EP0920415A1 - Substituted 2-phenylpyridine as herbicide - Google Patents
Substituted 2-phenylpyridine as herbicideInfo
- Publication number
- EP0920415A1 EP0920415A1 EP97938899A EP97938899A EP0920415A1 EP 0920415 A1 EP0920415 A1 EP 0920415A1 EP 97938899 A EP97938899 A EP 97938899A EP 97938899 A EP97938899 A EP 97938899A EP 0920415 A1 EP0920415 A1 EP 0920415A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- alkoxy
- formula
- hydrogen
- substituted
- 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.)
- Withdrawn
Links
- 150000005360 2-phenylpyridines Chemical class 0.000 title claims abstract description 35
- 239000004009 herbicide Substances 0.000 title claims abstract description 13
- VQGHOUODWALEFC-UHFFFAOYSA-N alpha-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 230000002363 herbicidal effect Effects 0.000 title claims description 17
- -1 C1-C6-akylsulfonyl Chemical group 0.000 claims abstract description 301
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 36
- 230000008569 process Effects 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 17
- 150000002367 halogens Chemical class 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims abstract description 6
- 230000008635 plant growth Effects 0.000 claims abstract description 3
- 125000004738 (C1-C6) alkyl sulfinyl group Chemical group 0.000 claims abstract 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- 239000001257 hydrogen Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 239000000460 chlorine Substances 0.000 claims description 20
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 150000002431 hydrogen Chemical class 0.000 claims description 15
- 230000035613 defoliation Effects 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 239000002274 desiccant Substances 0.000 claims description 8
- ORTFAQDWJHRMNX-UHFFFAOYSA-N hydroxidooxidocarbon(.) Chemical group O[C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-N 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 239000012954 diazonium Substances 0.000 claims description 7
- 150000001989 diazonium salts Chemical class 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 5
- FLIQYTXJLWGVBG-UHFFFAOYSA-N 6-phenylpyridin-3-amine Chemical class N1=CC(N)=CC=C1C1=CC=CC=C1 FLIQYTXJLWGVBG-UHFFFAOYSA-N 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 5
- 229910003106 Zn-Br Inorganic materials 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 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 description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 150000005749 2-halopyridines Chemical class 0.000 claims description 4
- 239000002837 defoliant Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- WJOAJTWVYTULDB-UHFFFAOYSA-N 5-nitro-2-phenylpyridine Chemical class N1=CC([N+](=O)[O-])=CC=C1C1=CC=CC=C1 WJOAJTWVYTULDB-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 4
- 241000251730 Chondrichthyes Species 0.000 claims 2
- 239000003701 inert diluent Substances 0.000 claims 2
- 239000012442 inert solvent Substances 0.000 claims 2
- KPSSHXSATPPVMZ-UHFFFAOYSA-N 2-(4-chloro-3-methoxyphenyl)-5-nitropyridine Chemical compound C1=C(Cl)C(OC)=CC(C=2N=CC(=CC=2)[N+]([O-])=O)=C1 KPSSHXSATPPVMZ-UHFFFAOYSA-N 0.000 claims 1
- KMMGNVLTIQHYFZ-UHFFFAOYSA-N 6-(4-chloro-3-methoxyphenyl)pyridin-3-amine Chemical compound C1=C(Cl)C(OC)=CC(C=2N=CC(N)=CC=2)=C1 KMMGNVLTIQHYFZ-UHFFFAOYSA-N 0.000 claims 1
- 125000004471 alkyl aminosulfonyl group Chemical group 0.000 claims 1
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 claims 1
- 239000012876 carrier material Substances 0.000 claims 1
- 239000002785 defoliant agent Substances 0.000 claims 1
- 125000004750 (C1-C6) alkylaminosulfonyl group Chemical group 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 28
- 241000196324 Embryophyta Species 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000004480 active ingredient Substances 0.000 description 24
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 19
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 17
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- 239000002243 precursor Substances 0.000 description 13
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000012043 crude product Substances 0.000 description 12
