsulfonylmethyl, in particular 2-(allylsulfonyl)ethyl;
- C3-C4-alkynylsulfonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by C3-C4-alkynylsulfonyl, such as propargylsulfonyl, but-1-yn-3-ylsulfonyl, but-1-yn-4-ylsulfonyl, but-2-yn-1-ylsulfonyl, 1-methylprop-2-ynylsulfonyl or 2-methylprop-2-ynylsulfonyl, preferably by propargylsulfonyl, ie., for example, propargylsulfonylmethyl or 2-propargylsulfonylethyl, in particular 2-(propargylsulfonyl)ethyl;
- C3-C6-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
- C3-CB_cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl;
- C3-CB-cycloalkyl-C1-C6-alkyl: for example cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, 2-(cyclopropyl)ethyl, 2-(cyclobutyl)ethyl, 2-(cyclopentyl)ethyl, 2-(cyclohexyl)ethyl, 2-(cycloheptyl)ethyl, 2-(cyclooctyl)ethyl, 3-(cyclopropyl)propyl, 3-(cyclobutyl)propyl, 3-(cyclopentyl)propyl, 3-(cyclohexyl)propyl, 3-(cycloheptyl)propyl, 3-(cyclooctyl)propyl, 4-(cyclopropyl)butyl, 4-(cyclobutyl)butyl, 4-(cyclopentyl)butyl, 4-(cyclohexyl)butyl, 4-(cycloheptyl)butyl, 4-(cyclooctyl)butyl, 5-(cyclopropyl)pentyl, 5-(cyclobutyl)pentyl, 5-(cyclopentyl)pentyl, 5-(cyclohexyl)pentyl, 5-(cycloheptyl)pentyl, 5-(cyclooctyl)pentyl, 6-(cyclopropyl)hexyl, 6-(cyclobutyl)hexyl, 6-(cyclopentyl)hexyl, 6-(cyclohexyl)hexyl, 6-(cycloheptyl)hexyl or 6-(cyclooctyl)hexyl;
- C3-Ce-cycloalkyloxy-C1-C4-alkyl: cyclopropyloxymethyl, 1-cyclopropyloxyethyl, 2-cyclopropyloxyethyl, 1-cyclopropyloxyprop-1-yl, 2-cyclopropyloxyprop-1-yl, 3-cyclopropyloxyprop-1-yl, 1-cyclopropyloxybut-1-yl, 2-cyclopropyloxybut-1-yl, 3-cyclopropyloxybut-1-yl, 4-cyclopropyloxybut-1-yl, 1-cyclopropyloxybut-2-yl, 2-cyclopropyloxybut-2-yl, 3-cyclopropyloxybut-2-yl, 3-cyclopropyloxybut-2-yl, 4-cyclopropyloxybut-2-yl, 1-(cyclopropyloxymethyl)eth-1-yl, 1-(cyclopropyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclopropylmethyloxy)prop-1-yl, cyclobutyloxymethyl, 1-cyclobutyloxyethyl, 2-cyclobutyloxyethyl, 1-cyclobutyloxyprop-1-yl, 2-cyclobutyloxyprop-1-yl, 3-cyclobutyloxyprop-1-yl, 1-cyclobutyloxybut-1-yl, 2-cyclobutyloxybut-1-yl, 3-cyclobutyloxybut-1-yl, 4-cyclobutyloxybut-1-yl, 1-cyclobutyloxybut-2-yl, 2-cyclobutyloxybut-2-yl, 3-cyclobutyloxybut-2-yl, 3-cyclobutyloxybut-2-yl, 4-cyclobutyloxybut-2-yl, 1-(cyclobutyloxymethyl)eth-1-yl, 1-(cyclobutyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclobutyloxymethyl)prop-1-yl, cyclopentyloxymethyl, 1-cyclopentyloxyethyl, 2-cyclopentyloxyethyl, 1-cyclopentyloxyprop-1-yl, 2-cyclopentyloxyprop-1-yl, 3-cyclopentyloxyprop-1-yl, 1-cyclopentyloxybut-1-yl, 2-cyclopentyloxybut-1-yl, 3-cyclopentyloxybut-1-yl, 4-cyclopentyloxybut-1-yl, 1-cyclopentyloxybut-2-yl, 2-cyclopentyloxybut-2-yl, 3-cyclopentyloxybut-2-yl, 3-cyclopentyloxybut-2-yl, 4-cyclopentyloxybut-2-yl, 1-(cyclopentyloxymethyl)eth-1-yl, 1-(cyclopentyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclopentyloxymethyl)prop-1-yl, cyclohexyloxymethyl, 1-cyclohexyloxyethyl, 2-cyclohexyloxyethyl, 1-cyclohexyloxyprop-1-yl, 2-cyclohexyloxyprop-1-yl, 3-cyclohexyloxyprop-1-yl, 1-cyclohexyloxybut-1-yl, 2-cyclohexyloxybut-1-yl, 3-cyclohexyloxybut-1-yl, 4-cyclohexyloxybut-1-yl, 1-cyclohexyloxybut-2-yl, 2-cyclohexyloxybut-2-yl, 3-cyclohexyloxybut-2-yl, 3-cyclohexyloxybut-2-yl, 4-cyclohexyloxybut-2-yl, 1-(cyclohexyloxymethyl)eth-1-yl, 1-(cyclohexyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclohexyloxymethyl)prop-1-yl, cycloheptyloxymethyl, 1-cycloheptyloxyethyl, 2-cycloheptyloxyethyl, 1-cycloheptyloxyprop-1-yl, 2-cycloheptyloxyprop-1-yl, 3-cycloheptyloxyprop-1-yl, 1-cycloheptyloxybut-1-yl, 2-cycloheptyloxybut-1-yl, 3-cycloheptyloxybut-1-yl, 4-cycloheptyloxybut-1-yl, 1-cycloheptyloxybut-2-yl, 2-cycloheptyloxybut-2-yl, 3-cycloheptyloxybut-2-yl, 3-cycloheptyloxybut-2-yl, 4-cycloheptyloxybut-2-yl, 1-(cycloheptyloxymethyl)eth-1-yl, 1-(cycloheptyloxymethyl)-1-(CH3)eth-1-yl, 1-(cycloheptyloxymethyl)prop-1-yl, cyclooctyloxymethyl, 1-cyclooctyloxyethyl, 2-cyclooctyloxyethyl, 1-cyclooctyloxyprop-1-yl, 2-cyclooctyloxyprop-1-yl, 3-cyclooctyloxyprop-1-yl, 1-cyclooctyloxybut-1-yl, 2-cyclooctyloxybut-1-yl, 3-cyclooctyloxybut-1-yl, 4-cyclooctyloxybut-1-yl, 1-cyclooctyloxybut-2-yl, 2-cyclooctyloxybut-2-yl, 3-cyclooctyloxybut-2-yl, 3-cyclooctyloxybut-2-yl, 4-cyclooctyloxybut-2-yl, 1-(cyclooctyloxymethyl)eth-1-yl, 1-(cyclooctyloxymethyl)-1-(CH3)eth-1-yl or 1-(cyclooctyloxymethyl)prop-1-yl, in particular C3-C6-cycloalkoxymethyl or 2-(C3-C6-cycloalkoxy)ethyl.
3- to 7-membered heterocyclyl is to be understood as meaning not only saturated, partially or fully unsaturated, but also aromatic, heterocycles having one to three hetero atoms selected from a group consisting of - one to three nitrogen atoms, - one to two oxygen and _ one or two sulfur atoms.
Examples of saturated heterocycles which can contain a carbonyl or thiocarbonyl ring member are:
oxiranyl, thiiranyl, aziridin-1-yl, aziridin-2-yl, diaziridin-1-yl, diaziridin-3-yl, oxetan-2-yl, oxetan-3-yl, thietan-2-yl, thietan-3-yl, azetidin-1-yl, azetidin-2-yl, azetidin-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, 1,3-dioxolan-2-yl, 1,3-dioxolan-4-yl, 1,3-oxathiolan-2-yl, 1,3-oxathiolan-4-yl, 1,3-oxathiolan-5-yl, 1,3-oxazolidin-2-yl, 1,3-oxazolidin-3-yl, 1,3-oxazolidin-4-yl, 1,3-oxazolidin-5-yl, 1,2-oxazolidin-2-yl, 1,2-oxazolidin-3-yl, 1,2-oxazolidin-4-yl, 1,2-oxazolidin-5-yl, 1,3-dithiolan-2-yl, 1,3-dithiolan-4-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-5-yl, tetrahydropyrazol-1-yl, tetrahydropyrazol-3-yl, tetrahydropyrazol-4-yl, tetrahydropyran-2-yl, tetrahydrogyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydropyran-4-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, 1,3-oxathian-2-yl, 1,3-oxathian-4-yl, 1,3-oxathian-5-yl, 1,3-oxathian-6-yl, 1,4-oxathian-2-yl, 1,4-oxathian-3-yl, morpholin-2-yl, morpholin-3-yl, morpholin-4-yl, hexahydropyridazin-1-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-1-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, piperazin-1-yl, piperazin-2-yl, piperazin-3-yl, hexahydro-1,3,5-triazin-1-yl, hexahydro-1,3,5-triazin-2-yl, oxepan-2-yl, oxepan-3-yl, oxepan-4-yl, thiepan-2-yl, thiepan-3-yl, thiepan-4-yl, 1,3-dioxepan-2-yl, 1,3-dioxepan-4-yl, 1,3-dioxepan-5-yl, 1,3-dioxepan-6-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,4-dioxepan-2-yl, 1,4-dioxepan-7-yl, hexahydroazepin-1-yl, hexahydroazepin-2-yl, hexahydroazepin-3-yl, hexahydroazepin-4-yl, hexahydro-1,3-diazepin-1-yl, hexahydro-1,3-diazepin-2-yl, hexahydro-1,3-diazepin-4-yl, hexahydro-1,4-diazepin-1-yl and hexahydro-1,4-diazepin-2-yl.
Examples of unsaturated heterocycles which can contain a carbonyl or thiocarbonyl ring member are:
dihydrofuran-2-yl, 1,2-oxazolin-3-yl, 1,2-oxazolin-5-yl, 1,3-oxazolin-2-yl;
Preferred amongst the heteroaromatic rings are the 5- and 6-membered rings, eg.
furyl such as 2-furyl and 3-furyl, thienyl such as 2-thienyl and 3-thienyl, pyrrolyl such as 2-pyrrolyl and 3-pyrrolyl, isoxazolyl such as 3-isoxazolyl, 4-isoxazolyl and 5-isoxazolyl, isothiazolyl such as 3-isothiazolyl, 4-isothiazolyl and 5-isothiazolyl, pyrazolyl such as 3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl such as 2-vxazolyl, 4-oxazolyl and 5-oxazolyl, thiazolyl such as 2-thiazolyl, 4-thiazolyl and 5-thiazolyl, imidazolyl such as 2-imidazolyl and 4-imidazolyl, oxadiazolyl such as 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl and 1,3,4-oxadiazol-2-yl, thiadiazolyl such as 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl and 1,3,4-thiadiazol-2-yl, triazolyl such as 1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl and 1,2,4-triazol-4-yl, pyridinyl such as 2-pyridinyl, 3-pyridinyl and 4-pyridinyl, pyridazinyl such as 3-pyridazinyl and 4-pyridazinyl, pyrimidinyl such as 2-pyrimidinyl, 4-pyrimidinyl and 5-pyrimidinyl, furthermore 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl, in particular pyridyl, pyrimidyl, furanyl and thienyl.
p,ll phenyl, carbocyclic and heterocyclic rings are preferably unsubstituted.
Preferred for the use of the 3-(benzazol-4-yl)pyrimidinedione derivatives I as herbicides are those compounds I where the variables have the following meanings, in each case alone or in combination:
X is oxygen;
R1 is hydrogen, amino or C1-C6-alkyl, in particular hydrogen or C1-C4-alkyl, especially preferably hydrogen or methyl;
R2 is hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl or C1_C6-alkylsulfonyl, in particular trifluoromethyl;
R3 is hydrogen;
R4 is hydrogen, fluorine or chlorine;
R5 is cyano or halogen, in particular chlorine;
=Y- is =N-N(R6)- or =C(ZR7)-5-, in particular =N-N(R6)-;
R6 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkylsulfonyl, (C1-C6-alkyl)carbonyl, (C1-C6-alkyl)thiocarbonyl, (C1-C6-alkoxy)carbonyl or C1-C6-alkyl which can be substituted by cyano, (C1-C6-alkoxy)carbonyl, di(C1-C6-alkyl)aminocarbonyl or (C1-C6-alkyl)carbonyloxy, in particular C1-C6-alkyl, C3-C6-alkynyl, C1-C6-alkylsulfonyl or (C~-C6-alkoxy)carbonyl.
Especially preferred are also the 3-(benzazol-4-yl)pyrimidine-dione derivatives Ia f~-- I where X = oxygen, R1 = methyl, RZ = trifluoromethyl, R3 = hydrogen, R4 = fluorine, R5 = chlorine and =Y- - =C(ZR7)-N(CH3)-}
~
N
F3C ~ N ~ ~ C1 Ia, O N\ 'N-CH3 10 in particular the compounds Ia.l to Ia.272 which follow:
Table 1 No . -ZR7 15Ia . l -H _ _ Ia.2 -CH3 Ia.3 -C3H5 Ia.4 -n-C3H~
20Ia.S -CH(CH3)2 Ia.6 -n-C4H9 Ia.7 -CH2-CH(CH3)2 Ia.8 -CH(CH3)-CyHS
25Ia.9 -C(CH3)s Ia.IO -CH2-CH=CHz Ia.ll -CH2-CH=CH-CH3 Ia.l2 -CH2-CHy-CH=CH2 Ia.l3 -CH2-C=CH
30Ia.l4 -CH2-OCH3 Ia.lS -CHZ-CH2-OCH3 Ia.l6 -CH2-CN
Ia.l7 -CHy-CH2F
35Ia.l8 -CH2-CF3 Ia.l9 -CHZ-CH2C1 Ia.20 -CH2-CO-OCH3 Ia.21 -CH2-CO-OC2H5 40Ia.22 -CH2-CO-N(CH3)3 Ia.23 -cyclobutyl Ia.24 -cyclopentyl Ia.25 -cyclohexyl Ia.26 -phenyl Ia.27 -CHZ-cyclobutyl Ia.28 -CH2-cyclopentyl No . -ZR7 Ia.29 -CH2-cyclohexyl Ia.30 -CHz-phenyl Ia.31 -N02 Ia.32 -CN
Ia.33 -F
Ia.34 -C1 Ia.35 -Br Ia.36 -OCH3 Ia.37 -OC2H5 Ia.38 -O(n-C3H7) Ia.39 -OCH(CH3)2 Ia.40 -0(n-C4H9) Ia.41 -OCH2-CH(CH3)2 Ia.42 -OCH(CH3)-C2H5 Ia.43 -OC(CH3)a Ia.44 -OCH2-CH=CH2 Ia.45 -OCHZ-CH=CH-CH3 Ia.46 -OCH2-CHZ-CH=CHZ
Ia.47 -OCH(CH3)-CH=CHZ
Ia.48 -OCH2-C=CH
Ia.49 -OCH(CH3)-C = CH
Ia.50 -OCHZ-OCH3 Ia.51 -OCH2-CH2-OCH3 Ia.52 -OCH2-CN
Ia.53 -OCH2-CHZF
Ia.54 -OCH2-CF3 Ia.55 -OCH2-CO-OCH3 Ia.56 -OCHZ-CO-OCZHS
Ia.57 -OCHz-CO-N(CH3)2 Ia.58 -O-cyclobutyl Ia.59 -O-cyclopentyl Ia.60 -O-cyclohexyl Ia.61 -0-phenyl Ia.62 -OCH2-cyclobutyl Ia.63 -OCH2-cyclopentyl Ia.64 -OCHZ-cyclohexyl Ia.65 -OCHZ-phenyl Ia.66 -CHZ-OH
Ia.67 -CH2-OCH3 No. -ZR~
Ia.68 -NHz Ia.69 -NH-CH3 Ia.70 -N(CH3)z Ia.71-.. -NH-C2H5 Ia.72 -N(C3H5)2 Ia.73 -NH-(n-C3H7) Ia.74 -N(n-C3H~)2 Ia.75 -NH-(n-C4H9) Ia.76 -N(n-CqH9)z Ia.77 -NH-CH(CH3)z Ia.78 -N[CH(CH3)212 15Ia,7g -NH-CH2-CH(CH3)z Ia.80 -N(CHZ-CH(CH3)z)2 Ia.81 -NH-CHz-CH=CHz Ia.82 -N(CHz-CH=CHz)2 20Ia.83 -NH-CHz-C = CH
Ia.84 -N(CHz-C=CH)z Ia.85 -CHZ-N(CH3)2 Ia.86 -SH
25Ia.87 -SCH3 Ia.88 -SCZHS
Ia.89 -S-(n-C3H7) Ia.90 -S-(n-CqH9) Ia.91 -SCH(CH3)z 30Ia.92 -SCHZ-CH(CH3)z Ia.93 -SCH(CH3)-C2H5 Ia.94 -SC(CH3)3 Ia.95 -SCHZ-CH=CHz 35Ia.96 -SCHz-CH=CH-CH3 Ia.97 -SCHZ-CHz-CH=CHz Ia.98 -SCH(CH3)-CH=CHz Ia.99 -SCHz-C=CH
40Ia.100 -SCH(CH3)-C = CH
Ia.101 -SCHz-OCH3 Ia.102 -SCHZ-CHz-OCH3 Ia.103 -SCHz-CN
Ia.104 -SCHZ-CH2F
Ia.105 -SCHZ-CF3 Ia.106 -SCHZ-CH2C1 No . -ZR~
Ia.107 -SCH2-CO-OCH3 Ia.108 -SCH2-CO-OC2H5 Ia.109 -SCHZ-CO-N(CH3)2 Ia.110 -S-cyclobutyl Ia.lll -S-cyclopentyl Ia.112 -S-cyclohexyl Ia.113 -S-phenyl Ia.114 -SCH2-cyclobutyl Ia.115 -SCH2-cyclopentyl Ia.116 -SCH2-cyclohexyl Ia.117 -SCH2-phenyl Ia.118 -CH2-SCH3 Ia.119 -SO-CH3 Ia.120 -SO-CyHs Ia.121 -SO-(n-C3H7) Ia.122 -SO-(n-CqH9) Ia.123 -SO-CH(CH3)2 Ia.124 -SO-CH2-CH(CH3)2 Ia.125 -SO-CH(CH3)-CZH5 Ia.126 -SO-C(CH3)3 Ia.127 -SO-CHZ-CH=CHz Ia.128 -SO-CHy-CH=CH-CH3 Ia.129 -SO-CH2-CH2-CH=CH2 Ia.130 -SO-CH(CH3)-CH=CH2 Ia.131 -SO-CH2-C=CH
Ia.132 -SO-CH(CH3)-C=CH
Ia.133 -SO-CHz-OCH3 Ia.134 -SO-CHy-CH2-OCH3 Ia.135 -SO-CH2-CN
Ia.136 -SO-CHy-CH2F
Ia.137 -SO-CH2-CF3 Ia.138 -SO-CHZ-CH2C1 Ia.139 -SO-CH2-CO-OCH3 Ia.140 -SO-CH2-CO-OC2H5 Ia.141 -SO-CHz-CO-N(CH3)2 Ia.142 -SO-cyclobutyl Ia.143 -SO-cyclopentyl Ia.144 -SO-cyclohexyl Ia.145 -SO-phenyl.
No . -ZR~
Ia.146 -SO-CHZ-cyclobutyl Ia.147 -SO-CHZ-cyclopentyl Ia.148 -SO-CH2-cyclohexyl Ia.149 -SO-CH2-phenyl Ia.150 -CHZ-SO-CH3 Ia.151 -SOz-CH3 Ia.152 -SOZ-C2H5 Ia.153 -SOZ-(n-C3H7) Ia.154 -SOZ-(n-C4H9) Ia.155 -S02-CH(CH3)2 Ia.156 -SOZ-CHZ-CH(CH3)2 Ia,157 -SOz-CH(CH3)-C2H5 Ia.158 -SOz-C(CH3)3 Ia.159 -S02-CHZ-CH=CHZ
Ia.160 -SOy-CHZ-CH=CH-CH3 Ia.161 -S02-CH2-CH2-CH=CHZ
Ia.162 -SOZ-CH(CH3)-CH=CHZ
Ia.163 -SOZ-CHZ-C=CH
Ia.164 -SOZ-CH(CH3)-C=CH
Ia.165 -SOZ-CHZ-OCH3 Ia.166 -SOz-CHZ-CHy-OCH3 Ia.167 -S02-CH2-CN
Ia.168 -SOZ-CH2-CHZF
Ia.169 -S02-CHZ-CF3 Ia.170 -S02-CHz-CHZCl Ia.171 -S02-CHy-CO-OCH3 Ia.172 -S02-CHZ-CO-OC2H5 Ia.173 -SOZ-CHZ-CO-N(CH3)2 Ia.174 -SOz-cyclobutyl Ia.175 -SOy-cyclopentyl Ia.176 -SOz-cyclohexyl Ia.177 -S02-phenyl Ia.178 -SOz-CH2-cyclobutyl Ia.179 -SOZ-CHZ-cyclopentyl Ia.180 -S02-CH2-cyclohexyl Ia.181 -S02-CHZ-phenyl Ia.182 -CH2-S02-CH3 Ia.183 -CHZ-CH(C1)-CO-OH
Ia.184 -CH2-CH(C1)-CO-OCH3 No. -ZR7 Ia.185 -CH2-CH(Cl)-CO-OC2H5 Ia.186 -CH2-CH(Cl)-CO-0(n-C3H7) 5 Ia.187 -CH2-CH(C1)-CO-0(n-C4Hg) Ia.188 -CH2-CH(C1)-CO-OCH(CH3)2 Ia.189 -CH2-CH(Cl)-CO-OCH2-CH(CH3)2 Ia.190 -CH2-CH(Cl)-CO-OCH(CH3)-C2H5 Ia.191 -CH2-CH(C1)-CO-OC(CH3)3 Ia.192 -CH2-CH(Hr)-CO-OH
Ia.193 -CH2-CH(Br)-CO-OCH3 Ia.194 -CH2-CH(Br)-CO-OC2H5 Ia.195 -CH2-CH(Br)-CO-O(n-C3H7) 15 Ia,196 -CH2-CH(Br)-CO-O(n-CQHg) Ia.197 -CH2-CH(Br)-CO-OCH(CH3)2 Ia.198 -CH2-CH(Br)-CO-OCH2-CH(CH3)2 Ia.199 -CH2-CH(Br)-CO-OCH(CH3)-C2H5 20 Ia.200 -CH2-CH(Br)-CO-OC(CH3)3 Ia.201 -CH=CH-CO-OH
Ia.202 -CH=CH-CO-OCH3 Ia.203 -CH=CH-CO-OC2H5 25 Ia.204 -CH=CH-CO-0(n-C3H7) Ia.205 -CH=CH-CO-0(n-C4Hg) Ia.206 -CH=CH-CO-OCH(CH3)2 Ia.207 -CH=CH-CO-OCH2-CH(CH3)2 Ia.208 -CH=GH-CO-OCH(CH3)-C2H5 30 Ia.209 -CH=CH-CO-OC(CH3)3 Ia.210 -CH=C(Cl)-CO-OH
Ia.211 -CH=C(C1)-CO-OCH3 Ia.212 -CH=C(C1)-CO-OC2H5 35 Ia.213 -CH=C(C1)-CO-0(n-C3H7) Ia.214 -CH=C(C1)-CO-0(n-C4Hg) Ia.215 -CH=C(C1)-CO-OCH(CH3)2 Ia.216 -CH=C(C1)-CO-OCH2-CH(CH3)2 Ia.217 -CH=C(C1)-CO-OCH(CH3)-C2H5 Ia.218 -CH=C(C1)-CO-OC(CH3)3 Ia.219 -CH=C(Br)-CO-OH
Ia.220 -CH=C(Br)-CO-OCH3 Ia.221 -CH=C(Br)-CO-OC2H5 Ia.222 -CH=C(Br)-CO-O(n-C3H7) Ia.223 -CH=C(Br)-CO-O(n-C4Hg) No . -2R7 Ia.224 -CH=C(Br)-CO-OCH(CH3)z Ia.225 -CH=C(Br}-CO-OCHZ-CH(CH3}z Ia.226 -CH=C(Br)-CO-OCH(CH3)-C2Hs Ia.227 -CH=C(Br}-CO-OC(CH3)3 Ia.228 -CHz-CH(C1)-CO-NHz Ia.229 -CHZ-CH(C1)-CO-NH-CH3 Ia.230 -CHZ-CH(C1)-CO-N(CH3)z Ia.231 -CHz-CH(C1)-CO-NH-CyHs Ia.232 -CHz-CH(C1)-CO-N(C2HS)z Ia.233 -CHz-CH(C1)-CO-NH-(n-C3H~) Ia.234 -CHz-CH(C1)-CO-N(n-C3H7)z Ia,235 -CHz-CH(C1)-CO-NH-(n-C4Hg) Ia.236 -CHz-CH(C1)-CO-N(n-C4Hg)z Ia.237 -CHz-CH(Br)-CO-NHz Ia.238 -CHz-CH(Br)-CO-NH-CH3 Ia.239 -CHZ-CH(Br)-CO-N(CH3)z Ia.240 -CHz-CH(Br)-CO-NH-C2Hs Ia.241 -CHz-CH(Br)-CO-N(C2H5)z Ia.242 -CHz-CH(Br)-CO-NH-(n-C3H7) Ia.243 ~CH2-CH(Br)-CO-N(n-C3H7)z Ia.244 -CHz-CH(Br)-CO-NH-(n-C4Hg) Ia.245 -CHz-CH(Br)-CO-N(n-C4Hg)z Ia.246 -CH=CH-CO-NHz Ia.247 -CH=CH-CO-NH-CH3 Ia.248 -CH=CH-CO-N(CH3)2 Ia.249 -CH=CH-CO-NH-C2Hs Ia.250 -CH=CH-CO-N(CzHs)z Ia.251 -CH=CH-CO-NH-(n-C3H7) Ia.252 -CH=CH-CO-N(n-C3H7)z Ia.253 -CH=CH-CO-NH-(n-C4Hg) Ia.254 -CH=CH-CO-N(n-C4Hg)z Ia.255 -CH=C(C1)-CO-NHz Ia256 -CH=C(C1)-CO-NH-CH3 Ia.257 -CH=C(C1)-CO-N(CH3)2 Ia.258 -CH=C(C1)-CO-NH-CZHs Ia.259 -CH=C(C1)-CO-N(CZHs)2 Ia.260 -CH=C(C1)-CO-NH-(n-C3H7) Ia.261 -CH=C(C1)-CO-N(n-C3H7)z Ia.262 -CH=C(Cl)-CO-NH-(n-C4H9}
No~. -ZR7 Ia.263 -CH=C(C1)-CO-N(n-C4Hg)Z
Ia.264 -CH=C(Br)-CO-NH2 Ia.265 -CH=C(Br)-CO-NH-CH3 Ia.266 -CH=C(Br)-CO-NH(CH3)2 Ia.267 -CH=C(Br)-CO-NH-C2H5 Ia.268 -CH=C(Br)-CO-N(C2H5)2 Ia.269 -CH=C(Br)-CO-NH-(n-C3H7) Ia.270 -CH=C(Br)-CO-N(n-C3H~)Z
Ia.271 -CH=C(Br)-CO-NH-(n-C4Hg) Ia.272 -CH=C(Br)-CO-N(n-CqH9)2 Furthermore, especially preferred 3-(benzazol-4-yl)-pyrimidinedione derivatives are those of the formulae Ib to Ih, in particular - the compounds Ib.l - Ib.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that R4 is hydrogen:
N
F3C ~ N ~ ~ C1 Ib O N~N-CH3 ~ZR~
- the compounds Ic.l - Ic.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that R1 is hydrogen:
H O F
N
F3C ~ N- ~ ~ C1 Ic O N ~ N- CH3 - the compounds Id.l - Id.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that R1 and R4 are hydrogen:
N
FgC ~ N- ~ ~ C1 Id 'O N~ N-CH3 _ the compounds Ie.l - Ie.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that Y
is =C(ZR7)-N(S02CH3)-.
N-F3C ~ N C1 Ie 0 N~N-S02-CH3 ~ZR7 - the compounds If.l - If.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that R4 is hydrogen and Y is =C(ZR7)-N(SOZCH3)-.
N
F3C ~ N- ~ ~ C1 If O N\ 'N-SOZ-CH3 - the compounds Ig.l - Ig.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that R1 is hydrogen and Y is =C(ZR7)-N(SOZCH3)-.
H O F
N-~ - / \
F3C ~ N C1 Ig 'O N~ N-~-S02-CH3 - the compounds Ih.l - Ih.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that R1 and RQ are hydrogen and Y is =C(ZR7)-N(S02CH3)-.
H O
\
N
F3C ~ N ~ ~ C1 Ih - the compounds Ii.l - Ii.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that =Y- is =C(ZR7)-O-:
N
F3C ~ N ~ ~ C1 Ii O N\ 'O
- the compounds Ik.l - Ik.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that =Y- is =C(ZR7)-O- and R4 is hydrogen:
\
N
F3C ~ N- ~ ~ C1 Ik 'O N ~ O
ZR~
- the compounds Im.l - Im.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that Y
is =C(ZR7)-O- and R1 is hydrogen:
H O F
N
F3C ~ N ~ ~ C1 Im 5 '0 N ~ O
10 _ the compounds In.l - In.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that Y
is =C(ZR~)-0- and R1 and R4 are hydrogen:
15 N--~ - /
F3C ~ N C1 In O N\ '0 20 IZR~
The 3-(benzazol-4-yl)pyrimidinedione derivatives of the formula I
can be obtained in various ways, for example by one of the 25 following processes:
Process A~:
Reaction of a 3-(benzazol-4-yl)pyrimidinedione derivative I where R1 is hydrogen with a compound II in a manner known per se:
\N~ L1-alkyl or \N-3 5 R2 \ N / \ RS + R2 N ~ ~ R5 L1-haloalkyl I (Rl = H) II I (Rl ~ H, NHZ) L1 is a customary leaving group such as halogen, preferably chlorine, bromine or iodine, (halo)alkylsulfonyloxy, preferably methylsulfonyloxy or trifluoromethylsulfonyloxy, arylsulfonyloxy, preferably toluenesulfonyloxy, and alkoxysulfonyloxy, preferably methoxysulfonyloxy or ethoxysulfonyloxy.
The process is normally carried out in an inert organic solvent, for example in a protic solvent such as the lower alcohols, preferably in methanol or ethanol, if desired as a mixture with water, or in an aprotic solvent, for example in an aliphatic or cyclic ether such as methyl tert-butyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aliphatic ketone such as acetone, diethyl ketone and ethyl methyl ketone, in an amide such as dimethylformamide and N-methylpyrrolidone, in a sulfoxide such as dimethyl sulfoxide, in a urea such as tetramethylurea and 1,3-dimethyltetrahydro-2(1H)-pyrimidinone, in a carboxylic acid ester such as ethyl acetate, or in a halogenated aliphatic or aromatic hydrocarbon such as dichloromethane, dichloroethane, chlorobenzene and the dichlorobenzenes.
If desired, the process can be carried out in the presence of a base, suitable bases being inorganic bases, eg, carbonates such as sodium carbonate and potassium carbonate, hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate or alkali metal hydrides such as sodium hydride and potassium hydride, and also organic bases, eg.
amines such as triethylamine, pyridine and N,N-diethylaniline, or alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide.
The amount of base and alkylating agent II is preferably in each case 0.5 times to twice the molar amount, based on the amount of starting compound I (where R1 = hydrogen).
In general, the reaction temperature is from 0°C to the boiling point of the reaction mixture, in particular from 0 to 60~C.
A preferred process variant consists in alkylating the salt of I, which has been obtained by cyclizing IV where R1 = H or V where R1 = H in accordance with process D) without isolating it from the reaction mixture, which may still contain excess base, eg. sodium hydride, sodium alkoxide or sodium carbonate.
Unless the salts of those compounds I where R1 is hydrogen cannot be prepared directly by the cyclization under basic conditions, which has been described as method D), they can also be obtained in a manner known per se from the process products of methods C) to F). To this end, for example, the aqueous solution of an inorganic or organic base is treated with the 3-(benzazol-4-yl)pyrimidinedione derivative I where Ri is hydrogen. Here, salt formation is normally sufficiently rapid at as little as 20 to 25~C.
It is especially advantageous to prepare the sodium salt by dissolving the 3-(benzazol-4-yl)pyrimidinedione derivative I
where Ri = hydrogen in an aqueous sodium hydroxide solution at 20 to 25~C, approximately equivalent amounts of 3-(benzazol-4-yl)pyrimidinedione derivative I (Where Ri = H) and sodium hydroxide being employed. The corresponding salt of the 3-(benzazol-4-yl)pyrimidinedione derivative I can then be isolated for example by precipitation with a suitable inert solvent or by evaporating the solvent.
Salts of the 3-(benzazol-4-yl)pyrimidinedione derivatives I
whose metal ion is other than an alkali metal ion can usually be prepared by double decomposition of the corresponding alkali metal salt in aqueous solution, and ammonium, Phosphonium, sulfonium and sulfoxonium salts by means of ammonia or phosphonium, sulfonium or sulfoxonium hydroxides.
Process B~
Reaction of a 3-(benzazol-4-yl)pyrimidinedione derivative of the formula I where Ri is hydrogen with an electrophilic aminating reagent in the presence of a base:
\ O R4 H2 \ O R9 R2 N~ / \ R5 aminating reagent 2 N ' / \ R5 N ~ R N
\ base \
I ~Ri = H} I ~R1 = NH2}
An aminating reagent which has proved itself especially to date is 2,4-dinitrophenoxyamine, but it is also possible to use, for example, hydroxylamine-O-sulfonic acid (HOSA), which is already known from the literature as an aminating reagent (cf., for example, E. Hofer et al., Synthesis 1983, 466; W.
Friedrichsen et al., Heterocycles 20 (1983) 1271; H. Hart et al., Tetrahedron Lett. 25 (1984) 2073; B. Vercek et al., Monatsh. Chem. ~4 (1983) 789; G. Sosnousky et al., Z.
Naturforsch. 38 (1983) 884; R.S. Atkinson et al., J. Chem.
Soc. Perkin Trans. 1987, 2787).
The amination can be carried out in a manner known per se (see, for example, T. Sheradsky, Tetrahedron Lett. 1968, 1909; M.P. Wentland et al., J. Med. Chem. 27 (1984) 1103 and in particular EP-A 240 194, EP-A 476 697 and EP-A 517 181, which teach the amination of uracils).
The reaction is normally carried out in a polar solvent, for example in dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or in ethyl acetate, which has proved to be especially suitable to date.
Suitable bases are, for example, alkali metal carbonates such as potassium carbonate, alkali metal alkoxides such as sodium methoxide and potassium tert-butoxide or alkali metal hydrides such as sodium hydride.
The amount of base and aminating agent is preferably in each case 0.5 times to twice the molar amount, based on the amount of starting compound.
Process C~
Sulfurization of a 3-(benzazol-4-yl)pyrimidinedione derivative of the formula I where X is oxygen:
Ri O R4 R1 0 R4 \N~ ~ \ 5 sulfurization 2 \N--~
R \ N R R \ N RS
\\ _ \\ N - Y
I (X = O) I (X = S) As a rule, sulfurization is effected in an inert solvent or diluent, for example in an aromatic hydrocarbon such as toluene and the xylenes, in an ether such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran, or in an organic amine such as pyridine.
Especially suitable sulfurization reagents are phosphorus(V) sulfide and 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-dithione ("Lawesson reagent").
Normally, once to five times the molar amount, based on the starting compound to be sulfurized, will suffice for an essentially complete reaction.
The reaction temperature is normally from 20 to 200~C, preferably 40~C to the boiling point of the reaction mixture.
Process D~
CYclization of an arylurea of the formula III or of an arylanilide of the formula IV in the presence of a base:
\ 0 R4 \ O
z N p' NH ~ ~ 5 2 N ' OLz R ~ / R or R ~ / O R4 R3 OLz N Y R3 NH ~ ~ RS
base N - Y
III IV
Ri 0 R4 \
N
Rz ~ ~ ~ 5 N R
R3 '~ N - Y
I (X = O) Lz is lower alkyl, preferably Ci-C4-alkyl, or phenyl.
As a rule cyclization is effected in an inert organic solvent or diluent which is aprotic, for example in an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aromatic such as benzene or toluene, or in a Polar solvent such as dimethylformamide or dimethyl sulfoxide. Mixtures of polar solvent and a hydrocarbon such as n-hexane are also suitable. Depending on the starting compound, water may also be suitable as diluent.
Suitable bases are, preferably, alkali metal alkoxides, in particular the sodium alkoxides, alkali metal hydroxides, in particular sodium hydroxide and potassium hydroxide, alkali ~
metal carbonates, in particular sodium carbonate and potassium carbonate, and metal hydrides, in particular sodium hydride. When using sodium hydride as the base, it has proved advantageous to carry out the process in an aliphatic or 5 cyclic ether, in dimethylformamide or in dimethyl sulfoxide.
Normally, 0.5 times to twice the molar amount of base, based on the amount of IV or V, will suffice for successfully carrying out the reaction.
In general, the reaction temperature is from (-78)~C to the boiling point of the reaction mixture in question, in particular (-60) to 60~C.
If Ri in formula III or IV is hydrogen, the process product is obtained as a metal salt, the metal corresponding to the cation of the base used. The salt can be isolated and purified in a manner known per se or, if desired, converted by means of acid to give the free compound I where Ri =
hydrogen.
Process E~
Treatment of a substituted 2-aminoaniline Va with nitrous acid R1 O R4 Ri O R4 \N~ ~ ~ "HNO2..
R ~ N R5 R2 \ N ~ ~ R5 R3 X NHy NHR6 R3 X N\ ~
Va I {=y- _ =N-N(R6)-}
The cyclization reaction can be carried out by processes known per se (cf., for example, Houben-Weyl, Methoden der organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Vol. EBd, Ist Edition 1994, pp.
409-415).
The reaction is preferably carried out in acidic aqueous media, but lower carboxylic acids such as acetic acid are also suitable diluents. Suitable acidic aqueous solvents are, in particular, dilute mineral acids, for example 10~ strength hydrochloric acid.
~
The nitrous acid is preferably prepared in situ by adding an alkali metal nitrite - in substance or in aqueous solution -to the reaction mixture, which is composed of the diaminobenzene in acidic aqueous solution or in a carboxylic acid.
A suitable reaction temperature is, in particular, 0 to 20~C, very especially approximately 5~C.
The starting materials are expediently employed in approximately stoichiometric amounts, or the process is carried out with an excess of the theoretically expected amount of nitrous acid, which is not more than 10 mold.
The following intermediate can be cyclized in a similar manner:
R5 --~,. ~ ~ R5 H2N NHR6 N~N~N~
VI VII
Process F~
Condensation of a substituted 2-aminophenol, 2-aminothiophenol or 2-aminoaniline (V) with carbonic acid derivatives or carboxylic acid derivatives:
O R4 carbonic acid R1 O R4 N // derivative or ~N~
scarboxylic acid R ~ N R derivative R ~ N R5 X N (O/S/I ) R3 X NH2 (O/S/I )-H R3 V
I (Z = chemical bond, O, NH;
R7 = H, unsubst. or subst.
alkyl, alkenyl or aryl) The condensation reaction of the bifunctional benzenes V with the carbonic acid derivatives or carboxylic acid derivatives are carried out in a manner known per se (cf., for example, Houben-Weyl, Methoden der organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Vol. EBc, ' CA 02312703 2000-06-OS
1st Edition 1994, pp. 247-284; Vol. EBb, 1st Edition 1994, pp. 881-901; Vol. EBa, 1st Edition 1993, pp. 1032-1078).
Preferred carbonic acid derivatives or carboxylic acid derivatives are the corresponding anhydrides, acid chlorides, ortho esters, diimides, nitriles, trichloromethyl-substituted compounds, isocyanates and their thio analogs.
Suitable solvents/diluents are, in particular, organic solvents, for example aromatic hydrocarbons such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, lower alcohols such as methanol and ethanol, aliphatic or cyclic ethers such as dimethoxyethane, tetrahydrofuran and dioxane, carboxylic esters such as ethyl acetate or aprotic polar solvents such as dimethylformamide and ~dimethyl sulfoxide.
If desired, the reaction can be accelerated by adding catalytic amounts of an acid. Suitable acids are, in Particular, mineral acids such as hydrochloric acids [sic] or sulfonic acids such as p-toluenesulfonic acid. The amounts of acid are preferably 0.1 to 5 mol percent, based on the amount of V.
The reaction temperatures are preferably from 20~C to reflux temperature of the reaction mixture in question, in particular 60~C to reflux temperature.
The carbonic acid derivative or carboxylic acid derivative is employed either in an approximately stoichiometric amount or in an excess. In suitable cases, a very large excess may also be employed, or else the process can be carried out in the absence of a solvent. Approximately stoichiometric amounts or an excess of up to 10 mole equivalents, based on the amount of V, are preferred.
The substituted 2-aminophenols, -thiophenols and -anilines (V) are expediently obtained by reducing the corresponding 2-nitrophenols, -thiophenols or -anilines VIII (cf., for example Houben-Weyl, Methoden der organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Vol.
XI/1, 4th Edition 1957, p. 431 et seq.):
Rl O R4 R1 O R4 2 \N ~ / \ \N
R \ N R5 reduction RZ \ N / \ R5 R3 X NOy (O/S/I )-H R3 X NH2 (0/S/I )-H
Suitable reducing agents are, in particular, - elemental metals such as iron, tin and zinc, - hydrogen in the presence of suitable catalysts such as palladium or platinum on charcoal or Raney nickel, or - complex hydrides such as LiAlH4 and NaBH4, in the presence or absence of catalysts.
Depending on the reducing agent, suitable solvents are normally carboxylic acids such as acetic acid or propionic acid, alcohols such as methanol and ethanol, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane, aromatics such as benzene and toluene, and mixtures of these.
The reactions can be carried out at from (-100)~C to the boiling point of the reaction mixture in question.
The starting compounds are normally employed in approximately stoichiometric amounts; however, in individual cases an excess of one or the other component of up to approximately 10 mold may also be advantageous.
The 2-nitrophenols, -thiophenols and -anilines VIII, in turn, can be set free from the corresponding protected nitro compounds IX:
N N
z ~ / \ 5 elimination 2 / \ s R N R R N R
\ reagent \
R3 X N02 (0/S/N)-protection R3 X N02 (0/S/I )-H
~
Protection = customary protective group which protects the phenols, or thiophenols, as ethers or the amino group as an amide.
The protective groups can be eliminated by processes known per se (cf., for example, Greene/Wuts: Protective Groups in Organic Synthesis, John Wiley & Sons, Inc., 2nd Edition 1991, p. 145 et seq. and p. 279 et seq.).
Suitable elimination reagents are, in particular:
- for alkylphenols: trimethylsilyl iodide, boron tribromide, boron trichloride, aluminum trichloride, lithium chloride or hydrogen bromide;
- for unsubstituted or substituted benzylphenols or -thiophenols: boron trifluoride, hydrofluoric acid or hydrogen/catalyst, preferably noble metal catalysts such as palladium or platinum.
The solvent/diluent is preferably chosen in such a way that it is inert to the elimination reagent in question. When using the halides trimethylsilyl iodide, boron tribromide, boron trichloride or aluminum trichloride, halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride and dichloroethane are especially preferred.
Hydrogen bromide is preferably used in aqueous solution, very especially preferably as a 48~ strength solution; lithium chloride is preferably employed in polar solvents such as lower alcohols, dimethyl sulfoxide and dimethylformamide;
hydrogenolytic methods are preferably carried out in lower alcohols or carboxylic acids, without or with the addition of a hydrogen transfer agent such as cyclohexene and cyclohexadiene.
The temperature for the elimination reaction is preferably from O~C to the boiling point of the reaction mixture in question.
The elimination reagent is preferably employed in approximately stoichiomeric amounts or in an excess. The excess is especially preferably between one and ten mole equivalents, based on the amount of IX.
Finally, the protected nitro compounds IX can be obtained in a manner known per se by nitrating (protected) phenols, thiophenols or anilines X (cf., for example, Houben-Weyl, Methoden der organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, VoI. 10/1, 1971, p. 479 et seq.):
5 2 ~N~ ~ ~ ~N~
R ~ N R5 R2 ~ N ~ ~ 5 R
nitration R3 X (O/S/N)-protection R3 X NOZ (0/S/N)-pro-10 I tection Rs R6 X IX
15 suitable nitration reagents are, in particular, nitric acid, as a mixture with sulfuric acid or acetic anhydride, or nitronium salts, specifically nitronium tetrafluoroborate.
The mixture composed of nitric acid and sulfuric acid can be composed of any desired weight ratios of the two components;
20 Preferred are those mixtures where the sulfuric acid predominates greatly or acts as the solvent. Similarly, this is also true for the mixture of nitric acid and acetic anhydride.
Nitronium tetrafluoroborate is preferably employed in aprotic 25 Polar solvents, eg. in acetonitrile or nitromethane.
The reaction temperature is generally from (-80) to 80~C, in particular (-20)~C to 30~C.
30 When using the reagent nitric acid in the nitration reactions, the process is preferably carried out with an approximately equimolar amount or especially preferably with an excess of nitration reagent. The excess can be many times the amount of X. Nitronium tetrafluoroborate is preferably 35 employed in equimolar amounts relative to the substrate, or in a small excess of between 1.1 and 1.5 mole equivalents.
The following intermediates may also be nitrated in a similar manner:
nitration RS pzN - ~ ~ R5 N- Y
N- Y
XI XII
3-(genzazol-4-yl)pyrimidinedione derivatives of the formula I
with one or more chiral centers are normally obtained as enantiomer or diastereomer mixtures which, if desired, can be resolved to give the essentially pure isomers by the methods conventionally used for this purpose, for example by means of crystallization or chromatography on an optically active adsorbate. Pure optically active isomers can be prepared advantageously from corresponding optically active starting materials.
Those 3-(benzazol-4-yl)pyrimidinedione derivatives of the formula I where R1 is hydrogen can be converted into their salts in a manner known per se (see, in this context, what has been said for process A)).
The arylureas of the formula III are novel. They can be prepared by methods known per se, for example by one of the following processes:
' CA 02312703 2000-06-OS
Process G~
Reaction of a (3-ketocarboxylic ester XIII with a urea XIV:
O /N~ NH ~ ~ 5 R2 0 + H R
XIII XIV
R1. 0 R4 (Cat.) N
---~~. R2 ~ NH ~ ~ 5 R
III
LZ is lower alkyl, preferably C1-C4-alkyl, or phenyl.
The process is preferably carried out under essentially anhydrous conditions in an inert solvent or diluent, especially preferably in the presence of an acidic or basic catalyst.
Suitable solvents or diluents are, in particular, organic solvents which are miscible with water to give azeotropic mixtures, for example aromatics such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, aliphatic and cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or cyclohexane, but also alcohols such as methanol and ethanol.
Suitable acidic catalysts are, preferably, strong mineral acids such as sulfuric acid and hydrochloric acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid, organic acids such as p-toluenesulfonic acid, and acidic cation exchangers such as "Amberlyst 15"
(Fluka).
Examples of suitable basic catalysts are alkali metal hydrides such as sodium hydride and, especially preferably, alkali metal alkoxides such as sodium methoxide and sodium ethoxide.
XIV and the ~-ketocarboxylic ester XIII are expediently employed in approximately stoichiometric amounts, or else the process is carried out with a small excess of one or the other component, of up to approximately 10 mold.
An amount of 0.5 to 2 molg of catalyst, based on the amount of one of the starting compounds, will normally suffice.
The reaction is generally effected at from 60 to 120~C so as rapidly to eliminate water which forms, preferably at the boiling point of the reaction mixture.
Process H~
Reaction of an enol ether XV with a urea XVI:
OL3 \ N-RZ O + H NH ~ \ R5 \ OL2 N -~ Y
XV XVI
N
NH ~ \ 5 R \ ~ R
III
LZ and L3 are in each case lower alkyl, preferably C1-C4-alkyl, or phenyl.
The reaction is preferably carried out in an inert organic solvent which is miscible with water, eg. an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or a lower alcohol, in particular ethanol, the reaction temperature normally being from 50 to 100~C, preferably the boiling point of the reaction mixture.
However, the reaction can also be carried out in an aromatic diluent such as benzene, toluene and o-, m-, p-xylene, in which case the addition of either an acidic catalyst such as hydrochloric acid and p-toluenesulfonic acid or of a base, for example an alkali metal alkoxide such as sodium methoxide and sodium ethoxide, is recommended. In this process variant, again, the reaction temperature is normally from 50 to 100~C, but preferably 60 to 80~C.
As regards the ratios by weight, what has been said for method G) also applies here.
Process J~
Reaction of an et~aminoester XVII with an isocyanate XVIII:
R1 Rq R1 O R4 \ NH OLZ OCN ~ ~ R5 ~,. R2 N p _ NH ~ ~ 5 R + ~ ~ R
R3 \p N Y R3 OL2 N - Y
XVII XVIII III
L2 is lower alkyl, preferably C1-C4-alkyl, or phenyl.
The reaction is expediently carried out in the presence of an essentially anhydrous aprotic organic solvent or diluent, for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and o-, m-, p-xylene, a halogenated aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichlorethane and chlorobenzene, an aprotic polar solvent such as dimethylformamide, hexamethyl phosphoric triamide and dimethyl sulfoxide, or a mixture of these.
If desired, the process can also be carried out in the presence of a metal hydride base such as sodium hydride and potassium hydride, or an organic tertiary base such as ~
triethylamine and pyridine, it being possible for the organic base to act simultaneously as the solvent.
The starting materials are expediently employed in 5 stoichiometric amounts, or else the process is carried out with a small excess of one or the other component, of up to approximately 10 mol%. If the process is carried out in the absence of a solvent in the presence of an organic base, the latter will be present in a larger excess.
The reaction temperature is preferably from (-80) to 50~C, in particular (-60) to 30~C.
In an especially preferred embodiment, the resulting enamine ester III is converted directly (ie. "in situ") with an excess of base in accordance with process D) to give the corresponding product of value I.
Process K~
Reaction of an enaminoester XVII with a urethane XIX:
~ L40- ~
NH OL2 NH ~ ~ RS RZ N o'NH
R
R -I-(base N - Y N -- Y
XVII XIX III
L2 and L4 independently of one another are lower alkyl, preferably C1-C4-alkyl, or phenyl.
This reaction is expediently carried out in an aprotic polar solvent or diluent such as dimethylformamide, 2-butanone, dimethyl sulfoxide and acetonitrile, advantageously in the presence of a base, for example an alkali metal alkoxide or alkaline earth metal alkoxide, in particular a sodium alkoxide such as sodium methoxide, an alkali metal carbonate or alkaline earth metal carbonate, in particular sodium carbonate, or an alkali metal hydride such as lithium hydride and sodium hydride.
Once to twice the molar amount of base, based on the amount of XVII or XIX, will normally suffice.
The reaction temperature is generally from 80 to 180~C, preferably the boiling point of the reaction mixture.
As regards the weight ratio of the starting compounds, what has been said for method G) also applies here.
In an especially preferred embodiment, a sodium alkoxide is used as the base, and the alcohol which is formed in the course of the reaction is distilled off continuously. The resulting enaminoesters IV can be cyclized in accordance with process D), without being isolated from the reaction mixture, to give a salt of the substituted benzothiazoles I (where R1 = H).
The urethanes XIX, in turn, can be prepared, for example, from the carbonyl chlorides XX and anilines XXI:
O + H N ~ ~ Rs base La ~ N ~ ~ Rs XX ' XXI XIX
To avoid an excess of aniline, it is necessary, as a rule, to add an auxiliary base such as triethylamine, pyridine or the alkali metal carbonates to scavenge the hydrogen chloride which is formed during the reacton. Pyridine is especially suitable since it can be used simultaneously as the solvent.
Suitable solvents/diluents other than pyridine are, in Particular, aromatic hydrocarbons such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, lower alcohols such as methanol and ethanol, aliphatic or cyclic ethers such as dimethoxyethane, tetrahydrofuran and dioxane, carboxylic esters such as ethyl acetate or aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide.
~
The reaction temperature is generally from O~C to reflux temperature of the reaction mixture in question.
The starting materials are expediently employed either in 5 approximately stoichiometric amounts, or else an excess of carbonyl chloride of not more than 10 mol percent is chosen.
The auxiliary base is normally used in an approximately equimalar 10 ~°unt - based on the amount of XX or XXI - or in an excess of up to approx. twice the molar amount. When using pyridine as the auxiliary base, an even larger excess is recommended, in which case the process can be carried out without an additional solvent.
Process L~
Reaction of an isocyanate XXII with an aniline derivative XXI:
\
NCO
O H N ~ ~ 5 ~ Rz N~ NH ~ ~ 5 Rz~ .f. 2 R ~ ~ R
~~ OL2 N - Y N - Y
R3. R3 OL2 XXII XXI III (R1 = H) Lz is lower alkyl, preferably C1-C4-alkyl, or phenyl.
This reaction is expediently carried out in an essentially anhydrous aprotic organic solvent or diluent, for example in the presence of an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and o-, m-, p-xylene, a halogenated aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic polar solvent such as dimethylformamide, hexamethyl phosphoric triamide and dimethyl sulfoxide, or a mixture of these.
If desired, the process can be carried out in the presence of a metal hydride base such as sodium hydride and potassium hydride, an alkali metal or alkaline earth metal alkoxide such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, or of an organic nitrogen base such as ' CA 02312703 2000-06-OS
triethylamine and pyridine, it being possible for the organic base to act simultaneously as the solvent.
The starting materials are expediently employed in approximately stoichiometric amounts, or else one of the components is used in an excess, of up to approximately 20 mol%. If the process is carried out in the absence of a solvent in the presence of an organic base, the latter will advantageously be present in an even larger excess.