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229940125890 compound Ia Drugs 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- 238000006193 diazotization reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 5
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 241000219146 Gossypium Species 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 239000004359 castor oil Substances 0.000 description 5
- 235000019438 castor oil Nutrition 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 244000038559 crop plants Species 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 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 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 235000002595 Solanum tuberosum Nutrition 0.000 description 4
- 244000061456 Solanum tuberosum Species 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- JOHAPTKVNIVCFM-UHFFFAOYSA-N 2,3-dichloro-5-ethylsulfanylpyridine Chemical compound CCSC1=CN=C(Cl)C(Cl)=C1 JOHAPTKVNIVCFM-UHFFFAOYSA-N 0.000 description 3
- XZCPODHGXMYVSR-UHFFFAOYSA-N 2,3-dichloro-5-propan-2-ylsulfanylpyridine Chemical compound CC(C)SC1=CN=C(Cl)C(Cl)=C1 XZCPODHGXMYVSR-UHFFFAOYSA-N 0.000 description 3
- HLTDBMHJSBSAOM-UHFFFAOYSA-N 2-nitropyridine Chemical class [O-][N+](=O)C1=CC=CC=N1 HLTDBMHJSBSAOM-UHFFFAOYSA-N 0.000 description 3
- XTCHZNJJTQACES-UHFFFAOYSA-N 5,6-dichloropyridin-3-amine Chemical compound NC1=CN=C(Cl)C(Cl)=C1 XTCHZNJJTQACES-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 3
- 235000004341 Gossypium herbaceum Nutrition 0.000 description 3
- 240000002024 Gossypium herbaceum Species 0.000 description 3
- 244000020551 Helianthus annuus Species 0.000 description 3
- 235000003222 Helianthus annuus Nutrition 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000003818 flash chromatography Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000003306 harvesting Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000006072 paste Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 235000012015 potatoes Nutrition 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 125000005537 sulfoxonium group Chemical group 0.000 description 3
- GCQRPPPUHXEHJO-UHFFFAOYSA-N (4-chloro-2-fluoro-5-methoxyphenyl)boronic acid Chemical compound COC1=CC(B(O)O)=C(F)C=C1Cl GCQRPPPUHXEHJO-UHFFFAOYSA-N 0.000 description 2
- 125000004739 (C1-C6) alkylsulfonyl group Chemical group 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- RQZNNGOGJZIWIH-UHFFFAOYSA-N 2,3-dichloro-5-ethylsulfinylpyridine Chemical compound CCS(=O)C1=CN=C(Cl)C(Cl)=C1 RQZNNGOGJZIWIH-UHFFFAOYSA-N 0.000 description 2
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 2
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 235000021533 Beta vulgaris Nutrition 0.000 description 2
- 241000335053 Beta vulgaris Species 0.000 description 2
- 240000002791 Brassica napus Species 0.000 description 2
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- 231100001184 nonphytotoxic Toxicity 0.000 description 1
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- 235000016709 nutrition Nutrition 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 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
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- 235000009566 rice Nutrition 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
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- 229960001922 sodium perborate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
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- 229940124530 sulfonamide Drugs 0.000 description 1
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- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 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
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
-
- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
- C07D213/71—Sulfur atoms to which a second hetero atom is attached
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D411/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms
- C07D411/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D411/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
Definitions
- the present invention relates to new substituted 2-phenylpyridines of the formula I.