The reaction temperature is generally from (-80) to 150~C, preferably (-30)~C to the boiling point of the reaction mixture in question.
The arylanilides of the formula IV are also novel; they, too, can be prepared in a manner known per se, for example by reacting an amide XXIII with a urethane XXIV
in accordance with process M~:
R4 R1 O ~ 0 O
R2 ~ ~ ~ ~ ~OL2 R2 N~OLZ RQ
HN g5 XXIV
H
R3 O N - Y R3 NH ~ ~ RS
N- Y
XXIII IV (R1 = H) Lz is lower alkyl, preferably C1-C4-alkyl, or phenyl.
The reaction is advantageously carried out in an essentially anhydrous solvent/diluent under atmospheric pressure, especially preferably in the presence of an acidic catalyst.
To prepare enamine carboxylates IV where R1 = amino, it is recommended to employ compounds XXIV with protected amino group (for example as hydrazone).
Suitable solvents/diluents are, in particular, organic fluids which can be mixed with water to give an azeotropic mixture, for example aromatics such as benzene, toluene and o-, m-, p-xylene, or halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene.
Suitable catalysts are, in particular, strong mineral acids such as sulfuric acid, organic acids such as p-toluenesulfonic acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid, or acidic cation exchangers such as "Amberlyst 15" (Fluka).
In general, a reaction temperature from approximately 70 to 150~C is sufficient; however, to remove the resulting water of reaction rapidly, the process is expediently carried out at the boiling point of the reaction mixture in question.
XXIII and XXIV are normally employed in approximately stoichiometric amounts; preferably, XXIV is used in a slight excess of up to approximately 20 mol%.
The amide XXIII can be prepared as follows (Process N~):
O
O
~ '~ H2N / \ R5 O \ O N - Y ---~ XXI I I ( R3 = H ) O~ CH3 XXV XXI
The reaction is preferably carried out in an anhydrous inert aprotic solvent, for example in a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, an aromatic hydrocarbon such as benzene, toluene and o-, m-, p-xylene, or an aliphatic or cyclic ether such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane.
The reaction temperature is generally from approximately 70 to 140~C, in particular from 100 to 120~C.
XXV and XXI are normally employed in approximately stoichiometric amounts, or else one of the components is used in an excess of up to approximately 10 mold.
The isocyanates XVIII can be obtained, for example, from the aniline derivatives XXI in accordance with process O~:
HzN ~ ~ R5 + "COC12" -! OCN ~ ~ R5 N- Y N- Y
The process can be carried out in an inert, essentially anhydrous solvent or diluent or in the absence of solvents, 15 the aniline derivatives XXI preferably being reacted with phosgene, a "phosgene equivalent", such as diphosgene, triphosgene and carbonyldiimidazole, or with trichloromethyl chloroformate.
20 Suitable solvents or diluents are, in particular, aprotic organic solvents, for example dimethylformamide or aromatics such as toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic or cyclic 25 ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or esters such as ethyl acetate, and mixtures of these.
The starting materials are expediently employed in 30 approximately stoichiometric amounts, or else one of the components is employed in an excess of up to approx.
200 mol%.
Depending on the aniline derivative XXI employed, it may be 35 advantageous to add a base such as triethylamine, for example in 0.5 times to twice the molar amount, based on the amount of XXI.
40 The reaction temperature is generally from (-20)~C to the reflux temperature of the solvent or reaction mixture in question.
The aniline derivatives XXI, in turn, can be obtained in a manner 45 known per se (cf., for example, Houben-Weyl, Methoden der organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Vol. XI/1, 4th Edition 1957, p. 431 et seq.) by reducing the corresponding nitro derivatives XXVI:
02N ~ ~ R5 - reduction H N ~ ~ 5 2 ~R
N -Y N- Y
XXVI XXI
As regards reducing agents, solvents, reaction temperatures and weight ratios, reference may be made to what has been said above for process F~.
The compounds XXVIII and XXI can also contain one or more chiral centers, in which case they are normally obtained as enantiomer or diastereomer mixtures. If desired, the mixtures can be resolved into the essentially pure isomers by the methods conventionally used for this purpose, for example by means of crystallization or chromatography on an optically active adsorbate. Pure optically active isomers can also be prepared, for example, from corresponding optically active starting materials.
Unless otherwise specified, all the processes described above are expediently carried out under atmospheric pressure or under the inherent pressure of the reaction mixture in question.
In general, the reactants are employed in a molar ratio of 0.95:1 to 5:1.
As a rule, the reaction mixtures are worked up by methods known per se, for example by diluting the reaction solution with water and subsequently isolating the product by means of filtration, crystallization or solvent extraction, or by removing the solvent, partitioning the residue in a mixture of water and a suitable organic solvent and working up the organic phase to give the product.
The compounds I and their agriculturally useful salts are suitable as herbicides, both in the form of isomer mixtures and in the form of the pure isomers. The herbicidal compositions which comprise I effect very good control of vegetation on non-crop areas, especially at high rates of application. In crops such as wheat, rice, maize, Soya and cotton, they act against broad-leaved weeds and grass weeds without inflicting substantial ' CA 02312703 2000-06-OS
damage to the crop plants. This effect is observed mainly at low rates of application.
Depending on the application method in question, the compounds I, or herbicidal compositions comprising them, can also be employed in a further number of crop plants for eliminating undesirable plants. Examples of suitable crops are the following:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec.
rapa, Brassica napus var. napus, Brassica napus var.
napobrassica, Brassica raps var, silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifoliurn), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
In addition, the compounds I can also be used in crops which, by means of breeding, including genetic engineering methods, have been made tolerant to the action of herbicides.
The compounds I, or the herbicidal compositions comprising them, can be used, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring.
The use forms depend on the intended purposes; in any case, they should guarantee the finest possible distribution of the active ingredients according to the invention.
Suitable inert auxiliaries are essentially: mineral oil fractions of medium to high boiling point such as kerosine and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. paraffins, ' CA 02312703 2000-06-OS
tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, eg.
amines such as N-methylpyrrolidone, and water.
Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substrates [sic], as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and these concentrates are suitable for dilution with water.
Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acid, eg, ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylarylsulfonates, of alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.
Powders, materials for spreading and dusts can be prepared by mixing or binding the active substances together with a solid carrier.
Granules, eg. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.
The concentration of the active ingredients I in the ready-to-use preparations can be varied within wide ranges. In general, the formulations comprise approximately from 0.001 to 98% by weight, preferably from 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (in accordance with NMR
spectra).
The formulation examples which follow illustrate the preparation °f such products:
I. 20 parts by weight of Compound No. 1 are dissolved in a mixture composed of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate and 5 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
II. 20 parts by weight of Compound No. 2 are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and 35 finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
III. 20 parts by weight of Active Ingredient No. 4 are dissolved in a mixture composed of 25 parts by weight of 40 cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280~C and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil.
Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
~ CA 02312703 2000-06-OS
IV. 20 parts by weight of Active Ingredient No. 6 are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-a-sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite 5 waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1~ by weight of the active ingredient.
V. 3 parts by weight of Active Ingredient No. 8 are mixed with 97 parts by weight of finely divided kaolin. This gives a dust which comprises 3~ by weight of the active ingredient.
VI. 20 parts by weight of Active Ingredient No. 12 are mixed intimately with 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. This gives a stable oily dispersion.
VII. 1 part by weight of Compound No. 14 is dissolved in a mixture composed of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. The mixture can subsequently be diluted with water to give the desired concentration of active ingredient. This gives a stable emulsion concentrate.
VIII. 1 part by weight of Compound No. 19 is dissolved in a mixture composed of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol~ EM 31 (= nonionic emulsifier based on ethoxylated castor oil; BASF AG). Then, the mixture can be diluted with water to give the desired concentration of active ingredient. This gives a stable emulsion concentrate.
The active ingredients I, or the herbicidal compositions, may be applied pre- or post-emergence. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that they come in as little contact as possible, if any, with the leaves of the sensitive crop plants while reaching the leaves of undesirable plants which grow underneath, or the bare soil surface (post-directed, lay-by).
Depending on the control target, the season, the target plants and the growth stage, the rates of application of active ingredient I are from 0.001 to 3.0, preferably 0.01 to 1.0, kg/ha active substance (a.s.).
To widen the spectrum of action and to achieve synergistic effects, the 3-(benzazol-4-yl)pyrimidinedione derivatives I may be mixed with a large number of representatives of other groups of herbicidal or growth-regulating active ingredients and applied jointly. Suitable components for mixtures are, for example, 12,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy/heteroaryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-(hetaroyl/aroyl)-1,3-cyclohexanediones, heteroaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, areas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and heteroaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.
Furthermore, it may be advantageous to apply the compounds I, alone or in combination with other herbicides, also as a mixture with other crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are employed for remedying nutritional and trace-element deficiencies. Nonphytotoxic oils and oil concentrates may also be added.
Preparation examples:
Example 1 3-[7-Chloro-5-fluoro-1-methyl-1H-benzotriazol-4-yl]-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (Comp. 2) 0.12 g of methyl iodide was added dropwise at 20~C to a mixture of 0.25 g of 3-[7-chloro-5-fluoro-1-methyl-1H-benzotriazol-4-Y1]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione, 0.12 g of potassium carbonate and 20 ml of absolute dimethylformamide. The reaction mixture was subsequently stirred for a further 18 hours, whereupon it was treated with 50 ml of water. Then, the mixture was extracted three times using in each case 20 ml of ethyl acetate. The combined organic phases were washed with water, dried over sodium sulfate and finally concentrated. The crude product was purified by chromatography on silica gel (eluent:
cyclohexane/ethyl acetate = 1:1). Yield: 0.07 g;
1H NMR (270 MHz, in CDC13): 8 [ppm] = 7.45 (d,lH), 6.45 (s,lH), 4.55 (s,3H), 3.60 (s,3H).
Example 2 3-[7-Chloro-5-fluoro-1-methyl-1H-benzotriazol-4-yl]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (Comp. 1) 0.43 g of ethyl 3-amino-4,4,4-trifluorobut-2-enoate in 3 ml of dimethylforinamide was added at O~C in the course of 15 minutes under a nitrogen atmosphere to 0.13 g of sodium methoxide in 7 ml of absolute dimethylformamide. The mixture was first stirred for one and a half hours at 10~C, whereupon a solution of 0.57 g of ethyl 7-chloro-5-fluoro-1-methyl-1H-benzotriazol-4-ylcarbamate in 20 ml of dimethylformamide was added dropwise to the reaction mixture in the course of 15 minutes. The mixture was subsequently heated to 20~C and stirring was continued for 5 minutes. The mixture was then heated to 60~C, and 0.35 g of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was added. Finally, stirring was continued for 4 hours at 120~C and for 18 hours at 20~C.
For working-up, the mixture was poured into 100 ml of a 10~ by weight aqueous potassium carbonate solution. The product of value was extracted by means of diethyl ether (twice 50 ml) and, after the aqueous phase which remained had been brought to a pH of 1 with hydrochloric acid, by means of ethyl acetate (three times 30 ml).
The combined organic phases were then washed with approx. 20 ml of saturated aqueous sodium chloride solution and 30 ml of 10% by weight aqueous lithium chloride solution, then dried over sodium sulfate and finally concentrated. Yield: 0.25 g;
1H NMR (250 MHz, in CDC13): b [ppm) = 10.25 (br,lH), 7.45 (d,lH), 6.30 (s,lH), 4.60 (s,3H).
Step 2.1 2-Chloro-4-fluoro-N-trifluoroacetylaniline 144.3 g of trifluoroacetic anhydride in 150 ml of diethyl ether were added dropwise at 0°C to 100 g of 2-chloro-4-fluoroaniline in 800 ml of absolute diethyl ether. After the mixture had been heated to 20°C, 500 ml of water were added. The organic phase was separated off and washed three times with water, then dried over sodium sulfate and finally concentrated. Yield: 151.5 g;
1H NMR (270 MHz, in CDC13): b [ppm] = 8.35 (br,lH), 8.25 (dd,lH), 7.20 (dd,lH), 7.05 (dt,lH).
Step 2.2 3-Chloro-5-fluoro-2N-trifluoroacetylaminonitrobenzene 375 ml of 98% strength nitric acid were slowly added dropwise at (-5)°C to 75 g of 2-chloro-4-fluoro-N-trifluoroacetylaniline in 753 ml of acetic anhydride. The mixture was then stirred for one hour at (-5)°C, whereupon it was heated to 20°C. The course of the reaction was monitored by means of high-pressure liquid chromatography on an RP1~-18 column (eluent: acetonitrile/water - 7:3). As soon as starting material was no longer detectable, the reaction mixture was poured into an ice-cold saturated aqueous sodium chloride solution. The solid product of value was subsequently separated off, washed with water and dried for several hours in a drying oven under reduced pressure at 20°C.
Yield: 62.3 g;
1H NMR (270 MHz, in CDC13): b [ppm] = 8.50 (br,lH), 7.80 (dd,lH), 7.60 (dd,lH).
1) reversed phase, on silica gel Step 2.3 3-Chloro-5-fluoro-2-(N-methyl-N-trifluoroacetylamino)-nitrobenzene 12.0 g of methyl iodide were added to a mixture of 16.1 g of 3-chloro-5-fluoro-2N-trifluoroacetylaminonitrobenzene, 11.6 g of potassium carbonate and 100 ml of absolute dimethylformamide. The reaction mixture was subsequently stirred for 18 hours at 20~C, whereupon 500 ml of water were added. Then, the mixture was extracted three times with 100 ml of ethyl acetate in each case.
The combined organic phases were dried over sodium sulfate and finally concentrated.
Yield: 16.3 g;
1H NMR (270 MHz, in CDC13): b [ppm] = 7.80 (m,lH), 7.60 (m,lH), 3.40 (s,3H).
Step 2.4 3-Chloro-5-fluoro-2-methylaminonitrobenzene 173 ml of a 1-normal sodium hydroxide solution were added to a solution of 16.3 g of 3-chloro-5-fluoro-2-(N-methyl-N-trifluoro-acetylamino)nitrobenzene in 173 ml of ethanol. The mixture was subsequently stirred for 1 hour, whereupon it was diluted with 500 ml of water. Then, it was extracted three times with 80 ml of ethyl acetate. The combined organic phases were washed with water, dried over sodium sulfate and finally concentrated. Yield:
10.1 g;
1H NMR (270 MHz, in CDC13): b [ppmj = 7.70 (dd,lH), 7.35 (dd,lH), 6.70-6.50 (br,lH), 3.10 (d,3H).
Step 2.5 2-Amino-6-chloro-4-fluoro-N-methylaniline 55.94 g of tin dichloride dehydrate were added to 10.1 g of 3-chloro-5-fluoro-2-methylaminonitrobenzene in 207 ml of absolute ethanol. The mixture was subsequently heated at 50~C, and 0.94 g of sodium boranate in 55 ml of absolute ethanol was added dropwise in such a way that the temperature of the mixture did not exceed 60~C. For working-up, the mixture was poured into 1 1 of ice-water, whereupon the pH was brought to 14 with sodium hydroxide solution. Then, the mixture was extracted three times with 100 ml of tert-butyl methyl ether. The combined organic phases were washed with water, dried over sodium sulfate and finally concentrated. Yield: 7.5 g;
1H NMR (270 MHz, in CDC13): b [ppm] = 6.50 (dd,lH), 6.35 (dd,lH), 3.90-3.60 (br,3H), 2.65 (s,3H).
Step 2.6 5 7-Chloro-5-~luoro-1-methylbenzotriazole A solution of 3.25 g of sodium nitrite in 19 ml of water was added at 5°C to 7.5 g of 2-amino-6-chloro-4-fluoro-N-methylaniline 10 in 117 ml of 10% strength hydrochloric acid. After the reaction mixture had been stirred for one hour at 5°C, it was diluted with 200 ml of water. Then, the solids were separated off, washed with 3x50 ml of water and dried in a vacuum drying oven at 20°C. Yield:
7.2 g;
15 1H NMR (270 MHz, in CDC13): b [ppm] = 7.60 (dd,lH), 7.30 (dd,lH), 4.55 (s,3H).
Step 2.7 20 7-Chloro-5-fluoro-1-methyl-4-nitrobenzotriazole 0.65 ml of 98% strength nitric acid were slowly added dropwise at (-20)°C to 1.5 g of 7-chloro-5-fluoro-1-methylbenzotriazole in 28 ml of concentrated sulfuric acid. Then, the mixture was 25 stirred for one hour at 0°C, whereupon it was heated to 20°C.
Stirring was subsequently continued for 18 hours, and the reaction mixture was then poured into 500 ml of ice-water. The solids were separated off, washed with water and dried in a vacuum drying oven at 20°C. Yield: 1.66 g;
30 1H NMR (270 MHz, in CDC13): b [ppm] = 7.50 (d,lH), 4.65 (s,3H).
Step 2.8 4-Amino-7-chloro-5-fluoro-1-methylbenzotriazole 1.66 g of 7-chloro-5-fluoro-1-methyl-4-nitrobenzotriazole were reduced with tin dichloride/sodium boranate by a method similar to what has been said for step 2.5. Yield: 1.27 g;
1H NMR (250 MHz, in (CD3)2S0): b [ppm] = 7.45 (d,lH), 6.25 (br,2H), 4.45 (s,3H), 4.30 (q,2H), 1.35 (t,3H).
Step 2.9 Ethyl 7-chloro-5-fluoro-1-methyl-1H-benzotriazol-4-ylcarbamate 2.28 g of ethyl chloroformate were slowly added dropwise to 13 ml of absolute pyridine at O~C, whereupon the mixture was stirred at this temperature for 15 minutes. Then, 1.27 g of 4-amino-7-chloro-5-flu4ro-1-methylbenzotriazole in 20 ml of pyridine were added dropwise at O~C. Stirring was subsequently continued, first for 30 minutes at O~C, and the mixture was then heated at 20~C and again stirred for 18 hours. Finally, the reaction mixture was poured into 100 ml of 10~ strength hydrochloric acid. Then, the mixture was extractd three times with 50 ml of tert-butyl methyl ether. The combined organic phases were washed with 100 ml of water and then concentrated.
50 ml of diethyl ether were added to the residue. The undissolved component was separated off and washed with 3x30 ml of diethyl ether. The combined ether phases were concentrated. Yield:
0.37 g;
1H NMR (250 MHz, in CDC13): 8 [ppm] = 7.35 (d,lH), 6.90 (br,lH), 4.55 (s,3H).
Example 3 3-[7-Chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl]-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (Comp. I.5) 2.46 g of 3-[7-chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H
benzimidazol-4-yl]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione were alkylated with methyl iodide by a method similar to the one described in Example 1. The crude product was purified by chromatography on silica gel (eluent: cyclohexane/ethyl acetate =
2:1). Yield: 1.4 g;
1H NMR (250 MHz, in CDC13): b [ppm] = 7.35 (d,lH), 6.40 (s,lHj, 4.30 (s,3H), 3.55 (s,3H).
Example 4 3-[7-Chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl]-1-amino-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (Comp.
6) 0.25 g of 2,4-dinitro-O-aminophenol was added to a mixture of 0.5 g of 3-[7-chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione, 2.35 g of potassium carbonate and 5 ml of ethyl acetate. After the mixture had been stirred for 18 hours at 20~C, it was diluted with 50 ml of ethyl acetate. The resulting mixture was washed with 3x30 ml of water, dried over sodium sulfate and finally concentrated. The crude product was purified by means of medium-pressure liquid chromatography (MPLC; eluent:
cyclohexane/ethyl acetate = 2:1). Yield: 0.4 g;
1H NMR (250 MHz, in CDC13): b [ppm] = 7.35 (d,lH), 6.30 (s,lH), 4.65 (s,2H), 4.25 (s,3H).
Example 5 3-[7-Chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (Comp. 4) 4.31 g of ethyl 3-amino-4,4,4-trifluorobut-2-enoate in 20 ml of dimethylformamide were added dropwise at 0 bis 5~C to 0.82 g of sodium hydride in 50 ml of absolute dimethylformamide. The mixture was then stirred for one hour at the same temperature, whereupon 7-chloro-5-fluoro-4-isocyanato-1-methyl-2-trifluoromethylbenzimidazole (from step 5.4) in 40 ml of dimethylformamide were added at (-30)~C. Stirring was subsequently continued for one hour at (-30)~C and for a further hour at 20~C.
For working-up, the reaction mixture was carefully poured into 200 ml of ice-water. Acidification with 10~ strength hydrochloric acid gave a solid which was filtered off, washed with water and dried in a vacuum drying oven at 20~C. After purification by flash chromatography (eluent: cyclohexane/ethyl acetate = 2:1), 5.08 g of product of value were obtained.
After the solids had been separated off, product of value which still remained in the filtrate (2.46 g) was isolated by extracting the filtrate three times with 200 ml of tert-butyl methyl ether, washing the combined ether phases, drying them over sodium sulfate and concentrating them.
Total yield: 7.54 g;
1H NMR (250 MHz, in CDC13): b [ppm] = 7.40 (d,lH), 6.30 (s,lH), 4.30 (s,3H).
Step 5.1 7-Chloro-5-fluoro-1-methyl-2-trifluoromethylbenzimidazole 15.5 g of 3-chloro-5-fluoro-2-(N-methyl-N-trifluoroacetyl-amino)nitrobenzene (step 2.3) were reduced with tin dichloride/sodium boranate without intermediate isolation by a method similar to what has been said for step 2.5 to give the corresponding amino compound which then underwent spontaneous cyclization, with the elimination of water, to give the product of value. Yield: 9.32 g;
1H NMR (250 MHz, in CDC13): b [ppm] = 7.45 (d,lH), 7.20 (d,lH), 4.25 (s,3H).
Step 5.2 7-Chloro-5-fluoro-1-methyl-4-nitro-2-trifluoromethylbenzimidazole 46.3 ml of 98~ strength nitric acid were slowly added dropwise at O~C to 9.65 g of 7-chloro-5-fluoro-1-methyl-2-trifluoromethyl-benzimidazole in 96.5 ml of acetic anhydride. After the mixture had been stirred for one hour at O~C, it was heated carefully to 20~C. (In the event that an exothermal reaction did commence, the temperature was kept below 25~C by means of an ice bath.) The reaction mixture was subsequently first stirred for another two hours at 20~C and then poured into ice-cold saturated aqueous sodium chloride solution. The solids formed were separated off, washed with water and dried at 20~C in a vacuum drying oven.
Yield: 8.5 g;
1H NMR (400 MHz, in CDC13): 8 [ppm] = 7.40 (d,lH), 4.35 (s,3H).
Step 5.3 4-Amino-7-chloro-5-fluoro-1-methyl-2-trifluoromethylbenzimidazole 8.71 g of 7-chloro-5-fluoro-1-methyl-4-nitro-2-trifluoromethyl-benzimidazole were reduced by means of tin dichloride/sodium boranate by a method similar to what has been said for step 2.5.
Yield: 6.3 g;
1H NMR (270 MHz, in CDC13): 8 [ppm] = 7.05 (d,lH), 4.45 (br,2H), 4.20 (s,3H).
Step 5.4 7-Chloro-5-fluoro-4-isocyanato-1-methyl-2-trifluoromethyl-benzimidazole 23.32 g of diphosgene were added to 6.3 g of 4-amino-7-chloro-5-fluoro-1-methyl-2-trifluoromethylbenzimidazole in 100 ml of absolute toluene. The mixture Was subsequently refluxed for 6 hours. After the reaction mixture had been stirred for a further 18 hours at 20~C, it was concentrated. The crude product obtained was reacted directly, without purification, to give the end product I.4.
Example 6 3-[7-Chloro-1,2-dimethyl-5-fluoro-IH-benzimidazol-4-yl]-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (Comp. 8) 0.33 g of 3-[7-chloro-1,2-dimethyl-5-fluoro-1H-benzimidazol-4-yl]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione was alkylated with methyl iodide by a method similar to what has been said for Example 1. Yield: 0.04 g;
1H NMR (250 MHz, in CDC13): 8 [ppm] = 7.10 (d,lH), 6.40 (s,lH), 4.00 (s,3H), 3.55 (s,3H), 2.55 (s,3H).
Example 7 3-[7-Chloro-1,2-dimethyl-5-fluoro-1H-benzimidazol-4-yl]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (Comp. 7) 7-Chloro-1,2-dimethyl-5-fluoro-4-isocyanatobenzimidazole, from step 7.4, was reacted with ethyl 3-amino-4,4,4-trifluorobut-2-enoate by a method similar to what has been said for Example 5.
The crude product was purified by means of medium-pressure liquid chromatography (eluent: ethyl acetate/methanol = 15:1). Yield:
0.7 g;
iH NMR (270 MHz, in CDC13): b [ppm] = 7.15 (d,lH), 6.20 (s,lH), 4.05 (s,3H), 2.55 (s,3H).
Step 7.I
7-Chloro-1,2-dimethyl-5-fluorobenzimidazole 100 ml of 10~ strength hydrochloric acid were added to 6.96 g of 2-amino-6-chloro-4-fluoro-N-methylaniline (from step 2.5) in 4.1 g of acetic anhydride. The mixture was subsequently refluxed for 4 hours. After cooling, the mixture was taken up in ice-water. It was then neutralized carefully with an aqueous sodium carbonate solution. The solid crude product which had formed was separated off, washed with water and dried in a vacuum drying oven at 20~C. Yield: 7.92 g;
1H NMR (270 MHz, in CDC13): b [ppm] = 7.25 (dd,lH), 6.95 (dd,lH), 4.00 (s,3H), 2.55 (s,3H).
Step 7.2 7-Chloro-1,2-dimethyl-5-fluoro-4-nitrobenzimidazole 5 98% strength nitric acid was added dropwise at from (-5) to not more than O~C to 7.92 g of 7-chloro-1,2-dimethyl-5-fluorobenzimidazole in 139 ml of concentrated sulfuric acid, during which process the course of the reaction was monitored by means of high-performance liquid chromatography (HPLC) on an 10 RP-18 column (eluent: acetonitrile/water = 1:1). As soon as starting material was no longer detectable, the reaction mixture was poured into ice-water, whereupon the pH was brought to 14 by means of sodium hydroxide solution. The solids were separated off, washed with water and dried at 20~C in a vacuum drying oven.
15 The two regioisomeric nitro compounds which had formed were separated by means of flash chromatography on silica gel (eluent:
.ethyl acetate; the product which eluted first was the desired regioisomer). Yield: 5.6 g;
1H NMR (400 MHz, in CDC13): 8 [ppm] = 7.05 (d,lH), 4.10 (s,3H), 20 2~65 (s,3H).
Step 7.3 4-Amino-7-chloro-1,2-dimethyl-5-fluorobenzimidazole 5.6 g of 7-chloro-1,2-dimethyl-5-fluoro-4-nitrobenzimidazole were reduced by means of tin dichloride/sodium boranate by a method similar to what has been said for step 2.5. The crude product obtained was employed directly, without purification, in step ~'4~ Yield: 4.1 g.
Step 7.4 7-Chloro-1,2-dimethyl-5-fluoro-4-isocyanatobenzimidazole 4,1 g of 4-amino-7-chloro-1,2-dimethyl-5-fluorobenzimidazole were reacted with diphosgene by a method similar to what has been said for step 5.4. The crude product obtained was reacted directly, again without purification, to give the end product I.7.
Example 8 3-[7-Chloro-2-dimethylamino-5-fluorobenzoxazol-4-yl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione (Comp. 19) 1.0 g of 3-[2-amino-4-chloro-6-fluoro-3-hydroxyphenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione and 0.5 g of dichloromethyleneimmonium chloride were mixed in 100 ml of ~
1,2-dichloroethane, whereupon the mixture was filled into a glass holder for pressurized containers and heated for 5 hours at 120°C
in a sealed pressurized container. During this process, the inherent pressure of the container climbed to approx. 5 bar. The container was subsequently cooled. The clear product solution was washed with dilute aqueous potassium carbonate solution.
The organic phase was dried over sodium sulfate and finally concentrated. The crude product was purified by flash chromatography using a short column (eluent:
cyclohexane/tert-butyl methyl ether = 8:2). Yield: 0.5 g;
1H NMR (270 MHz, in CDC13): 8 [ppm) = 6.85 (d,lH), 6.4 (s,lH), 3.6 (s,3H), 3.25 (s,6H).
Step 8.1 3-[4-Chloro-6-fluoro-3-methoxy-2-nitrophenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione Nitrating acid, composed of 20.4 ml of concentrated sulfuric acid and 25.5 ml of 98~ strength nitric acid, was slowly added dropwise with cooling to (-20)~C to 51.0 g of 3-[4-chloro-6-fluoro-3-methoxyphenylj-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione in 1 1 of concentrated sulfuric acid.
After the addition had ended, stirring was continued for 30 minutes at (-20)~C. The reaction mixture was then stirred into 1 1 of ice-water. The solids formed were separated off, washed with water and dried in a vacuum drying oven at 20~C. Yield:
57.0 g;
1H NMR (270 MHz, in CDC13): 8 [ppmj = 7.55 (d,lH), 6.35 (s,lH), 4.05 (s,3H), 3.55 (s,3H).
Step 8.2 3-[4-Chloro-6-fluoro-3-hydroxy-2-nitrophenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione 19.0 g of lithium chloride were added to 57.0 g of 3-[4-chloro-6-fluoro-3-methoxy-2-nitrophenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione in approx. 500 ml of absolute dimethylformamide. The mixture was subsequently stirred for 3 hours at 80-90~C. After cooling, 1 1 of water was added to the reaction mixture. The product of value was extracted with 3x200 ml of methyl tert-butyl ether. The ether phase was repeatedly washed with water and then dried and finally concentrated. Yield: 46.1 g;
1H NMR (250 MHz, in CDC13): 8 [ppm] = 7.65 (d,lH), 6.35 (s,lH), 3.60 (s,3H).
Step 8.3 3-[2-Amino-4-chloro-6-fluoro-3-hydroxyphenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione 34 g of iron powder were added at 65~C, a little at a time, to 46.0 g of 3-[4-chloro-6-fluoro-3-hydroxy-2-nitrophenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione in 423 ml of water and 36.8 ml of concentrated hydrochloric acid. The mixture was subsequently refluxed for 3 hours. After cooling, the mixture was shaken with 500 ml of ethyl acetate. The organic phase was freed from the remaining inorganic material by means of filtration on Celite~ (Manville Corporation). The filtrate was dried over sodium sulfate and finally concentrated. Yield: 37.5 g:
1H NMR (270 MHz, in CDC13): 8 [ppm] = 6.65 (d,lH), 6.40 (s,lH), 3.60 (s,3H).
Example 9 3-[7-Chloro-5-fluorobenzoxazol-4-yl]-1-methyl-6-trifluoromethyl-2'4-(1H,3H)-pyrimidinedione (Comp. 12) 0.5 g of trimethyl orthoformate was added to a solution of 0.5 g of 3-[2-amino-4-chloro-6-fluoro-3-hydroxyphenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione (from step 8.3) in 30 ml of absolute methanol. The mixture was then refluxed for 20 hours. Solvent and excess ortho ester were subsequently removed under reduced pressure. The residue was dissolved in ethyl acetate. The organic phase was washed with water and then dried over sodium sulfate and finally concentrated. The crude Product was purified by means of flash chromatography (eluent:
cyclohexane/tert-butyl methyl ether = 3:1). Yield: 0.26 g;
1H NMR (250 MHz, in CDC13): 8 [ppm] = 8.20 (s,lH), 7.40 (d,lH), 6.40 (s,lH), 3.60 (s,3H).
Example 10 3-[7-Chloro-5-fluoro-2-methoxybenzoxazol-4-yl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione (Comp. 14) 1.0 g of 3-[2-amino-4-chloro-6-fluoro-3-hydroxyphenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione (from step 8.3) was reacted with tetramethyl orthocarbonate by a method similar to what has been said for Example 9. Yield: 0.7 g;
1H NMR (250 MHz, in CDC13): 8 [ppm] = 7.10 (d,lH), 6.40 (s,lH), 4.20 (s,3H), 3.60 (s,3H).
In addition to the 3-(benzazol-4-yl)pyrimidinedione derivatives of the formula I which have been described above, others which were, or can be, prepared in a similar manner are listed in Table 2 which follows:
U
O d' N l0 N M M
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I i I I 1 I
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x x x x x x x x x x x x U z x U z x U z U U U U
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e-1rlrl c!rlri O rl rlO riri rl (~'~
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I I I I I r i I I I I I I I I I I x x x I
O O O O O O O O O O O O O O cn v7v7 U U U O
I I I I I I I I I I I I I I I I I N N N I
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n n n n n n n n n n n n n n n n n Ulf!7V1 n P4 ~'P4 GGP4'fx W'W' W'f~ fYP:P: RSCYOR.'C4'~.-...
N N N N N N N N N N N N N N N N N ~..,,'t.,"~,N
IIII ItII IIIIII IIII IIII flIIII IIII IIII IIIIII ll PdW W W W W W W W fs.~W W W W W U U U W W W W
M M M M M M M M M M M M M M M N M M M
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z M M M M c~"1~ ch ' CA 02312703 2000-06-OS
Use examples The herbicidal action of the 3-(benzazol-4-yl)pyrimidinedione derivatives I was demonstrated by the following greenhouse experiments:
The culture containers used were plastic flowerpots containing, as substrate, loamy sand with approx. 3.0% of humus. The seeds of the test plants were sown in separately for each species.
In the case of the pre-emergence treatment, the active ingredients which were suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with translucent plastic hoods until the plants had rooted. This cover caused uniform germination of the test plants, unless this was adversely affected by the active ingredients.
For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which were suspended or emulsified in water. The test plants for this purpose were either sown directly and grown on in the same containers, or they were raised separately as seedlings and transplanted into the test containers a few days prior to treatment. The rate of application for the post-emergence treatment was 15.6 or 7.8 g/ha a.s. (active substance).
The plants were kept at 10 - 25~C or 20 - 35~C, depending on the species. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.
Evaluation was done on a scale of from 0 to 100. 100 means no plant emergence, or complete destruction of least the aerial parts of the plant, and 0 means no damage, or normal course of growth.
The plants used in the greenhouse experiments belonged to the following species:
Scientific name English name Amaranthus redroot pigweed retroflexus Chenopodium album lambsquarters (goosefoot) Galium aparine catchweed bedstraw Solanum nigrum black nightshade veronica species speedwell species At rates of application of 15.6 and 7.8 g/ha a.s. post-emergence, Compound No. 18 had a very good herbicidal effect against the abovementioned weeds.
2-(2,2,2-trifluoroethylsulfonyl)ethyl;
- C1-C4-alkylamino-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-Cq-alkylamino such as H3C-NH-, H5C2-NH-, n-propyl-NH-, 1-methylethyl-NH-, n-butyl-NH-, 1-methylpropyl-NH-, 2-methylpropyl-NH- and 1,1-dimethylethyl-NH-, preferably H3C-NH- or H5C2-NH-, ie., for example, CHZCHZ-NH-CH3, CH2CH2-N(CH3)2, CH2CHy-NH-CyHS or CHZCH2-N(CZHS)2;
- (C1-CQ-alkylamino)carbonyl: CO-NH-CH3, CO-NH-CZHS, n-propylamino, CO-NH-CH(CH3)Z, CO-NH-CH2CHy-CZHS, CO-NH-CH(CH3)-CzHS, CO-NH-CH2-CH(CH3)z or CO-NH-C(CH3)3.
preferably CO-NH-CH3 or CO-NH-CZHS;
- (C1-C6-alkylamino)carbonyl: one of the (C1-C4-alkylamino)carbonyl radicals mentioned above or, for example, CO-NH-(n-CSH11), 1-methylbutyl-NHCO-, 2-methylbutyl-NHCO-, 3-methylbutyl-NHCO-, 2,2-dimethylpropyl-NHCO-, 1-ethylpropyl-NHCO-, CO-NH-(n-C6H13).
1,1-dimethylpropyl-NHCO-; 1,2-dimethylpropyl-NHCO-, 1-methylpentyl-NHCO-, 2-methylpentyl-NHCO-, 3-methylpentyl-NHCO-, 4-methylpentyl-NHCO-, 1,1-dimethylbutyl-NHCO-, 1,2-dimethylbutyl-NHCO-, 1,3-dimethylbutyl-NHCO-, 2,2-dimethylbutyl-NHCO-, 2,3-dimethylbutyl-NHCO-, 3,3-dimethylbutyl-NHCO-, 1-ethylbutyl-NHCO-, 2-ethylbutyl-NHCO-, 1,1,2-trimethylpropyl-NHCO-, 1,2,2-trimethylpropyl-NHCO-, 1-ethyl-1-methylpropyl-NHCO- or 1-ethyl-2-methylpropyl-NHCO-, preferably CO-NH-CH3, CO-NH-CZHS, CO-NH-CHZ-CZHS, CO-NH-CH(CH3)Z, CO-NH-(n-C4H9), CO-NH-C(CH3)3, CO-NH-(n-C5H11) or CO-NH-(n-C6H13)f - (C1-C4-alkylamino)carbonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted [lacuna] (C1-C4-alkylamino)carbonyl as mentioned above, preferably by CO-NH-CH3 or CO-NH-CZHS, as [sic] eg.
CHZ-CO-NH-CH3, CH2-CO-NH-C2H5, CH2-CO-NH-CHy-CzHS, CH2-CO-NH-CH(CH3)2, CHZ-CO-NH-CH2CHz-CzHS, CHZ-CO-NH-CH(CH3)-C2H5, CH2-CO-NH-CHZ-CH(CH3)p, CHy-CO-NH-C(CH3)3, CH(CH3)-CO-NH-CH3, CH(CH3)-CO-NH-CzHS, 2-(CO-NH-CH3)ethyl, 2-(CO-NH-CZHS)ethyl, 2-(CO-NH-CHZ-C2H5)ethyl, 2-[CH2-CO-NH-CH(CH3)2]ethyl, 2-(CO-NH-CHZCHZ-CzHS)ethyl, 2-[CO-NH-CH(CH3)-CZHS]ethyl, 2-[CO-NH-CHZ-CH(CHg)2Jethyl, 2-[CO-NH-C(CH3)3]ethyl, 2-(CO-NH-CH3)propyl, 2-(CO-NH-C2H5)propyl, 2-(CO-NH-CHZ-C2H5)propyl, 2-[CHZ-CO-NH-CH(CH3)z]propyl, 2-(CO-NH-CH2CH2-CzHS)propyl, 2-[CO-NH-CH(CH3)-C2H5]propyl, 2-[CO-NH-CHZ-CH(CH3)2]propyl, 2-[CO-NH-C(CH3)3]propyl, 3-(CO-NH-CHg)propyl, 3-(CO-NH-CZHS)propyl, 3-(CO-NH-CHZ-CZHS)propyl, 3-[CHy-CO-NH-CH(CH3)z]propyl, 3-(CO-NH-CHyCH2-C2H5)propyl, 3-[CO-NH-CH(CH3)-C2Hg]propyl, 3-[CO-NH-CH2-CH(CH3)y]propyl, 3-(CO-NH-C(CH3)3]propyl, 2~(CO-NH-CH3)butyl, 2-(CO-NH-C2H5)butyl, 2-(CO-NH-CHZ-CZHS)butyl, 2-[CH2-CO-NH-CH(CH3)2]butyl, 2-(CO-NH-CHZCH2-CyHS)butyl, 2-[CO-NH-CH(CH3)-C2H5]butyl, 2-[CO-NH-CH2-CH(CH3)2]butyl, 2-[CO-NH-C(CH3)3]butyl, 3-(CO-NH-CH3)butyl, 3-(CO-NH-C2H5)butyl, 3-(CO-NH-CH2-C2H5)butyl, 3-[CHz-CO-NH-CH(CH3)y]butyl, 3-(CO-NH-CHZCHZ-CZHS)butyl, 3-[CO-NH-CH(CH3)-CZHS]butyl, 3-[CO-NH-CHZ-CH(CH3)2]butyl, 3-[CO-NH-C(CH3)3]butyl, 4-(CO-NH-CH3)butyl, 4-(CO-NH-CZHS)butyl, 4-(CO-NH-CH2-C2H5)butyl, 4-[CH2-CO-NH-CH(CH3)2]butyl, 4-(CO-NH-CH2CH2-C2H5)butyl, 4-[CO-NH-CH(CH3)-CZHS]butyl, 4-[CO-NH-CH2-CH(CH3)2]butyl or 4-[CO-NH-C(CH3)3]butyl, preferably CHZ-CO-NH-CH3, CHZ-CO-NH-C2H5, CH(CH3)-CO-NH-CH3 or CH(CHg)-CO-NH-C2H5;
- di(C1-C4-alkyl)amino: N(CH3)Z, N(C2H5)2, N,N-dipropylamino, N,N-di(1-methylethyl)amino, N,N-dibutylamino, N,N-di(1-methylpropyl)amino, N,N-di(2-methylpropyl)amino, N.N-di(1,1-dimethylethyl)amino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-methyl-N-(1-methylethyl)amino, N-butyl-N-methylamino, N-methyl-N-(1-methylpropyl)amino, N-methyl-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-methylamino, N-ethyl-N-propylamino, N-ethyl-N-(1-methylethyl)amino, N-butyl-N-ethylamino, N-ethyl-N-(1-methylpropyl)amino, N-ethyl-N-(2-methylpropyl)amino, N-ethyl-N-(1,1-dimethylethyl)amino, N-(1-methylethyl)-N-propylamino, N-butyl-N-propylamino, N-(1-methylpropyl)-N-propylamino, N-(2-methylpropyl)-N-propylamino, N-(1,1-dimethylethyl)-N-propylamino, N-butyl-N-(1-methylethyl)amino, N-(1-methylethyl)-N-(1-methylpropyl)amino, N-(1-methylethyl)-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-(1-methylethyl)amino, N-butyl-N-(1-methylpropyl)amino, N-butyl-N-(2-methylpropyl)amino, N-butyl-N-(1,1-dimethylethyl)amino, N-(1-methylpropyl)-N-(2-methylpropyl)amino, N_(1,1-dimethylethyl)-N-(1-methylpropyl)amino or N-(1,1-dimethylethyl)-N-(2-methylpropyl)amino, preferably N(CH3)2 or N(CzHS)27 - di(C1-C4-alkyl)amino-C1-C4-alkyl: C1-C4-alkyl which is 5 substituted by di(C1-C4-alkyl)amino as mentioned above, eg.
CH2N(CH3)2, CH2N(CZHS)Z, N,N-dipropylaminomethyl, N,N-di[CH(CH3)Z]aminomethyl, N,N-dibutylaminomethyl, N,N-di-(1-methylpropyl)aminomethyl, N,N-di(2-methylpropyl)aminomethyl, N,N-di[C(CH3)3]aminomethyl, N-ethyl-N-methylaminomethyl, 10 N-methyl-N-propylaminomethyl, N-methyl-N-[CH(CH3)2]aminomethyl, N-butyl-N-methylaminomethyl, N-methyl-N-(1-methylpropyl)aminomethyl, N-methyl-N-(2-methylpropyl)aminomethyl, N-[C(CH3)3]-N-methylaminomethyl, N-ethyl-N-propylaminomethyl, 15 N-ethyl-N-[CH(CH3)2]aminomethyl, N-butyl-N-ethylaminomethyl, N-ethyl-N-(1-methylpropyl)aminomethyl, N-ethyl-N-(2-methylpropyl)aminomethyl, N-ethyl-N-[C(CH3)3]aminomethyl, N-[CH(CH3)Z]-N-propylaminomethyl, N-butyl-N-propylaminomethyl, 20 N-(1-methylpropyl)-N-propylaminomethyl, N-(2-methylpropyl)-N-propylaminomethyl, N-[C(CH3)3]-N-propylaminomethyl, N-butyl-N-(1-methylethyl)-aminomethyl, N-[CH(CH3)2]-N-(1-methylpropyl)aminomethyl, N-[CH(CH3)2]-N-(2-methylpropyl)aminomethyl, N-[C(CH3)3]-N-[CH(CH3)Z]aminomethyl, N-butyl-N-(1-methylpropyl)aminomethyl, N-butyl-N-(2-methylpropyl)aminomethyl, N-butyl-N-[C(CH3)3]-aminomethyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminomethyl, N-[C(CH3)3]-N-(1-methylpropyl)aminomethyl, N-[C(CH3)a]-N-(2-methylpropyl)aminomethyl, N,N-dimethylaminoethyl, N~N-diethylaminoethyl, N,N-di(n-propyl)aminoethyl, N,N-di[CH(CH3)2]aminoethyl, N,N-dibutylaminoethyl, N,N-di(1-methylpropyl)aminoethyl, N,N-di(2-methylpropyl)aminoethyl, N,N-di[C(CH3)3]aminoethyl, N-ethyl-N-methylaminoethyl, N-methyl-N-propylaminoethyl, N-methyl-N-[CH(CH3)Z]aminoethyl, N-butyl-N-methylaminoethyl, N-methyl-N-(1-methylpropyl)aminoethyl, N-methyl-N-(2-methylpropyl)aminoethyl, N-[C(CH3)3]-N-methylaminoethyl, N-ethyl-N-propylaminoethyl, N-ethyl-N-[CH(CH3)2]aminoethyl, N-butyl-N-ethylaminoethyl, N-ethyl-N-(1-methylpropyl)aminoethyl, N_ethyl-N-(2-methylpropyl)aminoethyl, N-ethyl-N-[C(CH3)3]aminoethyl, N-[CH(CH3)2]-N-propylaminoethyl, N-butyl-N-propylaminoethyl, N-(1-methylpropyl)-N-propylaminoethyl, N-(2-methylpropyl)-N-propylaminoethyl, N-[C(CH3)3]-N-propylaminoethyl, N-butyl-N-[CH(CH3)2]aminoethyl, N-[CH(CH3)Z]-N-(1-methylpropyl)aminoethyl, N-[CH(CH3)Z]-N-(2-methylpropyl)aminoethyl, N-[C(CH3)3]-N-[CH(CH3)z]aminoethyl, N-butyl-N-(1-methylpropyl)aminoethyl, N-butyl-N-(2-methylpropyl)aminoethyl, N-butyl-N-[C(CH3)3]aminoethyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminoethyl, N-[C(CH3)3]-N-(1-methylpropyl)aminoethyl or N-[C(CH3)3]-N-(2-methylpropyl)aminoethyl, in particular N,N-dimethylaminoethyl or N,N-diethylaminoethyl;
- di(C1-C9-alkyl)aminocarbonyl: CO-N(CH3)z, CO-N(CzHs), CO-N(CHZ-CZHS)z, CO-N[CH(CH3)zlz. N,N-dibutylaminocarbonyl, CO-N[CH(CH3)-C2H5]z, CO-N[CHz-CH(CH3)z]z, CO-N[C(CH3)3]2.
N-ethyl-N-methylaminocarbonyl, N-methyl-N-propylaminocarbonyl, N-methyl-N-[CH(CH3)2]aminocarbonyl, N-butyl-N-methylaminocarbonyl, N-methyl-N-(1-methylpropyl)aminocarbonyl, N-methyl-N-(2-methylpropyl)aminocarbonyl, N-[C(CH3)3]-N-methylaminocarbonyl, N-ethyl-N-propylaminocarbonyl, N-ethyl-N-[CH(CH3)z]aminocarbonyl, N-butyl-N-ethylaminocarbonyl, N-ethyl-N-(1-methylpropyl)aminocarbonyl, N-ethyl-N-(2-methylpropyl)aminocarbonyl, N-ethyl-N-[C(CH3)3]aminocarbonyl, N-[CH(CH3)z]-N-propylaminocarbonyl, N-butyl-N-propylaminocarbonyl, N-(1-methylpropyl)-N-propylaminocarbonyl, N-(2-methylpropyl)-N-propylaminocarbonyl, N-[C(CH3)3]-N-propylaminocarbonyl, N-butyl-N-[CH(CH3)z]aminocarbonyl, N-[CH(CH3)Z]-N-(1-methylpropyl)aminocarbonyl, N-[CH(CH3)z]-N-(2-methylpropyl)aminocarbonyl, N-[C(CH3)3]-N-[CH(CH3)z]aminocarbonyl, N-butyl-N-(1-methylpropyl)aminocarbonyl, N-butyl-N-(2-methylpropyl)aminocarbonyl, N-butyl-N-[C(CH3)3]aminocarbonyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminocarbonyl, N-[C(CH3)3)-N-(1-methylpropyl)aminocarbonyl or N-[C(CH3)3]-N-(2-methylpropyl)aminocarbonyl, preferably CO-N(CH3)z or CO-N(CZHS)2i - di(CI-C6-alkyl)aminocarbonyl: one of the abovementioned di(C1-C4-alkyl)aminocarbonyl radicals or, for example, N(CH3)-(n-C5H11)r N(C2H5)-(n-C5H11)r N(CH2-C2H5)-(n-C5H11)r N(n C4H9) (n C5H11)r N(n-C5H11)-(n-C5H11)r N(n-C6H13)-(n-C5H11)r N(CH3)-(n-C6H13)r N(C2H5)-(n-C6H13). N(CHz-CzHS)-(n-C6H13).
N(n-C4H9)-(n-C6H13)r N(n-C5H11)-(n-C6H13) Or N(n-C6H13)2i - di(C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl: Ci-C9-alkyl which is substituted by di(C1-C4-alkyl)aminocarbonyl as mentioned above, preferably by CO-N(CH3)2 or CO-N(C2H5)2, eg. CHZ-CO-N(CHg)2, CH2-CO-N(C2H5)Z, CH(CH3)-CO-N(CH3)Z or CH(CH3)-CO-N(CzHS)2.
preferably CHZ-CO-N(CH3)2 or CH(CH3)-CO-N(CH3)27 - di(C1-C4-alkyl)phosphonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by di(C1-C4-alkyl)phosphonyl such as -PO(OCH3)2, -PO(OCZHS)2, N,N-dipropylphosphonyl, N,N-di(1-methylethyl)phosphonyl, N,N-dibutylphosphonyl, N,N-di(1-methylpropyl)phosphonyl, N,N-di(2-methylpropyl)phosphonyl, N,N-di(l,l-dimethylethyl)phosphonyl, N-ethyl-N-methylphosphonyl, N-methyl-N-propylphosphonyl, N-methyl-N-(1-methylethyl)phosphonyl, N-butyl-N-methylphosphonyl, N-methyl-N-(1-methylpropyl)-phosphonyl, N-methyl-N-(2-methylpropyl)phosphonyl, N-(1,1-dimethylethyl)-N-methylphosphonyl, N-ethyl-N-propylphosphonyl, N-ethyl-N-(1-methylethyl)phosphonyl, N-butyl-N-ethylphosphonyl, N-ethyl-N-(1-methylpropyl)phosphonyl, N-ethyl-N-(2-methylpropyl)phosphonyl, N-ethyl-N-(1,1-dimethylethyl)phosphonyl, N-(1-methylethyl)-N-propylphosphonyl, N-butyl-N-propylphosphonyl, N-(1-methylpropyl)-N-propylphosphonyl, N-(2-methylpropyl)-N-propylphosphonyl, N-(1,1-dimethylethyl)-N-propylphosphonyl, N-butyl-N-(1-methylethyl)phosphonyl, N-(1-methylethyl)-N-(1-methylpropyl)phosphonyl, N-(1-methylethyl)-N-(2-methylpropyl)phosphonyl, N-(1,1-dimethylethyl)-N-(1-methylethyl)phosphonyl, N-butyl-N-(1-methylpropyl)phosphonyl, N-butyl-N-(2-methylpropyl)phosphonyl, N-butyl-N-(1,1-dimethylethyl)phosphonyl, N-(1-methylpropyl)-N-(2-methylpropyl)phosphonyl, N-(1,1-dimethylethyl)-N-(1-methylpropyl)phosphonyl or N-(1,1-dimethylethyl)-N-(2-methylpropyl)phosphonyl, preferably by -PO(OCH3)2 or -PO(OC2H5)2, eg. CH2-PO(OCH3)Z, CH2-PO(OC2H5)2, CH(CH3)-PO(OCH3)2 or CH(CH3)-PO(OCZHS)2:
- C3-C6-alkenyl: prop-1-en-1-yl, allyl, 1-methylethenyl, 1-buten-1-yl, 1-buten-2-yl, 1-buten-3-yl, 2-buten-1-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1-ethylprop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl, n-hex-3-en-1-yl, n-hex-4-en-1-yl, n-hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, I.3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl or 1-ethyl-2-methylprop-2-en-1-yl;
- C3-C6-haloalkenyl: C3-C6-alkenyl as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. 2-chloroallyl, 3-chloroallyl, 2,3-dichloroallyl, 3,3-dichloroallyl, 2,3,3-trichloroallyl, 2,3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2~3-dibromoallyl, 3,3-dibromoallyl, 2,3,3-tribromoallyl or 2,3-dibromobut-2-enyl;
- cyano-C3-C6-alkenyl: for example 2-cyanoallyl, 3-cyanoallyl, 4-cyanobut-2-enyl, 4-cyanobut-3-enyl or 5-cyanopent-4-enyl;
- C3-C6-alkynyl: prop-1-yn-1-yl, prop-2-yn-1-yl, n-but-1-yn-1-yl, n-but-1-yn-3-yl, n-but-1-yn-4-yl, n-but-2-yn-1-yl, n-pent-1-yn-1-yl, n-pent-1-yn-3-yl, n-pent-1-yn-4-yl, n-pent-1-yn-5-yl, n-pent-2-yn-1-yl, n-pent-2-yn-4-yl, n-pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, n-hex-1-yn-I-yl, n-hex-1-yn-3-yl, n-hex-1-yn-4-yl, n-hex-1-yn-5-yl, n-hex-1-yn-6-yl, n-hex-2-yn-1-yl, n-hex-2-yn-4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yI, n-hex-3-yn-1-yl, n-hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl and 4-methylpent-2-yn-5-yl, preferably prop-2-yn-1-yl;
- C3-C6-haloalkynyl: C3-C6-alkynyl as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. 1,1-difluoroprop-2-yn-1-yl, 4-fluorobut-2-yn-1-yI, 4-chlorobut-2-yn-1-yl, 1,1-difluorobut-2-yn-1-yl, 5-fluoropent-3-yn-1-yl or 6-fluorohex-4-yn-1-yl;
- cyano-C3-C6-alkynyl: for example 3-cyanopropargyl, 4-cyanobut-2-yn-1-yl, 5-cyanopent-3-yn-1-yl and 6-cyanohex-4-yn-1-yl;
- C3-Cq-alkenyloxy-C1-Cq-alkyl: C1-Cq-alkyl which is substituted by C3-Cq-alkenyloxy such as allyloxy, but-I-en-3-yloxy, but-1-en-4-yloxy, but-2-en-1-yloxy, 1-methylprop-2-enyloxy or 2-methylprop-2-enyloxy, ie., for example, allyloxymethyl, 2-allyloxyethyl or but-1-en-4-yloxymethyl, in particular 2-allyloxyethyl;
- C3-Cq-alkynyloxy-C1-Cq-alkyl: C1-Cq-alkyl which is substituted by C3-Cq-alkynyloxy such as propargyloxy, but-1-yn-3-yloxy, but-1-yn-4-yloxy, but-2-yn-1-yloxy, 1-methylprop-2-ynyloxy or 2-methylprop-2-ynyloxy, preferably propargyloxy, ie., for example, propargyloxymethyl or 2-propargyloxyethyl, in particuar 2-propargyloxyethyl;
- C3-Cq-alkenylthio-C1-Cq-alkyl: C1-Cq-alkyl which is substituted by C3-Cq-alkenylthio such as allylthio, but-1-en-3-ylthio, but-1-en-4-ylthio, but-2-en-1-ylthio, 1-methylprop-2-enylthio or 2-methylprop-2-enylthio, ie., for example, allylthiomethyl, 2-allylthioethyl or but-1-en-4-ylthiomethyl, in particular 2-(allylthio)ethyl;
- C3-Cq-alkynylthio-C1-Cq-alkyl: C1-Cq-alkyl which is substituted by C3-Cq-alkynylthio, such as propargylthio, but-1-yn-3-ylthio, but-1-yn-4-ylthio, but-2-yn-1-ylthio, 1-methylprop-2-ynylthio or 2-methylprop-2-ynylthio, preferably propargylthio, ie., for example, propargylthiomethyl or 2-propargylthioethyl, in particular 2-(propargylthio)ethyl;
- C3-C4-alkenylsulfinyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by C3-C4-alkenylsulfinyl, such as allylsulfinyl, but-1-en-3-ylsulfinyl, but-1-en-4-ylsulfinyl, but-2-en-1-ylsulfinyl, 1-methylprop-2-enylsulfinyl or 5 2-methylprop-2-enylsulfinyl, ie., for example, allylsulfinylmethyl, 2-allylsulfinylethyl or but-1-en-4-ylsulfinylmethyl, in particular 2-(allylsulfinyl)ethyl;
10 - C3-CQ-alkynylsulfinyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by C3-C4-alkynylsulfinyl, such as propargylsulfinyl, but-1-yn-3-ylsulfinyl, but-1-yn-4-ylsulfinyl, but-2-yn-1-ylsulfinyl, 1-methylprop-2-ynylsulfinyl or 2-methylprop-2-ynylsulfinyl, 15 preferably propargylsulfinyl, ie., for example, propargylsulfinylmethyl or 2-propargylsulfinylethyl, in particular 2-(propargylsulfinyl)ethyl;
- C3-C4-alkenylsulfonyl-C1-C4-alkyl: C1-C4-alkyl which is 20 substituted by C3-C4-alkenylsulfonyl, such as allylsulfonyl, but-1-en-3-ylsulfonyl, but-1-en-4-ylsulfonyl, but-2-en-1-ylsulfonyl, 1-methylprop-2-enylsulfonyl or 2-methylprop-2-enylsulfonyl, ie., for example, allylsulfonylmethyl, 2-allylsulfonylethyl or 25 but-1-en-4-ylsulfonylmethyl, in particular 2-(allylsulfonyl)ethyl;
- C3-C4-alkynylsulfonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by C3-C4-alkynylsulfonyl, such as propargylsulfonyl, but-1-yn-3-ylsulfonyl, but-1-yn-4-ylsulfonyl, but-2-yn-1-ylsulfonyl, 1-methylprop-2-ynylsulfonyl or 2-methylprop-2-ynylsulfonyl, preferably by propargylsulfonyl, ie., for example, propargylsulfonylmethyl or 2-propargylsulfonylethyl, in particular 2-(propargylsulfonyl)ethyl;
- C3-C6-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
- C3-CB_cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl;
- C3-CB-cycloalkyl-C1-C6-alkyl: for example cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, 2-(cyclopropyl)ethyl, 2-(cyclobutyl)ethyl, 2-(cyclopentyl)ethyl, 2-(cyclohexyl)ethyl, 2-(cycloheptyl)ethyl, 2-(cyclooctyl)ethyl, 3-(cyclopropyl)propyl, 3-(cyclobutyl)propyl, 3-(cyclopentyl)propyl, 3-(cyclohexyl)propyl, 3-(cycloheptyl)propyl, 3-(cyclooctyl)propyl, 4-(cyclopropyl)butyl, 4-(cyclobutyl)butyl, 4-(cyclopentyl)butyl, 4-(cyclohexyl)butyl, 4-(cycloheptyl)butyl, 4-(cyclooctyl)butyl, 5-(cyclopropyl)pentyl, 5-(cyclobutyl)pentyl, 5-(cyclopentyl)pentyl, 5-(cyclohexyl)pentyl, 5-(cycloheptyl)pentyl, 5-(cyclooctyl)pentyl, 6-(cyclopropyl)hexyl, 6-(cyclobutyl)hexyl, 6-(cyclopentyl)hexyl, 6-(cyclohexyl)hexyl, 6-(cycloheptyl)hexyl or 6-(cyclooctyl)hexyl;
- C3-Ce-cycloalkyloxy-C1-C4-alkyl: cyclopropyloxymethyl, 1-cyclopropyloxyethyl, 2-cyclopropyloxyethyl, 1-cyclopropyloxyprop-1-yl, 2-cyclopropyloxyprop-1-yl, 3-cyclopropyloxyprop-1-yl, 1-cyclopropyloxybut-1-yl, 2-cyclopropyloxybut-1-yl, 3-cyclopropyloxybut-1-yl, 4-cyclopropyloxybut-1-yl, 1-cyclopropyloxybut-2-yl, 2-cyclopropyloxybut-2-yl, 3-cyclopropyloxybut-2-yl, 3-cyclopropyloxybut-2-yl, 4-cyclopropyloxybut-2-yl, 1-(cyclopropyloxymethyl)eth-1-yl, 1-(cyclopropyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclopropylmethyloxy)prop-1-yl, cyclobutyloxymethyl, 1-cyclobutyloxyethyl, 2-cyclobutyloxyethyl, 1-cyclobutyloxyprop-1-yl, 2-cyclobutyloxyprop-1-yl, 3-cyclobutyloxyprop-1-yl, 1-cyclobutyloxybut-1-yl, 2-cyclobutyloxybut-1-yl, 3-cyclobutyloxybut-1-yl, 4-cyclobutyloxybut-1-yl, 1-cyclobutyloxybut-2-yl, 2-cyclobutyloxybut-2-yl, 3-cyclobutyloxybut-2-yl, 3-cyclobutyloxybut-2-yl, 4-cyclobutyloxybut-2-yl, 1-(cyclobutyloxymethyl)eth-1-yl, 1-(cyclobutyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclobutyloxymethyl)prop-1-yl, cyclopentyloxymethyl, 1-cyclopentyloxyethyl, 2-cyclopentyloxyethyl, 1-cyclopentyloxyprop-1-yl, 2-cyclopentyloxyprop-1-yl, 3-cyclopentyloxyprop-1-yl, 1-cyclopentyloxybut-1-yl, 2-cyclopentyloxybut-1-yl, 3-cyclopentyloxybut-1-yl, 4-cyclopentyloxybut-1-yl, 1-cyclopentyloxybut-2-yl, 2-cyclopentyloxybut-2-yl, 3-cyclopentyloxybut-2-yl, 3-cyclopentyloxybut-2-yl, 4-cyclopentyloxybut-2-yl, 1-(cyclopentyloxymethyl)eth-1-yl, 1-(cyclopentyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclopentyloxymethyl)prop-1-yl, cyclohexyloxymethyl, 1-cyclohexyloxyethyl, 2-cyclohexyloxyethyl, 1-cyclohexyloxyprop-1-yl, 2-cyclohexyloxyprop-1-yl, 3-cyclohexyloxyprop-1-yl, 1-cyclohexyloxybut-1-yl, 2-cyclohexyloxybut-1-yl, 3-cyclohexyloxybut-1-yl, 4-cyclohexyloxybut-1-yl, 1-cyclohexyloxybut-2-yl, 2-cyclohexyloxybut-2-yl, 3-cyclohexyloxybut-2-yl, 3-cyclohexyloxybut-2-yl, 4-cyclohexyloxybut-2-yl, 1-(cyclohexyloxymethyl)eth-1-yl, 1-(cyclohexyloxymethyl)-1-(CH3)eth-1-yl, 1-(cyclohexyloxymethyl)prop-1-yl, cycloheptyloxymethyl, 1-cycloheptyloxyethyl, 2-cycloheptyloxyethyl, 1-cycloheptyloxyprop-1-yl, 2-cycloheptyloxyprop-1-yl, 3-cycloheptyloxyprop-1-yl, 1-cycloheptyloxybut-1-yl, 2-cycloheptyloxybut-1-yl, 3-cycloheptyloxybut-1-yl, 4-cycloheptyloxybut-1-yl, 1-cycloheptyloxybut-2-yl, 2-cycloheptyloxybut-2-yl, 3-cycloheptyloxybut-2-yl, 3-cycloheptyloxybut-2-yl, 4-cycloheptyloxybut-2-yl, 1-(cycloheptyloxymethyl)eth-1-yl, 1-(cycloheptyloxymethyl)-1-(CH3)eth-1-yl, 1-(cycloheptyloxymethyl)prop-1-yl, cyclooctyloxymethyl, 1-cyclooctyloxyethyl, 2-cyclooctyloxyethyl, 1-cyclooctyloxyprop-1-yl, 2-cyclooctyloxyprop-1-yl, 3-cyclooctyloxyprop-1-yl, 1-cyclooctyloxybut-1-yl, 2-cyclooctyloxybut-1-yl, 3-cyclooctyloxybut-1-yl, 4-cyclooctyloxybut-1-yl, 1-cyclooctyloxybut-2-yl, 2-cyclooctyloxybut-2-yl, 3-cyclooctyloxybut-2-yl, 3-cyclooctyloxybut-2-yl, 4-cyclooctyloxybut-2-yl, 1-(cyclooctyloxymethyl)eth-1-yl, 1-(cyclooctyloxymethyl)-1-(CH3)eth-1-yl or 1-(cyclooctyloxymethyl)prop-1-yl, in particular C3-C6-cycloalkoxymethyl or 2-(C3-C6-cycloalkoxy)ethyl.
3- to 7-membered heterocyclyl is to be understood as meaning not only saturated, partially or fully unsaturated, but also aromatic, heterocycles having one to three hetero atoms selected from a group consisting of - one to three nitrogen atoms, - one to two oxygen and _ one or two sulfur atoms.
Examples of saturated heterocycles which can contain a carbonyl or thiocarbonyl ring member are:
oxiranyl, thiiranyl, aziridin-1-yl, aziridin-2-yl, diaziridin-1-yl, diaziridin-3-yl, oxetan-2-yl, oxetan-3-yl, thietan-2-yl, thietan-3-yl, azetidin-1-yl, azetidin-2-yl, azetidin-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, 1,3-dioxolan-2-yl, 1,3-dioxolan-4-yl, 1,3-oxathiolan-2-yl, 1,3-oxathiolan-4-yl, 1,3-oxathiolan-5-yl, 1,3-oxazolidin-2-yl, 1,3-oxazolidin-3-yl, 1,3-oxazolidin-4-yl, 1,3-oxazolidin-5-yl, 1,2-oxazolidin-2-yl, 1,2-oxazolidin-3-yl, 1,2-oxazolidin-4-yl, 1,2-oxazolidin-5-yl, 1,3-dithiolan-2-yl, 1,3-dithiolan-4-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-5-yl, tetrahydropyrazol-1-yl, tetrahydropyrazol-3-yl, tetrahydropyrazol-4-yl, tetrahydropyran-2-yl, tetrahydrogyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydropyran-4-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, 1,3-oxathian-2-yl, 1,3-oxathian-4-yl, 1,3-oxathian-5-yl, 1,3-oxathian-6-yl, 1,4-oxathian-2-yl, 1,4-oxathian-3-yl, morpholin-2-yl, morpholin-3-yl, morpholin-4-yl, hexahydropyridazin-1-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-1-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, piperazin-1-yl, piperazin-2-yl, piperazin-3-yl, hexahydro-1,3,5-triazin-1-yl, hexahydro-1,3,5-triazin-2-yl, oxepan-2-yl, oxepan-3-yl, oxepan-4-yl, thiepan-2-yl, thiepan-3-yl, thiepan-4-yl, 1,3-dioxepan-2-yl, 1,3-dioxepan-4-yl, 1,3-dioxepan-5-yl, 1,3-dioxepan-6-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,4-dioxepan-2-yl, 1,4-dioxepan-7-yl, hexahydroazepin-1-yl, hexahydroazepin-2-yl, hexahydroazepin-3-yl, hexahydroazepin-4-yl, hexahydro-1,3-diazepin-1-yl, hexahydro-1,3-diazepin-2-yl, hexahydro-1,3-diazepin-4-yl, hexahydro-1,4-diazepin-1-yl and hexahydro-1,4-diazepin-2-yl.
Examples of unsaturated heterocycles which can contain a carbonyl or thiocarbonyl ring member are:
dihydrofuran-2-yl, 1,2-oxazolin-3-yl, 1,2-oxazolin-5-yl, 1,3-oxazolin-2-yl;
Preferred amongst the heteroaromatic rings are the 5- and 6-membered rings, eg.
furyl such as 2-furyl and 3-furyl, thienyl such as 2-thienyl and 3-thienyl, pyrrolyl such as 2-pyrrolyl and 3-pyrrolyl, isoxazolyl such as 3-isoxazolyl, 4-isoxazolyl and 5-isoxazolyl, isothiazolyl such as 3-isothiazolyl, 4-isothiazolyl and 5-isothiazolyl, pyrazolyl such as 3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl such as 2-vxazolyl, 4-oxazolyl and 5-oxazolyl, thiazolyl such as 2-thiazolyl, 4-thiazolyl and 5-thiazolyl, imidazolyl such as 2-imidazolyl and 4-imidazolyl, oxadiazolyl such as 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl and 1,3,4-oxadiazol-2-yl, thiadiazolyl such as 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl and 1,3,4-thiadiazol-2-yl, triazolyl such as 1,2,4-triazol-1-yl, 1,2,4-triazol-3-yl and 1,2,4-triazol-4-yl, pyridinyl such as 2-pyridinyl, 3-pyridinyl and 4-pyridinyl, pyridazinyl such as 3-pyridazinyl and 4-pyridazinyl, pyrimidinyl such as 2-pyrimidinyl, 4-pyrimidinyl and 5-pyrimidinyl, furthermore 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl, in particular pyridyl, pyrimidyl, furanyl and thienyl.
p,ll phenyl, carbocyclic and heterocyclic rings are preferably unsubstituted.
Preferred for the use of the 3-(benzazol-4-yl)pyrimidinedione derivatives I as herbicides are those compounds I where the variables have the following meanings, in each case alone or in combination:
X is oxygen;
R1 is hydrogen, amino or C1-C6-alkyl, in particular hydrogen or C1-C4-alkyl, especially preferably hydrogen or methyl;
R2 is hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl or C1_C6-alkylsulfonyl, in particular trifluoromethyl;
R3 is hydrogen;
R4 is hydrogen, fluorine or chlorine;
R5 is cyano or halogen, in particular chlorine;
=Y- is =N-N(R6)- or =C(ZR7)-5-, in particular =N-N(R6)-;
R6 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkylsulfonyl, (C1-C6-alkyl)carbonyl, (C1-C6-alkyl)thiocarbonyl, (C1-C6-alkoxy)carbonyl or C1-C6-alkyl which can be substituted by cyano, (C1-C6-alkoxy)carbonyl, di(C1-C6-alkyl)aminocarbonyl or (C1-C6-alkyl)carbonyloxy, in particular C1-C6-alkyl, C3-C6-alkynyl, C1-C6-alkylsulfonyl or (C~-C6-alkoxy)carbonyl.
Especially preferred are also the 3-(benzazol-4-yl)pyrimidine-dione derivatives Ia f~-- I where X = oxygen, R1 = methyl, RZ = trifluoromethyl, R3 = hydrogen, R4 = fluorine, R5 = chlorine and =Y- - =C(ZR7)-N(CH3)-}
~
N
F3C ~ N ~ ~ C1 Ia, O N\ 'N-CH3 10 in particular the compounds Ia.l to Ia.272 which follow:
Table 1 No . -ZR7 15Ia . l -H _ _ Ia.2 -CH3 Ia.3 -C3H5 Ia.4 -n-C3H~
20Ia.S -CH(CH3)2 Ia.6 -n-C4H9 Ia.7 -CH2-CH(CH3)2 Ia.8 -CH(CH3)-CyHS
25Ia.9 -C(CH3)s Ia.IO -CH2-CH=CHz Ia.ll -CH2-CH=CH-CH3 Ia.l2 -CH2-CHy-CH=CH2 Ia.l3 -CH2-C=CH
30Ia.l4 -CH2-OCH3 Ia.lS -CHZ-CH2-OCH3 Ia.l6 -CH2-CN
Ia.l7 -CHy-CH2F
35Ia.l8 -CH2-CF3 Ia.l9 -CHZ-CH2C1 Ia.20 -CH2-CO-OCH3 Ia.21 -CH2-CO-OC2H5 40Ia.22 -CH2-CO-N(CH3)3 Ia.23 -cyclobutyl Ia.24 -cyclopentyl Ia.25 -cyclohexyl Ia.26 -phenyl Ia.27 -CHZ-cyclobutyl Ia.28 -CH2-cyclopentyl No . -ZR7 Ia.29 -CH2-cyclohexyl Ia.30 -CHz-phenyl Ia.31 -N02 Ia.32 -CN
Ia.33 -F
Ia.34 -C1 Ia.35 -Br Ia.36 -OCH3 Ia.37 -OC2H5 Ia.38 -O(n-C3H7) Ia.39 -OCH(CH3)2 Ia.40 -0(n-C4H9) Ia.41 -OCH2-CH(CH3)2 Ia.42 -OCH(CH3)-C2H5 Ia.43 -OC(CH3)a Ia.44 -OCH2-CH=CH2 Ia.45 -OCHZ-CH=CH-CH3 Ia.46 -OCH2-CHZ-CH=CHZ
Ia.47 -OCH(CH3)-CH=CHZ
Ia.48 -OCH2-C=CH
Ia.49 -OCH(CH3)-C = CH
Ia.50 -OCHZ-OCH3 Ia.51 -OCH2-CH2-OCH3 Ia.52 -OCH2-CN
Ia.53 -OCH2-CHZF
Ia.54 -OCH2-CF3 Ia.55 -OCH2-CO-OCH3 Ia.56 -OCHZ-CO-OCZHS
Ia.57 -OCHz-CO-N(CH3)2 Ia.58 -O-cyclobutyl Ia.59 -O-cyclopentyl Ia.60 -O-cyclohexyl Ia.61 -0-phenyl Ia.62 -OCH2-cyclobutyl Ia.63 -OCH2-cyclopentyl Ia.64 -OCHZ-cyclohexyl Ia.65 -OCHZ-phenyl Ia.66 -CHZ-OH
Ia.67 -CH2-OCH3 No. -ZR~
Ia.68 -NHz Ia.69 -NH-CH3 Ia.70 -N(CH3)z Ia.71-.. -NH-C2H5 Ia.72 -N(C3H5)2 Ia.73 -NH-(n-C3H7) Ia.74 -N(n-C3H~)2 Ia.75 -NH-(n-C4H9) Ia.76 -N(n-CqH9)z Ia.77 -NH-CH(CH3)z Ia.78 -N[CH(CH3)212 15Ia,7g -NH-CH2-CH(CH3)z Ia.80 -N(CHZ-CH(CH3)z)2 Ia.81 -NH-CHz-CH=CHz Ia.82 -N(CHz-CH=CHz)2 20Ia.83 -NH-CHz-C = CH
Ia.84 -N(CHz-C=CH)z Ia.85 -CHZ-N(CH3)2 Ia.86 -SH
25Ia.87 -SCH3 Ia.88 -SCZHS
Ia.89 -S-(n-C3H7) Ia.90 -S-(n-CqH9) Ia.91 -SCH(CH3)z 30Ia.92 -SCHZ-CH(CH3)z Ia.93 -SCH(CH3)-C2H5 Ia.94 -SC(CH3)3 Ia.95 -SCHZ-CH=CHz 35Ia.96 -SCHz-CH=CH-CH3 Ia.97 -SCHZ-CHz-CH=CHz Ia.98 -SCH(CH3)-CH=CHz Ia.99 -SCHz-C=CH
40Ia.100 -SCH(CH3)-C = CH
Ia.101 -SCHz-OCH3 Ia.102 -SCHZ-CHz-OCH3 Ia.103 -SCHz-CN
Ia.104 -SCHZ-CH2F
Ia.105 -SCHZ-CF3 Ia.106 -SCHZ-CH2C1 No . -ZR~
Ia.107 -SCH2-CO-OCH3 Ia.108 -SCH2-CO-OC2H5 Ia.109 -SCHZ-CO-N(CH3)2 Ia.110 -S-cyclobutyl Ia.lll -S-cyclopentyl Ia.112 -S-cyclohexyl Ia.113 -S-phenyl Ia.114 -SCH2-cyclobutyl Ia.115 -SCH2-cyclopentyl Ia.116 -SCH2-cyclohexyl Ia.117 -SCH2-phenyl Ia.118 -CH2-SCH3 Ia.119 -SO-CH3 Ia.120 -SO-CyHs Ia.121 -SO-(n-C3H7) Ia.122 -SO-(n-CqH9) Ia.123 -SO-CH(CH3)2 Ia.124 -SO-CH2-CH(CH3)2 Ia.125 -SO-CH(CH3)-CZH5 Ia.126 -SO-C(CH3)3 Ia.127 -SO-CHZ-CH=CHz Ia.128 -SO-CHy-CH=CH-CH3 Ia.129 -SO-CH2-CH2-CH=CH2 Ia.130 -SO-CH(CH3)-CH=CH2 Ia.131 -SO-CH2-C=CH
Ia.132 -SO-CH(CH3)-C=CH
Ia.133 -SO-CHz-OCH3 Ia.134 -SO-CHy-CH2-OCH3 Ia.135 -SO-CH2-CN
Ia.136 -SO-CHy-CH2F
Ia.137 -SO-CH2-CF3 Ia.138 -SO-CHZ-CH2C1 Ia.139 -SO-CH2-CO-OCH3 Ia.140 -SO-CH2-CO-OC2H5 Ia.141 -SO-CHz-CO-N(CH3)2 Ia.142 -SO-cyclobutyl Ia.143 -SO-cyclopentyl Ia.144 -SO-cyclohexyl Ia.145 -SO-phenyl.
No . -ZR~
Ia.146 -SO-CHZ-cyclobutyl Ia.147 -SO-CHZ-cyclopentyl Ia.148 -SO-CH2-cyclohexyl Ia.149 -SO-CH2-phenyl Ia.150 -CHZ-SO-CH3 Ia.151 -SOz-CH3 Ia.152 -SOZ-C2H5 Ia.153 -SOZ-(n-C3H7) Ia.154 -SOZ-(n-C4H9) Ia.155 -S02-CH(CH3)2 Ia.156 -SOZ-CHZ-CH(CH3)2 Ia,157 -SOz-CH(CH3)-C2H5 Ia.158 -SOz-C(CH3)3 Ia.159 -S02-CHZ-CH=CHZ
Ia.160 -SOy-CHZ-CH=CH-CH3 Ia.161 -S02-CH2-CH2-CH=CHZ
Ia.162 -SOZ-CH(CH3)-CH=CHZ
Ia.163 -SOZ-CHZ-C=CH
Ia.164 -SOZ-CH(CH3)-C=CH
Ia.165 -SOZ-CHZ-OCH3 Ia.166 -SOz-CHZ-CHy-OCH3 Ia.167 -S02-CH2-CN
Ia.168 -SOZ-CH2-CHZF
Ia.169 -S02-CHZ-CF3 Ia.170 -S02-CHz-CHZCl Ia.171 -S02-CHy-CO-OCH3 Ia.172 -S02-CHZ-CO-OC2H5 Ia.173 -SOZ-CHZ-CO-N(CH3)2 Ia.174 -SOz-cyclobutyl Ia.175 -SOy-cyclopentyl Ia.176 -SOz-cyclohexyl Ia.177 -S02-phenyl Ia.178 -SOz-CH2-cyclobutyl Ia.179 -SOZ-CHZ-cyclopentyl Ia.180 -S02-CH2-cyclohexyl Ia.181 -S02-CHZ-phenyl Ia.182 -CH2-S02-CH3 Ia.183 -CHZ-CH(C1)-CO-OH
Ia.184 -CH2-CH(C1)-CO-OCH3 No. -ZR7 Ia.185 -CH2-CH(Cl)-CO-OC2H5 Ia.186 -CH2-CH(Cl)-CO-0(n-C3H7) 5 Ia.187 -CH2-CH(C1)-CO-0(n-C4Hg) Ia.188 -CH2-CH(C1)-CO-OCH(CH3)2 Ia.189 -CH2-CH(Cl)-CO-OCH2-CH(CH3)2 Ia.190 -CH2-CH(Cl)-CO-OCH(CH3)-C2H5 Ia.191 -CH2-CH(C1)-CO-OC(CH3)3 Ia.192 -CH2-CH(Hr)-CO-OH
Ia.193 -CH2-CH(Br)-CO-OCH3 Ia.194 -CH2-CH(Br)-CO-OC2H5 Ia.195 -CH2-CH(Br)-CO-O(n-C3H7) 15 Ia,196 -CH2-CH(Br)-CO-O(n-CQHg) Ia.197 -CH2-CH(Br)-CO-OCH(CH3)2 Ia.198 -CH2-CH(Br)-CO-OCH2-CH(CH3)2 Ia.199 -CH2-CH(Br)-CO-OCH(CH3)-C2H5 20 Ia.200 -CH2-CH(Br)-CO-OC(CH3)3 Ia.201 -CH=CH-CO-OH
Ia.202 -CH=CH-CO-OCH3 Ia.203 -CH=CH-CO-OC2H5 25 Ia.204 -CH=CH-CO-0(n-C3H7) Ia.205 -CH=CH-CO-0(n-C4Hg) Ia.206 -CH=CH-CO-OCH(CH3)2 Ia.207 -CH=CH-CO-OCH2-CH(CH3)2 Ia.208 -CH=GH-CO-OCH(CH3)-C2H5 30 Ia.209 -CH=CH-CO-OC(CH3)3 Ia.210 -CH=C(Cl)-CO-OH
Ia.211 -CH=C(C1)-CO-OCH3 Ia.212 -CH=C(C1)-CO-OC2H5 35 Ia.213 -CH=C(C1)-CO-0(n-C3H7) Ia.214 -CH=C(C1)-CO-0(n-C4Hg) Ia.215 -CH=C(C1)-CO-OCH(CH3)2 Ia.216 -CH=C(C1)-CO-OCH2-CH(CH3)2 Ia.217 -CH=C(C1)-CO-OCH(CH3)-C2H5 Ia.218 -CH=C(C1)-CO-OC(CH3)3 Ia.219 -CH=C(Br)-CO-OH
Ia.220 -CH=C(Br)-CO-OCH3 Ia.221 -CH=C(Br)-CO-OC2H5 Ia.222 -CH=C(Br)-CO-O(n-C3H7) Ia.223 -CH=C(Br)-CO-O(n-C4Hg) No . -2R7 Ia.224 -CH=C(Br)-CO-OCH(CH3)z Ia.225 -CH=C(Br}-CO-OCHZ-CH(CH3}z Ia.226 -CH=C(Br)-CO-OCH(CH3)-C2Hs Ia.227 -CH=C(Br}-CO-OC(CH3)3 Ia.228 -CHz-CH(C1)-CO-NHz Ia.229 -CHZ-CH(C1)-CO-NH-CH3 Ia.230 -CHZ-CH(C1)-CO-N(CH3)z Ia.231 -CHz-CH(C1)-CO-NH-CyHs Ia.232 -CHz-CH(C1)-CO-N(C2HS)z Ia.233 -CHz-CH(C1)-CO-NH-(n-C3H~) Ia.234 -CHz-CH(C1)-CO-N(n-C3H7)z Ia,235 -CHz-CH(C1)-CO-NH-(n-C4Hg) Ia.236 -CHz-CH(C1)-CO-N(n-C4Hg)z Ia.237 -CHz-CH(Br)-CO-NHz Ia.238 -CHz-CH(Br)-CO-NH-CH3 Ia.239 -CHZ-CH(Br)-CO-N(CH3)z Ia.240 -CHz-CH(Br)-CO-NH-C2Hs Ia.241 -CHz-CH(Br)-CO-N(C2H5)z Ia.242 -CHz-CH(Br)-CO-NH-(n-C3H7) Ia.243 ~CH2-CH(Br)-CO-N(n-C3H7)z Ia.244 -CHz-CH(Br)-CO-NH-(n-C4Hg) Ia.245 -CHz-CH(Br)-CO-N(n-C4Hg)z Ia.246 -CH=CH-CO-NHz Ia.247 -CH=CH-CO-NH-CH3 Ia.248 -CH=CH-CO-N(CH3)2 Ia.249 -CH=CH-CO-NH-C2Hs Ia.250 -CH=CH-CO-N(CzHs)z Ia.251 -CH=CH-CO-NH-(n-C3H7) Ia.252 -CH=CH-CO-N(n-C3H7)z Ia.253 -CH=CH-CO-NH-(n-C4Hg) Ia.254 -CH=CH-CO-N(n-C4Hg)z Ia.255 -CH=C(C1)-CO-NHz Ia256 -CH=C(C1)-CO-NH-CH3 Ia.257 -CH=C(C1)-CO-N(CH3)2 Ia.258 -CH=C(C1)-CO-NH-CZHs Ia.259 -CH=C(C1)-CO-N(CZHs)2 Ia.260 -CH=C(C1)-CO-NH-(n-C3H7) Ia.261 -CH=C(C1)-CO-N(n-C3H7)z Ia.262 -CH=C(Cl)-CO-NH-(n-C4H9}
No~. -ZR7 Ia.263 -CH=C(C1)-CO-N(n-C4Hg)Z
Ia.264 -CH=C(Br)-CO-NH2 Ia.265 -CH=C(Br)-CO-NH-CH3 Ia.266 -CH=C(Br)-CO-NH(CH3)2 Ia.267 -CH=C(Br)-CO-NH-C2H5 Ia.268 -CH=C(Br)-CO-N(C2H5)2 Ia.269 -CH=C(Br)-CO-NH-(n-C3H7) Ia.270 -CH=C(Br)-CO-N(n-C3H~)Z
Ia.271 -CH=C(Br)-CO-NH-(n-C4Hg) Ia.272 -CH=C(Br)-CO-N(n-CqH9)2 Furthermore, especially preferred 3-(benzazol-4-yl)-pyrimidinedione derivatives are those of the formulae Ib to Ih, in particular - the compounds Ib.l - Ib.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that R4 is hydrogen:
N
F3C ~ N ~ ~ C1 Ib O N~N-CH3 ~ZR~
- the compounds Ic.l - Ic.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that R1 is hydrogen:
H O F
N
F3C ~ N- ~ ~ C1 Ic O N ~ N- CH3 - the compounds Id.l - Id.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that R1 and R4 are hydrogen:
N
FgC ~ N- ~ ~ C1 Id 'O N~ N-CH3 _ the compounds Ie.l - Ie.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that Y
is =C(ZR7)-N(S02CH3)-.
N-F3C ~ N C1 Ie 0 N~N-S02-CH3 ~ZR7 - the compounds If.l - If.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that R4 is hydrogen and Y is =C(ZR7)-N(SOZCH3)-.
N
F3C ~ N- ~ ~ C1 If O N\ 'N-SOZ-CH3 - the compounds Ig.l - Ig.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that R1 is hydrogen and Y is =C(ZR7)-N(SOZCH3)-.
H O F
N-~ - / \
F3C ~ N C1 Ig 'O N~ N-~-S02-CH3 - the compounds Ih.l - Ih.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that R1 and RQ are hydrogen and Y is =C(ZR7)-N(S02CH3)-.
H O
\
N
F3C ~ N ~ ~ C1 Ih - the compounds Ii.l - Ii.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that =Y- is =C(ZR7)-O-:
N
F3C ~ N ~ ~ C1 Ii O N\ 'O
- the compounds Ik.l - Ik.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that =Y- is =C(ZR7)-O- and R4 is hydrogen:
\
N
F3C ~ N- ~ ~ C1 Ik 'O N ~ O
ZR~
- the compounds Im.l - Im.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that Y
is =C(ZR7)-O- and R1 is hydrogen:
H O F
N
F3C ~ N ~ ~ C1 Im 5 '0 N ~ O
10 _ the compounds In.l - In.272, which differ from the corresponding compounds Ia.l - Ia.272 only by the fact that Y
is =C(ZR~)-0- and R1 and R4 are hydrogen:
15 N--~ - /
F3C ~ N C1 In O N\ '0 20 IZR~
The 3-(benzazol-4-yl)pyrimidinedione derivatives of the formula I
can be obtained in various ways, for example by one of the 25 following processes:
Process A~:
Reaction of a 3-(benzazol-4-yl)pyrimidinedione derivative I where R1 is hydrogen with a compound II in a manner known per se:
\N~ L1-alkyl or \N-3 5 R2 \ N / \ RS + R2 N ~ ~ R5 L1-haloalkyl I (Rl = H) II I (Rl ~ H, NHZ) L1 is a customary leaving group such as halogen, preferably chlorine, bromine or iodine, (halo)alkylsulfonyloxy, preferably methylsulfonyloxy or trifluoromethylsulfonyloxy, arylsulfonyloxy, preferably toluenesulfonyloxy, and alkoxysulfonyloxy, preferably methoxysulfonyloxy or ethoxysulfonyloxy.
The process is normally carried out in an inert organic solvent, for example in a protic solvent such as the lower alcohols, preferably in methanol or ethanol, if desired as a mixture with water, or in an aprotic solvent, for example in an aliphatic or cyclic ether such as methyl tert-butyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aliphatic ketone such as acetone, diethyl ketone and ethyl methyl ketone, in an amide such as dimethylformamide and N-methylpyrrolidone, in a sulfoxide such as dimethyl sulfoxide, in a urea such as tetramethylurea and 1,3-dimethyltetrahydro-2(1H)-pyrimidinone, in a carboxylic acid ester such as ethyl acetate, or in a halogenated aliphatic or aromatic hydrocarbon such as dichloromethane, dichloroethane, chlorobenzene and the dichlorobenzenes.
If desired, the process can be carried out in the presence of a base, suitable bases being inorganic bases, eg, carbonates such as sodium carbonate and potassium carbonate, hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate or alkali metal hydrides such as sodium hydride and potassium hydride, and also organic bases, eg.
amines such as triethylamine, pyridine and N,N-diethylaniline, or alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide.
The amount of base and alkylating agent II is preferably in each case 0.5 times to twice the molar amount, based on the amount of starting compound I (where R1 = hydrogen).
In general, the reaction temperature is from 0°C to the boiling point of the reaction mixture, in particular from 0 to 60~C.
A preferred process variant consists in alkylating the salt of I, which has been obtained by cyclizing IV where R1 = H or V where R1 = H in accordance with process D) without isolating it from the reaction mixture, which may still contain excess base, eg. sodium hydride, sodium alkoxide or sodium carbonate.
Unless the salts of those compounds I where R1 is hydrogen cannot be prepared directly by the cyclization under basic conditions, which has been described as method D), they can also be obtained in a manner known per se from the process products of methods C) to F). To this end, for example, the aqueous solution of an inorganic or organic base is treated with the 3-(benzazol-4-yl)pyrimidinedione derivative I where Ri is hydrogen. Here, salt formation is normally sufficiently rapid at as little as 20 to 25~C.
It is especially advantageous to prepare the sodium salt by dissolving the 3-(benzazol-4-yl)pyrimidinedione derivative I
where Ri = hydrogen in an aqueous sodium hydroxide solution at 20 to 25~C, approximately equivalent amounts of 3-(benzazol-4-yl)pyrimidinedione derivative I (Where Ri = H) and sodium hydroxide being employed. The corresponding salt of the 3-(benzazol-4-yl)pyrimidinedione derivative I can then be isolated for example by precipitation with a suitable inert solvent or by evaporating the solvent.
Salts of the 3-(benzazol-4-yl)pyrimidinedione derivatives I
whose metal ion is other than an alkali metal ion can usually be prepared by double decomposition of the corresponding alkali metal salt in aqueous solution, and ammonium, Phosphonium, sulfonium and sulfoxonium salts by means of ammonia or phosphonium, sulfonium or sulfoxonium hydroxides.
Process B~
Reaction of a 3-(benzazol-4-yl)pyrimidinedione derivative of the formula I where Ri is hydrogen with an electrophilic aminating reagent in the presence of a base:
\ O R4 H2 \ O R9 R2 N~ / \ R5 aminating reagent 2 N ' / \ R5 N ~ R N
\ base \
I ~Ri = H} I ~R1 = NH2}
An aminating reagent which has proved itself especially to date is 2,4-dinitrophenoxyamine, but it is also possible to use, for example, hydroxylamine-O-sulfonic acid (HOSA), which is already known from the literature as an aminating reagent (cf., for example, E. Hofer et al., Synthesis 1983, 466; W.
Friedrichsen et al., Heterocycles 20 (1983) 1271; H. Hart et al., Tetrahedron Lett. 25 (1984) 2073; B. Vercek et al., Monatsh. Chem. ~4 (1983) 789; G. Sosnousky et al., Z.
Naturforsch. 38 (1983) 884; R.S. Atkinson et al., J. Chem.
Soc. Perkin Trans. 1987, 2787).
The amination can be carried out in a manner known per se (see, for example, T. Sheradsky, Tetrahedron Lett. 1968, 1909; M.P. Wentland et al., J. Med. Chem. 27 (1984) 1103 and in particular EP-A 240 194, EP-A 476 697 and EP-A 517 181, which teach the amination of uracils).
The reaction is normally carried out in a polar solvent, for example in dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or in ethyl acetate, which has proved to be especially suitable to date.
Suitable bases are, for example, alkali metal carbonates such as potassium carbonate, alkali metal alkoxides such as sodium methoxide and potassium tert-butoxide or alkali metal hydrides such as sodium hydride.
The amount of base and aminating agent is preferably in each case 0.5 times to twice the molar amount, based on the amount of starting compound.
Process C~
Sulfurization of a 3-(benzazol-4-yl)pyrimidinedione derivative of the formula I where X is oxygen:
Ri O R4 R1 0 R4 \N~ ~ \ 5 sulfurization 2 \N--~
R \ N R R \ N RS
\\ _ \\ N - Y
I (X = O) I (X = S) As a rule, sulfurization is effected in an inert solvent or diluent, for example in an aromatic hydrocarbon such as toluene and the xylenes, in an ether such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran, or in an organic amine such as pyridine.
Especially suitable sulfurization reagents are phosphorus(V) sulfide and 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-dithione ("Lawesson reagent").
Normally, once to five times the molar amount, based on the starting compound to be sulfurized, will suffice for an essentially complete reaction.
The reaction temperature is normally from 20 to 200~C, preferably 40~C to the boiling point of the reaction mixture.
Process D~
CYclization of an arylurea of the formula III or of an arylanilide of the formula IV in the presence of a base:
\ 0 R4 \ O
z N p' NH ~ ~ 5 2 N ' OLz R ~ / R or R ~ / O R4 R3 OLz N Y R3 NH ~ ~ RS
base N - Y
III IV
Ri 0 R4 \
N
Rz ~ ~ ~ 5 N R
R3 '~ N - Y
I (X = O) Lz is lower alkyl, preferably Ci-C4-alkyl, or phenyl.
As a rule cyclization is effected in an inert organic solvent or diluent which is aprotic, for example in an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aromatic such as benzene or toluene, or in a Polar solvent such as dimethylformamide or dimethyl sulfoxide. Mixtures of polar solvent and a hydrocarbon such as n-hexane are also suitable. Depending on the starting compound, water may also be suitable as diluent.
Suitable bases are, preferably, alkali metal alkoxides, in particular the sodium alkoxides, alkali metal hydroxides, in particular sodium hydroxide and potassium hydroxide, alkali ~
metal carbonates, in particular sodium carbonate and potassium carbonate, and metal hydrides, in particular sodium hydride. When using sodium hydride as the base, it has proved advantageous to carry out the process in an aliphatic or 5 cyclic ether, in dimethylformamide or in dimethyl sulfoxide.
Normally, 0.5 times to twice the molar amount of base, based on the amount of IV or V, will suffice for successfully carrying out the reaction.
In general, the reaction temperature is from (-78)~C to the boiling point of the reaction mixture in question, in particular (-60) to 60~C.
If Ri in formula III or IV is hydrogen, the process product is obtained as a metal salt, the metal corresponding to the cation of the base used. The salt can be isolated and purified in a manner known per se or, if desired, converted by means of acid to give the free compound I where Ri =
hydrogen.
Process E~
Treatment of a substituted 2-aminoaniline Va with nitrous acid R1 O R4 Ri O R4 \N~ ~ ~ "HNO2..
R ~ N R5 R2 \ N ~ ~ R5 R3 X NHy NHR6 R3 X N\ ~
Va I {=y- _ =N-N(R6)-}
The cyclization reaction can be carried out by processes known per se (cf., for example, Houben-Weyl, Methoden der organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Vol. EBd, Ist Edition 1994, pp.
409-415).
The reaction is preferably carried out in acidic aqueous media, but lower carboxylic acids such as acetic acid are also suitable diluents. Suitable acidic aqueous solvents are, in particular, dilute mineral acids, for example 10~ strength hydrochloric acid.
~
The nitrous acid is preferably prepared in situ by adding an alkali metal nitrite - in substance or in aqueous solution -to the reaction mixture, which is composed of the diaminobenzene in acidic aqueous solution or in a carboxylic acid.
A suitable reaction temperature is, in particular, 0 to 20~C, very especially approximately 5~C.
The starting materials are expediently employed in approximately stoichiometric amounts, or the process is carried out with an excess of the theoretically expected amount of nitrous acid, which is not more than 10 mold.
The following intermediate can be cyclized in a similar manner:
R5 --~,. ~ ~ R5 H2N NHR6 N~N~N~
VI VII
Process F~
Condensation of a substituted 2-aminophenol, 2-aminothiophenol or 2-aminoaniline (V) with carbonic acid derivatives or carboxylic acid derivatives:
O R4 carbonic acid R1 O R4 N // derivative or ~N~
scarboxylic acid R ~ N R derivative R ~ N R5 X N (O/S/I ) R3 X NH2 (O/S/I )-H R3 V
I (Z = chemical bond, O, NH;
R7 = H, unsubst. or subst.
alkyl, alkenyl or aryl) The condensation reaction of the bifunctional benzenes V with the carbonic acid derivatives or carboxylic acid derivatives are carried out in a manner known per se (cf., for example, Houben-Weyl, Methoden der organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Vol. EBc, ' CA 02312703 2000-06-OS
1st Edition 1994, pp. 247-284; Vol. EBb, 1st Edition 1994, pp. 881-901; Vol. EBa, 1st Edition 1993, pp. 1032-1078).
Preferred carbonic acid derivatives or carboxylic acid derivatives are the corresponding anhydrides, acid chlorides, ortho esters, diimides, nitriles, trichloromethyl-substituted compounds, isocyanates and their thio analogs.
Suitable solvents/diluents are, in particular, organic solvents, for example aromatic hydrocarbons such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, lower alcohols such as methanol and ethanol, aliphatic or cyclic ethers such as dimethoxyethane, tetrahydrofuran and dioxane, carboxylic esters such as ethyl acetate or aprotic polar solvents such as dimethylformamide and ~dimethyl sulfoxide.
If desired, the reaction can be accelerated by adding catalytic amounts of an acid. Suitable acids are, in Particular, mineral acids such as hydrochloric acids [sic] or sulfonic acids such as p-toluenesulfonic acid. The amounts of acid are preferably 0.1 to 5 mol percent, based on the amount of V.
The reaction temperatures are preferably from 20~C to reflux temperature of the reaction mixture in question, in particular 60~C to reflux temperature.
The carbonic acid derivative or carboxylic acid derivative is employed either in an approximately stoichiometric amount or in an excess. In suitable cases, a very large excess may also be employed, or else the process can be carried out in the absence of a solvent. Approximately stoichiometric amounts or an excess of up to 10 mole equivalents, based on the amount of V, are preferred.
The substituted 2-aminophenols, -thiophenols and -anilines (V) are expediently obtained by reducing the corresponding 2-nitrophenols, -thiophenols or -anilines VIII (cf., for example Houben-Weyl, Methoden der organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Vol.
XI/1, 4th Edition 1957, p. 431 et seq.):
Rl O R4 R1 O R4 2 \N ~ / \ \N
R \ N R5 reduction RZ \ N / \ R5 R3 X NOy (O/S/I )-H R3 X NH2 (0/S/I )-H
Suitable reducing agents are, in particular, - elemental metals such as iron, tin and zinc, - hydrogen in the presence of suitable catalysts such as palladium or platinum on charcoal or Raney nickel, or - complex hydrides such as LiAlH4 and NaBH4, in the presence or absence of catalysts.
Depending on the reducing agent, suitable solvents are normally carboxylic acids such as acetic acid or propionic acid, alcohols such as methanol and ethanol, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane, aromatics such as benzene and toluene, and mixtures of these.
The reactions can be carried out at from (-100)~C to the boiling point of the reaction mixture in question.
The starting compounds are normally employed in approximately stoichiometric amounts; however, in individual cases an excess of one or the other component of up to approximately 10 mold may also be advantageous.
The 2-nitrophenols, -thiophenols and -anilines VIII, in turn, can be set free from the corresponding protected nitro compounds IX:
N N
z ~ / \ 5 elimination 2 / \ s R N R R N R
\ reagent \
R3 X N02 (0/S/N)-protection R3 X N02 (0/S/I )-H
~
Protection = customary protective group which protects the phenols, or thiophenols, as ethers or the amino group as an amide.
The protective groups can be eliminated by processes known per se (cf., for example, Greene/Wuts: Protective Groups in Organic Synthesis, John Wiley & Sons, Inc., 2nd Edition 1991, p. 145 et seq. and p. 279 et seq.).
Suitable elimination reagents are, in particular:
- for alkylphenols: trimethylsilyl iodide, boron tribromide, boron trichloride, aluminum trichloride, lithium chloride or hydrogen bromide;
- for unsubstituted or substituted benzylphenols or -thiophenols: boron trifluoride, hydrofluoric acid or hydrogen/catalyst, preferably noble metal catalysts such as palladium or platinum.
The solvent/diluent is preferably chosen in such a way that it is inert to the elimination reagent in question. When using the halides trimethylsilyl iodide, boron tribromide, boron trichloride or aluminum trichloride, halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride and dichloroethane are especially preferred.
Hydrogen bromide is preferably used in aqueous solution, very especially preferably as a 48~ strength solution; lithium chloride is preferably employed in polar solvents such as lower alcohols, dimethyl sulfoxide and dimethylformamide;
hydrogenolytic methods are preferably carried out in lower alcohols or carboxylic acids, without or with the addition of a hydrogen transfer agent such as cyclohexene and cyclohexadiene.
The temperature for the elimination reaction is preferably from O~C to the boiling point of the reaction mixture in question.
The elimination reagent is preferably employed in approximately stoichiomeric amounts or in an excess. The excess is especially preferably between one and ten mole equivalents, based on the amount of IX.
Finally, the protected nitro compounds IX can be obtained in a manner known per se by nitrating (protected) phenols, thiophenols or anilines X (cf., for example, Houben-Weyl, Methoden der organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, VoI. 10/1, 1971, p. 479 et seq.):
5 2 ~N~ ~ ~ ~N~
R ~ N R5 R2 ~ N ~ ~ 5 R
nitration R3 X (O/S/N)-protection R3 X NOZ (0/S/N)-pro-10 I tection Rs R6 X IX
15 suitable nitration reagents are, in particular, nitric acid, as a mixture with sulfuric acid or acetic anhydride, or nitronium salts, specifically nitronium tetrafluoroborate.
The mixture composed of nitric acid and sulfuric acid can be composed of any desired weight ratios of the two components;
20 Preferred are those mixtures where the sulfuric acid predominates greatly or acts as the solvent. Similarly, this is also true for the mixture of nitric acid and acetic anhydride.
Nitronium tetrafluoroborate is preferably employed in aprotic 25 Polar solvents, eg. in acetonitrile or nitromethane.
The reaction temperature is generally from (-80) to 80~C, in particular (-20)~C to 30~C.
30 When using the reagent nitric acid in the nitration reactions, the process is preferably carried out with an approximately equimolar amount or especially preferably with an excess of nitration reagent. The excess can be many times the amount of X. Nitronium tetrafluoroborate is preferably 35 employed in equimolar amounts relative to the substrate, or in a small excess of between 1.1 and 1.5 mole equivalents.
The following intermediates may also be nitrated in a similar manner:
nitration RS pzN - ~ ~ R5 N- Y
N- Y
XI XII
3-(genzazol-4-yl)pyrimidinedione derivatives of the formula I
with one or more chiral centers are normally obtained as enantiomer or diastereomer mixtures which, if desired, can be resolved to give the essentially pure isomers by the methods conventionally used for this purpose, for example by means of crystallization or chromatography on an optically active adsorbate. Pure optically active isomers can be prepared advantageously from corresponding optically active starting materials.
Those 3-(benzazol-4-yl)pyrimidinedione derivatives of the formula I where R1 is hydrogen can be converted into their salts in a manner known per se (see, in this context, what has been said for process A)).
The arylureas of the formula III are novel. They can be prepared by methods known per se, for example by one of the following processes:
' CA 02312703 2000-06-OS
Process G~
Reaction of a (3-ketocarboxylic ester XIII with a urea XIV:
O /N~ NH ~ ~ 5 R2 0 + H R
XIII XIV
R1. 0 R4 (Cat.) N
---~~. R2 ~ NH ~ ~ 5 R
III
LZ is lower alkyl, preferably C1-C4-alkyl, or phenyl.
The process is preferably carried out under essentially anhydrous conditions in an inert solvent or diluent, especially preferably in the presence of an acidic or basic catalyst.
Suitable solvents or diluents are, in particular, organic solvents which are miscible with water to give azeotropic mixtures, for example aromatics such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, aliphatic and cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or cyclohexane, but also alcohols such as methanol and ethanol.
Suitable acidic catalysts are, preferably, strong mineral acids such as sulfuric acid and hydrochloric acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid, organic acids such as p-toluenesulfonic acid, and acidic cation exchangers such as "Amberlyst 15"
(Fluka).
Examples of suitable basic catalysts are alkali metal hydrides such as sodium hydride and, especially preferably, alkali metal alkoxides such as sodium methoxide and sodium ethoxide.
XIV and the ~-ketocarboxylic ester XIII are expediently employed in approximately stoichiometric amounts, or else the process is carried out with a small excess of one or the other component, of up to approximately 10 mold.
An amount of 0.5 to 2 molg of catalyst, based on the amount of one of the starting compounds, will normally suffice.
The reaction is generally effected at from 60 to 120~C so as rapidly to eliminate water which forms, preferably at the boiling point of the reaction mixture.
Process H~
Reaction of an enol ether XV with a urea XVI:
OL3 \ N-RZ O + H NH ~ \ R5 \ OL2 N -~ Y
XV XVI
N
NH ~ \ 5 R \ ~ R
III
LZ and L3 are in each case lower alkyl, preferably C1-C4-alkyl, or phenyl.
The reaction is preferably carried out in an inert organic solvent which is miscible with water, eg. an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or a lower alcohol, in particular ethanol, the reaction temperature normally being from 50 to 100~C, preferably the boiling point of the reaction mixture.
However, the reaction can also be carried out in an aromatic diluent such as benzene, toluene and o-, m-, p-xylene, in which case the addition of either an acidic catalyst such as hydrochloric acid and p-toluenesulfonic acid or of a base, for example an alkali metal alkoxide such as sodium methoxide and sodium ethoxide, is recommended. In this process variant, again, the reaction temperature is normally from 50 to 100~C, but preferably 60 to 80~C.
As regards the ratios by weight, what has been said for method G) also applies here.
Process J~
Reaction of an et~aminoester XVII with an isocyanate XVIII:
R1 Rq R1 O R4 \ NH OLZ OCN ~ ~ R5 ~,. R2 N p _ NH ~ ~ 5 R + ~ ~ R
R3 \p N Y R3 OL2 N - Y
XVII XVIII III
L2 is lower alkyl, preferably C1-C4-alkyl, or phenyl.
The reaction is expediently carried out in the presence of an essentially anhydrous aprotic organic solvent or diluent, for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and o-, m-, p-xylene, a halogenated aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichlorethane and chlorobenzene, an aprotic polar solvent such as dimethylformamide, hexamethyl phosphoric triamide and dimethyl sulfoxide, or a mixture of these.
If desired, the process can also be carried out in the presence of a metal hydride base such as sodium hydride and potassium hydride, or an organic tertiary base such as ~
triethylamine and pyridine, it being possible for the organic base to act simultaneously as the solvent.
The starting materials are expediently employed in 5 stoichiometric amounts, or else the process is carried out with a small excess of one or the other component, of up to approximately 10 mol%. If the process is carried out in the absence of a solvent in the presence of an organic base, the latter will be present in a larger excess.
The reaction temperature is preferably from (-80) to 50~C, in particular (-60) to 30~C.
In an especially preferred embodiment, the resulting enamine ester III is converted directly (ie. "in situ") with an excess of base in accordance with process D) to give the corresponding product of value I.
Process K~
Reaction of an enaminoester XVII with a urethane XIX:
~ L40- ~
NH OL2 NH ~ ~ RS RZ N o'NH
R
R -I-(base N - Y N -- Y
XVII XIX III
L2 and L4 independently of one another are lower alkyl, preferably C1-C4-alkyl, or phenyl.
This reaction is expediently carried out in an aprotic polar solvent or diluent such as dimethylformamide, 2-butanone, dimethyl sulfoxide and acetonitrile, advantageously in the presence of a base, for example an alkali metal alkoxide or alkaline earth metal alkoxide, in particular a sodium alkoxide such as sodium methoxide, an alkali metal carbonate or alkaline earth metal carbonate, in particular sodium carbonate, or an alkali metal hydride such as lithium hydride and sodium hydride.
Once to twice the molar amount of base, based on the amount of XVII or XIX, will normally suffice.
The reaction temperature is generally from 80 to 180~C, preferably the boiling point of the reaction mixture.
As regards the weight ratio of the starting compounds, what has been said for method G) also applies here.
In an especially preferred embodiment, a sodium alkoxide is used as the base, and the alcohol which is formed in the course of the reaction is distilled off continuously. The resulting enaminoesters IV can be cyclized in accordance with process D), without being isolated from the reaction mixture, to give a salt of the substituted benzothiazoles I (where R1 = H).
The urethanes XIX, in turn, can be prepared, for example, from the carbonyl chlorides XX and anilines XXI:
O + H N ~ ~ Rs base La ~ N ~ ~ Rs XX ' XXI XIX
To avoid an excess of aniline, it is necessary, as a rule, to add an auxiliary base such as triethylamine, pyridine or the alkali metal carbonates to scavenge the hydrogen chloride which is formed during the reacton. Pyridine is especially suitable since it can be used simultaneously as the solvent.
Suitable solvents/diluents other than pyridine are, in Particular, aromatic hydrocarbons such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, lower alcohols such as methanol and ethanol, aliphatic or cyclic ethers such as dimethoxyethane, tetrahydrofuran and dioxane, carboxylic esters such as ethyl acetate or aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide.
~
The reaction temperature is generally from O~C to reflux temperature of the reaction mixture in question.
The starting materials are expediently employed either in 5 approximately stoichiometric amounts, or else an excess of carbonyl chloride of not more than 10 mol percent is chosen.
The auxiliary base is normally used in an approximately equimalar 10 ~°unt - based on the amount of XX or XXI - or in an excess of up to approx. twice the molar amount. When using pyridine as the auxiliary base, an even larger excess is recommended, in which case the process can be carried out without an additional solvent.
Process L~
Reaction of an isocyanate XXII with an aniline derivative XXI:
\
NCO
O H N ~ ~ 5 ~ Rz N~ NH ~ ~ 5 Rz~ .f. 2 R ~ ~ R
~~ OL2 N - Y N - Y
R3. R3 OL2 XXII XXI III (R1 = H) Lz is lower alkyl, preferably C1-C4-alkyl, or phenyl.
This reaction is expediently carried out in an essentially anhydrous aprotic organic solvent or diluent, for example in the presence of an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and o-, m-, p-xylene, a halogenated aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic polar solvent such as dimethylformamide, hexamethyl phosphoric triamide and dimethyl sulfoxide, or a mixture of these.
If desired, the process can be carried out in the presence of a metal hydride base such as sodium hydride and potassium hydride, an alkali metal or alkaline earth metal alkoxide such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, or of an organic nitrogen base such as ' CA 02312703 2000-06-OS
triethylamine and pyridine, it being possible for the organic base to act simultaneously as the solvent.
The starting materials are expediently employed in approximately stoichiometric amounts, or else one of the components is used in an excess, of up to approximately 20 mol%. If the process is carried out in the absence of a solvent in the presence of an organic base, the latter will advantageously be present in an even larger excess.
The reaction temperature is generally from (-80) to 150~C, preferably (-30)~C to the boiling point of the reaction mixture in question.
The arylanilides of the formula IV are also novel; they, too, can be prepared in a manner known per se, for example by reacting an amide XXIII with a urethane XXIV
in accordance with process M~:
R4 R1 O ~ 0 O
R2 ~ ~ ~ ~ ~OL2 R2 N~OLZ RQ
HN g5 XXIV
H
R3 O N - Y R3 NH ~ ~ RS
N- Y
XXIII IV (R1 = H) Lz is lower alkyl, preferably C1-C4-alkyl, or phenyl.
The reaction is advantageously carried out in an essentially anhydrous solvent/diluent under atmospheric pressure, especially preferably in the presence of an acidic catalyst.
To prepare enamine carboxylates IV where R1 = amino, it is recommended to employ compounds XXIV with protected amino group (for example as hydrazone).
Suitable solvents/diluents are, in particular, organic fluids which can be mixed with water to give an azeotropic mixture, for example aromatics such as benzene, toluene and o-, m-, p-xylene, or halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene.
Suitable catalysts are, in particular, strong mineral acids such as sulfuric acid, organic acids such as p-toluenesulfonic acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid, or acidic cation exchangers such as "Amberlyst 15" (Fluka).
In general, a reaction temperature from approximately 70 to 150~C is sufficient; however, to remove the resulting water of reaction rapidly, the process is expediently carried out at the boiling point of the reaction mixture in question.
XXIII and XXIV are normally employed in approximately stoichiometric amounts; preferably, XXIV is used in a slight excess of up to approximately 20 mol%.
The amide XXIII can be prepared as follows (Process N~):
O
O
~ '~ H2N / \ R5 O \ O N - Y ---~ XXI I I ( R3 = H ) O~ CH3 XXV XXI
The reaction is preferably carried out in an anhydrous inert aprotic solvent, for example in a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, an aromatic hydrocarbon such as benzene, toluene and o-, m-, p-xylene, or an aliphatic or cyclic ether such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane.
The reaction temperature is generally from approximately 70 to 140~C, in particular from 100 to 120~C.
XXV and XXI are normally employed in approximately stoichiometric amounts, or else one of the components is used in an excess of up to approximately 10 mold.
The isocyanates XVIII can be obtained, for example, from the aniline derivatives XXI in accordance with process O~:
HzN ~ ~ R5 + "COC12" -! OCN ~ ~ R5 N- Y N- Y
The process can be carried out in an inert, essentially anhydrous solvent or diluent or in the absence of solvents, 15 the aniline derivatives XXI preferably being reacted with phosgene, a "phosgene equivalent", such as diphosgene, triphosgene and carbonyldiimidazole, or with trichloromethyl chloroformate.
20 Suitable solvents or diluents are, in particular, aprotic organic solvents, for example dimethylformamide or aromatics such as toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic or cyclic 25 ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or esters such as ethyl acetate, and mixtures of these.
The starting materials are expediently employed in 30 approximately stoichiometric amounts, or else one of the components is employed in an excess of up to approx.
200 mol%.
Depending on the aniline derivative XXI employed, it may be 35 advantageous to add a base such as triethylamine, for example in 0.5 times to twice the molar amount, based on the amount of XXI.
40 The reaction temperature is generally from (-20)~C to the reflux temperature of the solvent or reaction mixture in question.
The aniline derivatives XXI, in turn, can be obtained in a manner 45 known per se (cf., for example, Houben-Weyl, Methoden der organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Vol. XI/1, 4th Edition 1957, p. 431 et seq.) by reducing the corresponding nitro derivatives XXVI:
02N ~ ~ R5 - reduction H N ~ ~ 5 2 ~R
N -Y N- Y
XXVI XXI
As regards reducing agents, solvents, reaction temperatures and weight ratios, reference may be made to what has been said above for process F~.
The compounds XXVIII and XXI can also contain one or more chiral centers, in which case they are normally obtained as enantiomer or diastereomer mixtures. If desired, the mixtures can be resolved into the essentially pure isomers by the methods conventionally used for this purpose, for example by means of crystallization or chromatography on an optically active adsorbate. Pure optically active isomers can also be prepared, for example, from corresponding optically active starting materials.
Unless otherwise specified, all the processes described above are expediently carried out under atmospheric pressure or under the inherent pressure of the reaction mixture in question.
In general, the reactants are employed in a molar ratio of 0.95:1 to 5:1.
As a rule, the reaction mixtures are worked up by methods known per se, for example by diluting the reaction solution with water and subsequently isolating the product by means of filtration, crystallization or solvent extraction, or by removing the solvent, partitioning the residue in a mixture of water and a suitable organic solvent and working up the organic phase to give the product.
The compounds I and their agriculturally useful salts are suitable as herbicides, both in the form of isomer mixtures and in the form of the pure isomers. The herbicidal compositions which comprise I effect very good control of vegetation on non-crop areas, especially at high rates of application. In crops such as wheat, rice, maize, Soya and cotton, they act against broad-leaved weeds and grass weeds without inflicting substantial ' CA 02312703 2000-06-OS
damage to the crop plants. This effect is observed mainly at low rates of application.
Depending on the application method in question, the compounds I, or herbicidal compositions comprising them, can also be employed in a further number of crop plants for eliminating undesirable plants. Examples of suitable crops are the following:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec.
rapa, Brassica napus var. napus, Brassica napus var.
napobrassica, Brassica raps var, silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifoliurn), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
In addition, the compounds I can also be used in crops which, by means of breeding, including genetic engineering methods, have been made tolerant to the action of herbicides.
The compounds I, or the herbicidal compositions comprising them, can be used, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring.
The use forms depend on the intended purposes; in any case, they should guarantee the finest possible distribution of the active ingredients according to the invention.
Suitable inert auxiliaries are essentially: mineral oil fractions of medium to high boiling point such as kerosine and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. paraffins, ' CA 02312703 2000-06-OS
tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, eg.
amines such as N-methylpyrrolidone, and water.
Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substrates [sic], as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and these concentrates are suitable for dilution with water.
Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acid, eg, ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylarylsulfonates, of alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.
Powders, materials for spreading and dusts can be prepared by mixing or binding the active substances together with a solid carrier.
Granules, eg. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.
The concentration of the active ingredients I in the ready-to-use preparations can be varied within wide ranges. In general, the formulations comprise approximately from 0.001 to 98% by weight, preferably from 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (in accordance with NMR
spectra).
The formulation examples which follow illustrate the preparation °f such products:
I. 20 parts by weight of Compound No. 1 are dissolved in a mixture composed of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate and 5 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
II. 20 parts by weight of Compound No. 2 are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and 35 finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
III. 20 parts by weight of Active Ingredient No. 4 are dissolved in a mixture composed of 25 parts by weight of 40 cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280~C and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil.
Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
~ CA 02312703 2000-06-OS
IV. 20 parts by weight of Active Ingredient No. 6 are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-a-sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite 5 waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1~ by weight of the active ingredient.
V. 3 parts by weight of Active Ingredient No. 8 are mixed with 97 parts by weight of finely divided kaolin. This gives a dust which comprises 3~ by weight of the active ingredient.
VI. 20 parts by weight of Active Ingredient No. 12 are mixed intimately with 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. This gives a stable oily dispersion.
VII. 1 part by weight of Compound No. 14 is dissolved in a mixture composed of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. The mixture can subsequently be diluted with water to give the desired concentration of active ingredient. This gives a stable emulsion concentrate.
VIII. 1 part by weight of Compound No. 19 is dissolved in a mixture composed of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol~ EM 31 (= nonionic emulsifier based on ethoxylated castor oil; BASF AG). Then, the mixture can be diluted with water to give the desired concentration of active ingredient. This gives a stable emulsion concentrate.
The active ingredients I, or the herbicidal compositions, may be applied pre- or post-emergence. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that they come in as little contact as possible, if any, with the leaves of the sensitive crop plants while reaching the leaves of undesirable plants which grow underneath, or the bare soil surface (post-directed, lay-by).
Depending on the control target, the season, the target plants and the growth stage, the rates of application of active ingredient I are from 0.001 to 3.0, preferably 0.01 to 1.0, kg/ha active substance (a.s.).
To widen the spectrum of action and to achieve synergistic effects, the 3-(benzazol-4-yl)pyrimidinedione derivatives I may be mixed with a large number of representatives of other groups of herbicidal or growth-regulating active ingredients and applied jointly. Suitable components for mixtures are, for example, 12,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy/heteroaryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-(hetaroyl/aroyl)-1,3-cyclohexanediones, heteroaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, areas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and heteroaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.
Furthermore, it may be advantageous to apply the compounds I, alone or in combination with other herbicides, also as a mixture with other crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are employed for remedying nutritional and trace-element deficiencies. Nonphytotoxic oils and oil concentrates may also be added.
Preparation examples:
Example 1 3-[7-Chloro-5-fluoro-1-methyl-1H-benzotriazol-4-yl]-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (Comp. 2) 0.12 g of methyl iodide was added dropwise at 20~C to a mixture of 0.25 g of 3-[7-chloro-5-fluoro-1-methyl-1H-benzotriazol-4-Y1]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione, 0.12 g of potassium carbonate and 20 ml of absolute dimethylformamide. The reaction mixture was subsequently stirred for a further 18 hours, whereupon it was treated with 50 ml of water. Then, the mixture was extracted three times using in each case 20 ml of ethyl acetate. The combined organic phases were washed with water, dried over sodium sulfate and finally concentrated. The crude product was purified by chromatography on silica gel (eluent:
cyclohexane/ethyl acetate = 1:1). Yield: 0.07 g;
1H NMR (270 MHz, in CDC13): 8 [ppm] = 7.45 (d,lH), 6.45 (s,lH), 4.55 (s,3H), 3.60 (s,3H).
Example 2 3-[7-Chloro-5-fluoro-1-methyl-1H-benzotriazol-4-yl]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (Comp. 1) 0.43 g of ethyl 3-amino-4,4,4-trifluorobut-2-enoate in 3 ml of dimethylforinamide was added at O~C in the course of 15 minutes under a nitrogen atmosphere to 0.13 g of sodium methoxide in 7 ml of absolute dimethylformamide. The mixture was first stirred for one and a half hours at 10~C, whereupon a solution of 0.57 g of ethyl 7-chloro-5-fluoro-1-methyl-1H-benzotriazol-4-ylcarbamate in 20 ml of dimethylformamide was added dropwise to the reaction mixture in the course of 15 minutes. The mixture was subsequently heated to 20~C and stirring was continued for 5 minutes. The mixture was then heated to 60~C, and 0.35 g of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was added. Finally, stirring was continued for 4 hours at 120~C and for 18 hours at 20~C.
For working-up, the mixture was poured into 100 ml of a 10~ by weight aqueous potassium carbonate solution. The product of value was extracted by means of diethyl ether (twice 50 ml) and, after the aqueous phase which remained had been brought to a pH of 1 with hydrochloric acid, by means of ethyl acetate (three times 30 ml).
The combined organic phases were then washed with approx. 20 ml of saturated aqueous sodium chloride solution and 30 ml of 10% by weight aqueous lithium chloride solution, then dried over sodium sulfate and finally concentrated. Yield: 0.25 g;
1H NMR (250 MHz, in CDC13): b [ppm) = 10.25 (br,lH), 7.45 (d,lH), 6.30 (s,lH), 4.60 (s,3H).
Step 2.1 2-Chloro-4-fluoro-N-trifluoroacetylaniline 144.3 g of trifluoroacetic anhydride in 150 ml of diethyl ether were added dropwise at 0°C to 100 g of 2-chloro-4-fluoroaniline in 800 ml of absolute diethyl ether. After the mixture had been heated to 20°C, 500 ml of water were added. The organic phase was separated off and washed three times with water, then dried over sodium sulfate and finally concentrated. Yield: 151.5 g;
1H NMR (270 MHz, in CDC13): b [ppm] = 8.35 (br,lH), 8.25 (dd,lH), 7.20 (dd,lH), 7.05 (dt,lH).
Step 2.2 3-Chloro-5-fluoro-2N-trifluoroacetylaminonitrobenzene 375 ml of 98% strength nitric acid were slowly added dropwise at (-5)°C to 75 g of 2-chloro-4-fluoro-N-trifluoroacetylaniline in 753 ml of acetic anhydride. The mixture was then stirred for one hour at (-5)°C, whereupon it was heated to 20°C. The course of the reaction was monitored by means of high-pressure liquid chromatography on an RP1~-18 column (eluent: acetonitrile/water - 7:3). As soon as starting material was no longer detectable, the reaction mixture was poured into an ice-cold saturated aqueous sodium chloride solution. The solid product of value was subsequently separated off, washed with water and dried for several hours in a drying oven under reduced pressure at 20°C.
Yield: 62.3 g;
1H NMR (270 MHz, in CDC13): b [ppm] = 8.50 (br,lH), 7.80 (dd,lH), 7.60 (dd,lH).
1) reversed phase, on silica gel Step 2.3 3-Chloro-5-fluoro-2-(N-methyl-N-trifluoroacetylamino)-nitrobenzene 12.0 g of methyl iodide were added to a mixture of 16.1 g of 3-chloro-5-fluoro-2N-trifluoroacetylaminonitrobenzene, 11.6 g of potassium carbonate and 100 ml of absolute dimethylformamide. The reaction mixture was subsequently stirred for 18 hours at 20~C, whereupon 500 ml of water were added. Then, the mixture was extracted three times with 100 ml of ethyl acetate in each case.
The combined organic phases were dried over sodium sulfate and finally concentrated.
Yield: 16.3 g;
1H NMR (270 MHz, in CDC13): b [ppm] = 7.80 (m,lH), 7.60 (m,lH), 3.40 (s,3H).
Step 2.4 3-Chloro-5-fluoro-2-methylaminonitrobenzene 173 ml of a 1-normal sodium hydroxide solution were added to a solution of 16.3 g of 3-chloro-5-fluoro-2-(N-methyl-N-trifluoro-acetylamino)nitrobenzene in 173 ml of ethanol. The mixture was subsequently stirred for 1 hour, whereupon it was diluted with 500 ml of water. Then, it was extracted three times with 80 ml of ethyl acetate. The combined organic phases were washed with water, dried over sodium sulfate and finally concentrated. Yield:
10.1 g;
1H NMR (270 MHz, in CDC13): b [ppmj = 7.70 (dd,lH), 7.35 (dd,lH), 6.70-6.50 (br,lH), 3.10 (d,3H).
Step 2.5 2-Amino-6-chloro-4-fluoro-N-methylaniline 55.94 g of tin dichloride dehydrate were added to 10.1 g of 3-chloro-5-fluoro-2-methylaminonitrobenzene in 207 ml of absolute ethanol. The mixture was subsequently heated at 50~C, and 0.94 g of sodium boranate in 55 ml of absolute ethanol was added dropwise in such a way that the temperature of the mixture did not exceed 60~C. For working-up, the mixture was poured into 1 1 of ice-water, whereupon the pH was brought to 14 with sodium hydroxide solution. Then, the mixture was extracted three times with 100 ml of tert-butyl methyl ether. The combined organic phases were washed with water, dried over sodium sulfate and finally concentrated. Yield: 7.5 g;
1H NMR (270 MHz, in CDC13): b [ppm] = 6.50 (dd,lH), 6.35 (dd,lH), 3.90-3.60 (br,3H), 2.65 (s,3H).
Step 2.6 5 7-Chloro-5-~luoro-1-methylbenzotriazole A solution of 3.25 g of sodium nitrite in 19 ml of water was added at 5°C to 7.5 g of 2-amino-6-chloro-4-fluoro-N-methylaniline 10 in 117 ml of 10% strength hydrochloric acid. After the reaction mixture had been stirred for one hour at 5°C, it was diluted with 200 ml of water. Then, the solids were separated off, washed with 3x50 ml of water and dried in a vacuum drying oven at 20°C. Yield:
7.2 g;
15 1H NMR (270 MHz, in CDC13): b [ppm] = 7.60 (dd,lH), 7.30 (dd,lH), 4.55 (s,3H).
Step 2.7 20 7-Chloro-5-fluoro-1-methyl-4-nitrobenzotriazole 0.65 ml of 98% strength nitric acid were slowly added dropwise at (-20)°C to 1.5 g of 7-chloro-5-fluoro-1-methylbenzotriazole in 28 ml of concentrated sulfuric acid. Then, the mixture was 25 stirred for one hour at 0°C, whereupon it was heated to 20°C.
Stirring was subsequently continued for 18 hours, and the reaction mixture was then poured into 500 ml of ice-water. The solids were separated off, washed with water and dried in a vacuum drying oven at 20°C. Yield: 1.66 g;
30 1H NMR (270 MHz, in CDC13): b [ppm] = 7.50 (d,lH), 4.65 (s,3H).
Step 2.8 4-Amino-7-chloro-5-fluoro-1-methylbenzotriazole 1.66 g of 7-chloro-5-fluoro-1-methyl-4-nitrobenzotriazole were reduced with tin dichloride/sodium boranate by a method similar to what has been said for step 2.5. Yield: 1.27 g;
1H NMR (250 MHz, in (CD3)2S0): b [ppm] = 7.45 (d,lH), 6.25 (br,2H), 4.45 (s,3H), 4.30 (q,2H), 1.35 (t,3H).
Step 2.9 Ethyl 7-chloro-5-fluoro-1-methyl-1H-benzotriazol-4-ylcarbamate 2.28 g of ethyl chloroformate were slowly added dropwise to 13 ml of absolute pyridine at O~C, whereupon the mixture was stirred at this temperature for 15 minutes. Then, 1.27 g of 4-amino-7-chloro-5-flu4ro-1-methylbenzotriazole in 20 ml of pyridine were added dropwise at O~C. Stirring was subsequently continued, first for 30 minutes at O~C, and the mixture was then heated at 20~C and again stirred for 18 hours. Finally, the reaction mixture was poured into 100 ml of 10~ strength hydrochloric acid. Then, the mixture was extractd three times with 50 ml of tert-butyl methyl ether. The combined organic phases were washed with 100 ml of water and then concentrated.
50 ml of diethyl ether were added to the residue. The undissolved component was separated off and washed with 3x30 ml of diethyl ether. The combined ether phases were concentrated. Yield:
0.37 g;
1H NMR (250 MHz, in CDC13): 8 [ppm] = 7.35 (d,lH), 6.90 (br,lH), 4.55 (s,3H).
Example 3 3-[7-Chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl]-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (Comp. I.5) 2.46 g of 3-[7-chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H
benzimidazol-4-yl]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione were alkylated with methyl iodide by a method similar to the one described in Example 1. The crude product was purified by chromatography on silica gel (eluent: cyclohexane/ethyl acetate =
2:1). Yield: 1.4 g;
1H NMR (250 MHz, in CDC13): b [ppm] = 7.35 (d,lH), 6.40 (s,lHj, 4.30 (s,3H), 3.55 (s,3H).
Example 4 3-[7-Chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl]-1-amino-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (Comp.
6) 0.25 g of 2,4-dinitro-O-aminophenol was added to a mixture of 0.5 g of 3-[7-chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione, 2.35 g of potassium carbonate and 5 ml of ethyl acetate. After the mixture had been stirred for 18 hours at 20~C, it was diluted with 50 ml of ethyl acetate. The resulting mixture was washed with 3x30 ml of water, dried over sodium sulfate and finally concentrated. The crude product was purified by means of medium-pressure liquid chromatography (MPLC; eluent:
cyclohexane/ethyl acetate = 2:1). Yield: 0.4 g;
1H NMR (250 MHz, in CDC13): b [ppm] = 7.35 (d,lH), 6.30 (s,lH), 4.65 (s,2H), 4.25 (s,3H).
Example 5 3-[7-Chloro-5-fluoro-1-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (Comp. 4) 4.31 g of ethyl 3-amino-4,4,4-trifluorobut-2-enoate in 20 ml of dimethylformamide were added dropwise at 0 bis 5~C to 0.82 g of sodium hydride in 50 ml of absolute dimethylformamide. The mixture was then stirred for one hour at the same temperature, whereupon 7-chloro-5-fluoro-4-isocyanato-1-methyl-2-trifluoromethylbenzimidazole (from step 5.4) in 40 ml of dimethylformamide were added at (-30)~C. Stirring was subsequently continued for one hour at (-30)~C and for a further hour at 20~C.
For working-up, the reaction mixture was carefully poured into 200 ml of ice-water. Acidification with 10~ strength hydrochloric acid gave a solid which was filtered off, washed with water and dried in a vacuum drying oven at 20~C. After purification by flash chromatography (eluent: cyclohexane/ethyl acetate = 2:1), 5.08 g of product of value were obtained.
After the solids had been separated off, product of value which still remained in the filtrate (2.46 g) was isolated by extracting the filtrate three times with 200 ml of tert-butyl methyl ether, washing the combined ether phases, drying them over sodium sulfate and concentrating them.
Total yield: 7.54 g;
1H NMR (250 MHz, in CDC13): b [ppm] = 7.40 (d,lH), 6.30 (s,lH), 4.30 (s,3H).
Step 5.1 7-Chloro-5-fluoro-1-methyl-2-trifluoromethylbenzimidazole 15.5 g of 3-chloro-5-fluoro-2-(N-methyl-N-trifluoroacetyl-amino)nitrobenzene (step 2.3) were reduced with tin dichloride/sodium boranate without intermediate isolation by a method similar to what has been said for step 2.5 to give the corresponding amino compound which then underwent spontaneous cyclization, with the elimination of water, to give the product of value. Yield: 9.32 g;
1H NMR (250 MHz, in CDC13): b [ppm] = 7.45 (d,lH), 7.20 (d,lH), 4.25 (s,3H).
Step 5.2 7-Chloro-5-fluoro-1-methyl-4-nitro-2-trifluoromethylbenzimidazole 46.3 ml of 98~ strength nitric acid were slowly added dropwise at O~C to 9.65 g of 7-chloro-5-fluoro-1-methyl-2-trifluoromethyl-benzimidazole in 96.5 ml of acetic anhydride. After the mixture had been stirred for one hour at O~C, it was heated carefully to 20~C. (In the event that an exothermal reaction did commence, the temperature was kept below 25~C by means of an ice bath.) The reaction mixture was subsequently first stirred for another two hours at 20~C and then poured into ice-cold saturated aqueous sodium chloride solution. The solids formed were separated off, washed with water and dried at 20~C in a vacuum drying oven.
Yield: 8.5 g;
1H NMR (400 MHz, in CDC13): 8 [ppm] = 7.40 (d,lH), 4.35 (s,3H).
Step 5.3 4-Amino-7-chloro-5-fluoro-1-methyl-2-trifluoromethylbenzimidazole 8.71 g of 7-chloro-5-fluoro-1-methyl-4-nitro-2-trifluoromethyl-benzimidazole were reduced by means of tin dichloride/sodium boranate by a method similar to what has been said for step 2.5.
Yield: 6.3 g;
1H NMR (270 MHz, in CDC13): 8 [ppm] = 7.05 (d,lH), 4.45 (br,2H), 4.20 (s,3H).
Step 5.4 7-Chloro-5-fluoro-4-isocyanato-1-methyl-2-trifluoromethyl-benzimidazole 23.32 g of diphosgene were added to 6.3 g of 4-amino-7-chloro-5-fluoro-1-methyl-2-trifluoromethylbenzimidazole in 100 ml of absolute toluene. The mixture Was subsequently refluxed for 6 hours. After the reaction mixture had been stirred for a further 18 hours at 20~C, it was concentrated. The crude product obtained was reacted directly, without purification, to give the end product I.4.
Example 6 3-[7-Chloro-1,2-dimethyl-5-fluoro-IH-benzimidazol-4-yl]-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (Comp. 8) 0.33 g of 3-[7-chloro-1,2-dimethyl-5-fluoro-1H-benzimidazol-4-yl]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione was alkylated with methyl iodide by a method similar to what has been said for Example 1. Yield: 0.04 g;
1H NMR (250 MHz, in CDC13): 8 [ppm] = 7.10 (d,lH), 6.40 (s,lH), 4.00 (s,3H), 3.55 (s,3H), 2.55 (s,3H).
Example 7 3-[7-Chloro-1,2-dimethyl-5-fluoro-1H-benzimidazol-4-yl]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (Comp. 7) 7-Chloro-1,2-dimethyl-5-fluoro-4-isocyanatobenzimidazole, from step 7.4, was reacted with ethyl 3-amino-4,4,4-trifluorobut-2-enoate by a method similar to what has been said for Example 5.
The crude product was purified by means of medium-pressure liquid chromatography (eluent: ethyl acetate/methanol = 15:1). Yield:
0.7 g;
iH NMR (270 MHz, in CDC13): b [ppm] = 7.15 (d,lH), 6.20 (s,lH), 4.05 (s,3H), 2.55 (s,3H).
Step 7.I
7-Chloro-1,2-dimethyl-5-fluorobenzimidazole 100 ml of 10~ strength hydrochloric acid were added to 6.96 g of 2-amino-6-chloro-4-fluoro-N-methylaniline (from step 2.5) in 4.1 g of acetic anhydride. The mixture was subsequently refluxed for 4 hours. After cooling, the mixture was taken up in ice-water. It was then neutralized carefully with an aqueous sodium carbonate solution. The solid crude product which had formed was separated off, washed with water and dried in a vacuum drying oven at 20~C. Yield: 7.92 g;
1H NMR (270 MHz, in CDC13): b [ppm] = 7.25 (dd,lH), 6.95 (dd,lH), 4.00 (s,3H), 2.55 (s,3H).
Step 7.2 7-Chloro-1,2-dimethyl-5-fluoro-4-nitrobenzimidazole 5 98% strength nitric acid was added dropwise at from (-5) to not more than O~C to 7.92 g of 7-chloro-1,2-dimethyl-5-fluorobenzimidazole in 139 ml of concentrated sulfuric acid, during which process the course of the reaction was monitored by means of high-performance liquid chromatography (HPLC) on an 10 RP-18 column (eluent: acetonitrile/water = 1:1). As soon as starting material was no longer detectable, the reaction mixture was poured into ice-water, whereupon the pH was brought to 14 by means of sodium hydroxide solution. The solids were separated off, washed with water and dried at 20~C in a vacuum drying oven.
15 The two regioisomeric nitro compounds which had formed were separated by means of flash chromatography on silica gel (eluent:
.ethyl acetate; the product which eluted first was the desired regioisomer). Yield: 5.6 g;
1H NMR (400 MHz, in CDC13): 8 [ppm] = 7.05 (d,lH), 4.10 (s,3H), 20 2~65 (s,3H).
Step 7.3 4-Amino-7-chloro-1,2-dimethyl-5-fluorobenzimidazole 5.6 g of 7-chloro-1,2-dimethyl-5-fluoro-4-nitrobenzimidazole were reduced by means of tin dichloride/sodium boranate by a method similar to what has been said for step 2.5. The crude product obtained was employed directly, without purification, in step ~'4~ Yield: 4.1 g.
Step 7.4 7-Chloro-1,2-dimethyl-5-fluoro-4-isocyanatobenzimidazole 4,1 g of 4-amino-7-chloro-1,2-dimethyl-5-fluorobenzimidazole were reacted with diphosgene by a method similar to what has been said for step 5.4. The crude product obtained was reacted directly, again without purification, to give the end product I.7.
Example 8 3-[7-Chloro-2-dimethylamino-5-fluorobenzoxazol-4-yl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione (Comp. 19) 1.0 g of 3-[2-amino-4-chloro-6-fluoro-3-hydroxyphenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione and 0.5 g of dichloromethyleneimmonium chloride were mixed in 100 ml of ~
1,2-dichloroethane, whereupon the mixture was filled into a glass holder for pressurized containers and heated for 5 hours at 120°C
in a sealed pressurized container. During this process, the inherent pressure of the container climbed to approx. 5 bar. The container was subsequently cooled. The clear product solution was washed with dilute aqueous potassium carbonate solution.
The organic phase was dried over sodium sulfate and finally concentrated. The crude product was purified by flash chromatography using a short column (eluent:
cyclohexane/tert-butyl methyl ether = 8:2). Yield: 0.5 g;
1H NMR (270 MHz, in CDC13): 8 [ppm) = 6.85 (d,lH), 6.4 (s,lH), 3.6 (s,3H), 3.25 (s,6H).
Step 8.1 3-[4-Chloro-6-fluoro-3-methoxy-2-nitrophenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione Nitrating acid, composed of 20.4 ml of concentrated sulfuric acid and 25.5 ml of 98~ strength nitric acid, was slowly added dropwise with cooling to (-20)~C to 51.0 g of 3-[4-chloro-6-fluoro-3-methoxyphenylj-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione in 1 1 of concentrated sulfuric acid.
After the addition had ended, stirring was continued for 30 minutes at (-20)~C. The reaction mixture was then stirred into 1 1 of ice-water. The solids formed were separated off, washed with water and dried in a vacuum drying oven at 20~C. Yield:
57.0 g;
1H NMR (270 MHz, in CDC13): 8 [ppmj = 7.55 (d,lH), 6.35 (s,lH), 4.05 (s,3H), 3.55 (s,3H).
Step 8.2 3-[4-Chloro-6-fluoro-3-hydroxy-2-nitrophenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione 19.0 g of lithium chloride were added to 57.0 g of 3-[4-chloro-6-fluoro-3-methoxy-2-nitrophenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione in approx. 500 ml of absolute dimethylformamide. The mixture was subsequently stirred for 3 hours at 80-90~C. After cooling, 1 1 of water was added to the reaction mixture. The product of value was extracted with 3x200 ml of methyl tert-butyl ether. The ether phase was repeatedly washed with water and then dried and finally concentrated. Yield: 46.1 g;
1H NMR (250 MHz, in CDC13): 8 [ppm] = 7.65 (d,lH), 6.35 (s,lH), 3.60 (s,3H).
Step 8.3 3-[2-Amino-4-chloro-6-fluoro-3-hydroxyphenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione 34 g of iron powder were added at 65~C, a little at a time, to 46.0 g of 3-[4-chloro-6-fluoro-3-hydroxy-2-nitrophenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione in 423 ml of water and 36.8 ml of concentrated hydrochloric acid. The mixture was subsequently refluxed for 3 hours. After cooling, the mixture was shaken with 500 ml of ethyl acetate. The organic phase was freed from the remaining inorganic material by means of filtration on Celite~ (Manville Corporation). The filtrate was dried over sodium sulfate and finally concentrated. Yield: 37.5 g:
1H NMR (270 MHz, in CDC13): 8 [ppm] = 6.65 (d,lH), 6.40 (s,lH), 3.60 (s,3H).
Example 9 3-[7-Chloro-5-fluorobenzoxazol-4-yl]-1-methyl-6-trifluoromethyl-2'4-(1H,3H)-pyrimidinedione (Comp. 12) 0.5 g of trimethyl orthoformate was added to a solution of 0.5 g of 3-[2-amino-4-chloro-6-fluoro-3-hydroxyphenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione (from step 8.3) in 30 ml of absolute methanol. The mixture was then refluxed for 20 hours. Solvent and excess ortho ester were subsequently removed under reduced pressure. The residue was dissolved in ethyl acetate. The organic phase was washed with water and then dried over sodium sulfate and finally concentrated. The crude Product was purified by means of flash chromatography (eluent:
cyclohexane/tert-butyl methyl ether = 3:1). Yield: 0.26 g;
1H NMR (250 MHz, in CDC13): 8 [ppm] = 8.20 (s,lH), 7.40 (d,lH), 6.40 (s,lH), 3.60 (s,3H).
Example 10 3-[7-Chloro-5-fluoro-2-methoxybenzoxazol-4-yl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione (Comp. 14) 1.0 g of 3-[2-amino-4-chloro-6-fluoro-3-hydroxyphenyl]-1-methyl-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione (from step 8.3) was reacted with tetramethyl orthocarbonate by a method similar to what has been said for Example 9. Yield: 0.7 g;
1H NMR (250 MHz, in CDC13): 8 [ppm] = 7.10 (d,lH), 6.40 (s,lH), 4.20 (s,3H), 3.60 (s,3H).
In addition to the 3-(benzazol-4-yl)pyrimidinedione derivatives of the formula I which have been described above, others which were, or can be, prepared in a similar manner are listed in Table 2 which follows:
U
O d' N l0 N M M
e1 O rl 01 I~r-1 I !~ 1 l0 ~Di W rl N I O r1O 1 I tl1n-1 r-I N 00~-~IrlM I~ II1M rl O ~ l0v-iO ri \O 1D-1O
U
II
u, x II
y fh t~1M M t~fM M t'f N
U U
1 I i U V U U U U x U
M
W
U
II
N
II
x H .f.~ ~ .i'.~ ~ G C ~ G'.
O O O O O O O O O O
N 1 1 I ,!a,.QJa ,~.G .O.sa,~.i7.fa U
I i I I 1 I
x x x x x x I I I z z z z z z o 0 0 0 ~ I I I I
o x x x ~ ~ '. ~ ~ ";!
o U U U ~ 0 ~ " ~ ~
_ 4 P4 fx GY,G4R:
z z z N N N N N N N N N N
z ~ I I I 1 ~ v v v v v ~
/ U U U U U U U U U U
U
M
W
a rl R:W W W W W W W W W U W W W
H1N f"1N Y~7N C~'1M M M
x x x x x x x x x x x x U z x U z x U z U U U U
N
O
r~
b O O riN M
z '-1N M C~ lf7l0 I~00 01ri ~-i'-1ri O
N ~D N I~ M
r1 ~' .-1O O
ri ri r-1r-1 r-i C~O rl.-ILC1r-IO N rl rlN '-1rl rl O
e-1rlrl c!rlri O rl rlO riri rl (~'~
E ~ O O ~ O ~ ~ O O ~'-~ O O O N
x N
U
O
N
I
x ~ '"
N
tI
U
x O O
U "
, U
x c~a, - O
~
~
~
M U U ~ x M U ii ~ x x M M M M
n x I I .ON x >,x x x U N x x x x x x G~U C C CLU U U V U V U U tl1U U U I I I O
_I
M
x '>~'d 'C'dU 1 'C7'L3"~ 'Lf 'CT1 TJ'C 'O
a a a a - x ~ a c s~ a s~ a a a ~ ~
N O .C,fa~7.OI .L7.L7.C7.CaO V1 .O.O .L7.~ i I I ,La I I I
M M M
I I I I I r i I I I I I I I I I I x x x I
O O O O O O O O O O O O O O cn v7v7 U U U O
I I I I I I I I I I I I I I I I I N N N I
......-..-..-..-.~....n O O O ...
n n n n n n n n n n n n n n n n n Ulf!7V1 n P4 ~'P4 GGP4'fx W'W' W'f~ fYP:P: RSCYOR.'C4'~.-...
N N N N N N N N N N N N N N N N N ~..,,'t.,"~,N
IIII ItII IIIIII IIII IIII flIIII IIII IIII IIIIII ll PdW W W W W W W W fs.~W W W W W U U U W W W W
M M M M M M M M M M M M M M M N M M M
~.x x x x x x x x x x x x x x x x x x x G:U U U U U U U U U U U U U U U x z x U U U
O d' u7~O l~CD01 O r-1N ch d t11t0 I~fb C1O ~-1N M er 'Zr~"~~ ~ ~ '~~ N N N N N N N N N M (~"1c'~M M M
U
O
,r t3.y l ~-1r-Irlr-Ir-IO
O rlr1 .-Ir-1-rirWC
O O O O O O O
N x 0 o x itr~ r V 5r ()N ~ M ~ Gi M N x ~
r w x U N ~ x x U U U a +~ z a~
b ~ ~ b b b ~ a c a a s~
0 0 0 0 0 o x N .17.Ja.L~tl1.G7.O ..L7z I
x U
U
N
x U
z o 0 0 0 0 0 0 I I t I 1 1 I 1 ., ..., ~ ~... ., r n r n n r . n n P4 t~R: OG4I:Ri A.'fh' N N N N N N N N
I
v ~ v v .r v v U U U U U U U U
x w w w w w w w w M M M M M
x x x x x x U U U x x x U U
O ~7 l0t~ CO01O riN
z M M M M c~"1~ ch ' CA 02312703 2000-06-OS
Use examples The herbicidal action of the 3-(benzazol-4-yl)pyrimidinedione derivatives I was demonstrated by the following greenhouse experiments:
The culture containers used were plastic flowerpots containing, as substrate, loamy sand with approx. 3.0% of humus. The seeds of the test plants were sown in separately for each species.
In the case of the pre-emergence treatment, the active ingredients which were suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with translucent plastic hoods until the plants had rooted. This cover caused uniform germination of the test plants, unless this was adversely affected by the active ingredients.
For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which were suspended or emulsified in water. The test plants for this purpose were either sown directly and grown on in the same containers, or they were raised separately as seedlings and transplanted into the test containers a few days prior to treatment. The rate of application for the post-emergence treatment was 15.6 or 7.8 g/ha a.s. (active substance).
The plants were kept at 10 - 25~C or 20 - 35~C, depending on the species. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.
Evaluation was done on a scale of from 0 to 100. 100 means no plant emergence, or complete destruction of least the aerial parts of the plant, and 0 means no damage, or normal course of growth.
The plants used in the greenhouse experiments belonged to the following species:
Scientific name English name Amaranthus redroot pigweed retroflexus Chenopodium album lambsquarters (goosefoot) Galium aparine catchweed bedstraw Solanum nigrum black nightshade veronica species speedwell species At rates of application of 15.6 and 7.8 g/ha a.s. post-emergence, Compound No. 18 had a very good herbicidal effect against the abovementioned weeds.
Claims
where the variables have the following meanings:
X is oxygen or sulfur;
R1 is hydrogen, amino, C1-C6-alkyl or C1-C6-haloalkyl;
R2 is hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylthio, C1-C6-alkylsulfinyl or C1-C6-alkylsulfonyl;
R3 is hydrogen, halogen or C1-C6-alkyl;
R4 is hydrogen or halogen;
R5 is cyano, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy;
=Y- is a group =N-N(R6)-, =C(ZR7)-N(R6)-, =C(ZR7)-O- or =C(ZR7)-S-;
R6 is C1-C6-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkylsulfonyl, (C1-C6-alkyl)carbonyl, (C1-C6-haloalkyl)carbonyl, (C1-C6-alkyl)thiocarbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6-alkoxy)thiocarbonyl or C1-C6-alkyl which can be substituted by cyano, C1-C6-alkoxy, C1-C6-alkylthio, (C1-C6-alkoxy)carbonyl, (C1-C6-alkylamino)carbonyl, di(C1-C6-alkyl)aminocarbonyl or (C1-C6-alkyl)carbonyloxy;
Z is a chemical bond, oxygen, sulfur, -S(O)-, -S(O)2-, -NH- or -N(R8)-;
R7 and R8 independently of one another are C1-C6-alkyl, C1-C6-haloalkyl, hydroxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C3-C4-alkenyloxy-C1-C4-alkyl, C3-C4-alkynyloxy-C1-C4-alkyl, C3-C8-cycloalkoxy-C1-C4-alkyl, amino-C1-C4-alkyl, C1-C4-alkylamino-C1-C4-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkylthio-C1-C4-alkyl, C3-C4-alkenylthio-C1-C4-alkyl, C3-C4-alkynylthio-C1-C4-alkyl, C1-C4-alkylsulfinyl-C1-C4-alkyl, C1-C4-haloalkylsulfinyl-C1-C4-alkyl, C3-C4-alkenylsulfinyl-C1-C4-alkyl, C3-C4-alkynylsulfinyl-C1-C4-alkyl, C1-C4-alkylsulfonyl-C1-C4-alkyl, C1-C4-haloalkylsulfonyl-C1-C4-alkyl, C3-C4-alkenylsulfonyl-C1-C4-alkyl, C3-C4-alkynylsulfonyl-C1-C4-alkyl, C3-C6-alkenyl, cyano-C3-C6-alkenyl, C3-C6-haloalkenyl, C3-C6-alkynyl, cyano-C3-C6-alkynyl, C3-C6-haloalkynyl, hydroxycarbonyl-C1-C4-alkyl, (C1-C4-alkoxy)carbonyl-C1-C4-alkyl, (C1-C4-alkylthio)carbonyl-C1-C4-alkyl, aminocarbonyl-C1-C4-alkyl, (C1-C4-alkylamino)carbonyl-C1-C4-alkyl, di(C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl, di(C1-C4-alkyl)phosphonyl-C1-C4-alkyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenyl-C1-C4-alkyl, 3- to 7-membered heterocyclyl or heterocyclyl-C1-C4-alkyl, it being possible for each heterocyclyl ring to contain a carbonyl or thiocarbonyl ring member, and it being possible for each cycloalkyl, phenyl and heterocyclyl ring to be unsubstituted or to have attached to it one to four substituents, in each case selected from the group consisting of cyano, nitro, amino, hydroxyl, carboxyl, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkyl)carbonyl, (C1-C4-haloalkyl)carbonyl, (C1-C4-alkyl)carbonyloxy, (C1-C4-haloalkyl)carbonyloxy and di(C1-C4-alkyl)amino, or, if Z is a chemical bond, R7 is, if desired, also hydrogen, hydroxyl, cyano, mercapto, amino, halogen, -CH(OH)-CH2-R9, -CH(halogen)-CH2-R9, -CH2-CH(halogen)-R9, -CH=CH-R9 or -CH=C(halogen)-R9, where R9 is hydroxycarbonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkylthio)carbonyl, aminocarbonyl, (C1-C4-alkylamino)carbonyl or di(C1-C4-alkyl)aminocarbonyl, or R7 and R8 together are a 1,3-propylene, tetramethylene, pentamethylene or ethyleneoxyethylene chain which can in each case be unsubstituted or have attached to it one to four C1-C4-alkyl groups or one or two (C1-C4-alkoxy)carbonyl groups;
or an agriculturally useful salt of a compound I.
2. A 3-(benzazol-4-yl)pyrimidinedione derivative of the formula I as claimed in claim 1 where X is oxygen, R1 is hydrogen, amino or C1-C6-alkyl, R2 is hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl or C1-C6-alkylsulfonyl, R3 is hydrogen, R4 is hydrogen, fluorine or chlorine, R5 is cyano or halogen and R6 is C1-C6-alkyl, C3-C6-alkynyl, C1-C6-alkylsulfonyl or (C1-C6-alkoxy)carbonyl.
3. The use of a 3-(benzazol-4-yl)pyrimidinedione derivative I or an agriculturally useful salt thereof as claimed in claim 1 as herbicide.
4. A herbicidal composition comprising a herbicidally effective amount of at least one 3-(benzazol-4-yl)pyrimidinedione derivative of the formula I or of a salt of I as claimed in claim 1 and at least one liquid and/or solid carrier and, if desired, at least one surfactant.
5. A process for the preparation of herbicidally active compositions, which comprises mixing a herbicidally active amount of at least one 3-(benzazol-4-yl)pyrimidinedione derivative of the formula I or of a salt of I as claimed in claim 1 and at least one inert liquid and/or solid carrier and, if desired, at least one surfactant.
6. A method of controlling undesirable vegetation, which comprises allowing a herbicidally active amount of at least one 3-(benzazol-4-yl)pyrimidinedione derivative of the formula I or of a salt of I as claimed in claim 1 to act on plants, their environment or on seed.
7. An arylurea of the formula III
where L2 is C1-C4-alkyl or phenyl and R1-R5 and Y have the meanings given in claim 1.
8. An arylanilide of the formula IV
where L2 is C1-C4-alkyl or phenyl and R1-R5 and Y have the meanings given in claim 1.
9. A substituted 2-aminophenol, -thiophenol or -aniline of the formula V
where the variables X and R1-R6 have the meanings given in
claim 1.
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DE19755926A DE19755926A1 (en) | 1997-12-17 | 1997-12-17 | Herbicidal 3- (benzazol-4-yl) pyrimidinedione derivatives |
PCT/EP1998/008098 WO1999031091A1 (en) | 1997-12-17 | 1998-12-11 | Herbicides 3-(benzazol-4-yl)pyrimidine-dione-derivatives |
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US8124818B2 (en) | 2004-07-22 | 2012-02-28 | Basf Aktiengesellschaft | Method for the production of 3-phenyl(thio) uracils and dithiouracils |
Families Citing this family (11)
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CN1195753C (en) | 1998-09-09 | 2005-04-06 | 石原产业株式会社 | Fused-benzene derivatives useful as herbicides |
EP1131319B1 (en) * | 1998-11-16 | 2003-09-03 | Basf Aktiengesellschaft | 3- benz(ox/thi)azol-7-yl -1h-pyrimidine-2,4-diones |
DE19937772A1 (en) * | 1999-08-10 | 2001-02-15 | Bayer Ag | Substituted heterocyclyl-2GH-chromenes |
DE50001813D1 (en) * | 1999-08-12 | 2003-05-22 | Basf Ag | SUBSTITUTED BENZOXAZOLES |
US20020111274A1 (en) * | 2000-07-15 | 2002-08-15 | Basf Aktiengesellschaft | 1-alkyl-3-[1-(substituted phenyl) benzotriazol-6-yl] uracils |
US7153583B2 (en) | 2003-05-07 | 2006-12-26 | Shin-Etsu Chemical Co., Ltd. | Liquid silicone rubber coating composition and airbag |
CN100398523C (en) * | 2005-06-13 | 2008-07-02 | 上海师范大学 | 2,4-dichlor phenoxyacetic amide pyrimidine derivative and its preparation method and agricultural composition |
DK2499136T3 (en) | 2009-11-13 | 2014-03-03 | Basf Se | 3- (3,4-dihydro-2H-benzo [1,4] oxazin-6-yl) -1H-pyrimidine-2,4-dione COMPOUNDS AS HERBICIDES |
CN105294671B (en) * | 2014-06-10 | 2018-03-20 | 华中师范大学 | A kind of hybar X class compound and its application |
CN114249710A (en) | 2016-05-24 | 2022-03-29 | 巴斯夫欧洲公司 | Herbicidal uracils |
WO2023205281A1 (en) * | 2022-04-20 | 2023-10-26 | Siemens Healthcare Diagnostics Inc. | Quantitation of alkylphenol ethoxylate compounds in aqueous samples |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
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BE795549A (en) * | 1972-02-18 | 1973-08-16 | Bayer Ag | NEW 1-AMINOURACILS AND THEIR SALTS, THEIR METHOD OF PREPARATION AND THEIR APPLICATION AS HERBICIDES |
JPH05262765A (en) * | 1992-03-18 | 1993-10-12 | Sumitomo Chem Co Ltd | Benzofuran derivative and herbicide containing the same as active ingredient |
DE4329096A1 (en) * | 1993-08-30 | 1995-03-02 | Bayer Ag | Heterocyclylbenzoheterocycles |
US5753595A (en) * | 1995-08-31 | 1998-05-19 | Fmc Corporation | Herbicidal 3-(substituted benzoxazol-7-yl) and 3-(Substituted benzothiazol-7-yl)-1-substituted-6-trifluoromethyl-2 4-(1h 3h)pyrimidinediones |
DE19532048A1 (en) * | 1995-08-31 | 1997-03-06 | Basf Ag | Substituted benzthiazoles as plant protection products |
EP0853620A1 (en) * | 1995-10-04 | 1998-07-22 | Fmc Corporation | Herbicidal heterocyclic benzisoxazoles and benzisoxazolidinones |
WO1997042188A1 (en) * | 1996-05-08 | 1997-11-13 | Kumiai Chemical Industry Co., Ltd. | Indolyl-substituted uracil derivatives and herbicides comprising them as active ingredients |
JP2001511140A (en) * | 1997-02-04 | 2001-08-07 | ビーエーエスエフ アクチェンゲゼルシャフト | Substituted 2- (2,4 (1H, 3H) -pyrimidindione-3-yl) benzothiazole |
US6077812A (en) * | 1997-02-26 | 2000-06-20 | Fmc Corporation | Cycloimido-substituted benzofused heterocyclic herbicides |
-
1997
- 1997-12-17 DE DE19755926A patent/DE19755926A1/en not_active Withdrawn
-
1998
- 1998-11-12 IL IL13630998A patent/IL136309A0/en unknown
- 1998-12-11 WO PCT/EP1998/008098 patent/WO1999031091A1/en not_active Application Discontinuation
- 1998-12-11 AU AU18785/99A patent/AU1878599A/en not_active Abandoned
- 1998-12-11 CA CA002312703A patent/CA2312703A1/en not_active Abandoned
- 1998-12-11 JP JP2000539015A patent/JP2002508369A/en not_active Withdrawn
- 1998-12-11 SK SK750-2000A patent/SK7502000A3/en unknown
- 1998-12-11 PL PL98341306A patent/PL341306A1/en unknown
- 1998-12-11 BR BR9813613-5A patent/BR9813613A/en not_active Application Discontinuation
- 1998-12-11 EP EP98963564A patent/EP1047693A1/en not_active Withdrawn
- 1998-12-11 KR KR1020007006580A patent/KR20010033195A/en not_active Application Discontinuation
- 1998-12-11 CN CN98812332A patent/CN1282331A/en active Pending
- 1998-12-15 ZA ZA9811490A patent/ZA9811490B/en unknown
- 1998-12-17 AR ARP980106442A patent/AR017885A1/en unknown
-
2000
- 2000-06-19 BG BG104546A patent/BG104546A/en unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8124818B2 (en) | 2004-07-22 | 2012-02-28 | Basf Aktiengesellschaft | Method for the production of 3-phenyl(thio) uracils and dithiouracils |
US8252925B2 (en) | 2004-07-22 | 2012-08-28 | Basf Aktiengesellschaft | Method for the production of 3-phenyl(thio)uracils and dithiouracils |
Also Published As
Publication number | Publication date |
---|---|
KR20010033195A (en) | 2001-04-25 |
AR017885A1 (en) | 2001-10-24 |
AU1878599A (en) | 1999-07-05 |
PL341306A1 (en) | 2001-04-09 |
ZA9811490B (en) | 2000-06-15 |
IL136309A0 (en) | 2001-05-20 |
JP2002508369A (en) | 2002-03-19 |
SK7502000A3 (en) | 2001-01-18 |
EP1047693A1 (en) | 2000-11-02 |
CN1282331A (en) | 2001-01-31 |
BR9813613A (en) | 2000-10-10 |
BG104546A (en) | 2001-08-31 |
WO1999031091A1 (en) | 1999-06-24 |
DE19755926A1 (en) | 1999-06-24 |
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