- R 1 ercapto, hydroxysulfonyl, chlorosulfonyl, aminosulfonyl, C 1 -C 6 -alkylthio, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -alkylsulfonyl,
- R 4 cyano, hydroxy, halogen, -CC 6 alkoxy or phenylmethoxy, where the phenyl ring can be unsubstituted or can carry one to three substituents, each selected from the group consisting of hydroxy, halogen, Ci-Cg-alkyl, C ⁇ -C 6 -haloalkyl, -C-C6-alkoxy, Ci-C ⁇ -haloalkoxy, hydroxycarbonyl, (C ⁇ -C 6 -alkoxy) carbonyl and (C ⁇ -C 6 -alkoxy) - carbonyl -C ⁇ -C 6 - alkoxy;
- R 8 is hydrogen, hydroxy, C ⁇ -C6 alkyl, hydroxycarbonyl -C -C ⁇ - alkyl, (Ci -C 6 -alkoxy) carbonyl -C -C 6 - alkyl, Ci-C6 - alkoxy, C ⁇ -C 6 - Halogenalkoxy, phenyl -C-C 6 alkoxy, C 3 -Cg -alkenyloxy or C 3 -C 6 -alkynyloxy or
- R 9 are hydrogen, C 6 alkyl, Ci -C 6 haloalkyl, C 3 -C 6 alkenyl, - C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl or C ⁇ -C 6 alkoxy C ⁇ -C 6 alkyl;
- R 1X -R 14 independently of one another are hydrogen, Ci-Cg-alkyl or (Ci-C ⁇ -alkoxy) carbonyl;
- the invention also relates to the use of the compounds I as herbicides or for
- Cx-C ⁇ alkoxy for: e.g. OCH 3 , OC 2 H 5 , n-propoxy, OCH (CH 3 ) 2 , n-butoxy, 0CH (CH 3 ) -C 2 H 5 , OCH 2 -CH (CH 3 ) 2 , OC (CH 3 ) 3 , n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2, 2-dimethylpropoxy, 1-ethyl- propoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy,
- (C ⁇ -C 6 -alkoxy) carbonyl-Ci-C ⁇ -alkyl for: C (-Ce-alkyl substituted by (C ⁇ -C 6 ⁇ alkoxy) carbonyl as mentioned above, e.g. for CH 2 COOCH 3 , CH 2 COOC 2 H 5 , CH 2 COOCH 2 -C 2 H 5 , CH 2 COOCH (CH 3 ) 2 , CH 2 COOCH 2 CH 2 -C 2 H 5 , (1-methylpropoxycarbonyl) methyl, (2-methylpropoxycarbonyl) methyl, CH 2 COOC (CH 3 ) 3 , CH 2 COO (CH 2 ) 3 -C 2 H 5 , CH 2 COO (CH 2 ) 4 -C 2 H 5 , CH (CH 3 ) COOCH 3 , CH (CH 3 ) COOC 2 H 5 , CH 2 CH 2 COOCH 3 , CH 2 CH 2 COOCH 3 , CH 2 CH 2 COOC 2 H 5 , CH 2
- C ⁇ -C 6 alkylthio for: for example SCH 3 , SC 2 H 5 , n-propylthio, SCH (CH 3 ) 2 , n-butylthio, 1-methylpropylthio, 2-methylpropylthio, SC (CH 3 ) 3 , 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 -Methylpentylthio, 4-methylpentylthio, 1, 1-dimethylbutylthio, 1, 2-dimethylbutylthio, 1, 3-dimethylbutylthio, 2, 2-dimethylbutylthio, 2,3-d
- C 3 -C 6 alkenyloxy for: for example prop-1-en-l-yloxy, allyloxy, 1-methylethenyloxy, n-buten-1-yloxy, n-buten-2-yloxy, n-buten-3-yloxy, 1-methylprop-l-en-l-yloxy, 2-methylprop-l-en-1-yloxy, l-methylprop-2-en-l-yloxy, 2-methylprop-2-en- 1-yloxy, n- Penten-1-yloxy, n-penten-2-yloxy, n-penten-3-yl - oxy, n-penten-4-yloxy, 1-methylbut-l-en-l-yloxy, 2-methyl-but- 1-en-l-yloxy, 3-methylbut-l-en-l-yloxy, l-methylbut-2-en-1-yloxy, 2-methylbut-2-en-l-yloxy, 3-methylbut-2- en-l-y
- R 5 is hydrogen, nitro, cyano, hydroxylamino, C ⁇ -C 6 alkyl
- R 6 is hydrogen, C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or -C-C 6 alkoxy-C -C 6 alkyl;
- R 15 C ⁇ -C 6 alkyl
- Suitable solvents are e.g. Water, sulfuric acid, carboxylic acids such as acetic acid and trifluoroacetic acid and halogenated hydrocarbons such as dichloromethane and chloroform.
- the oxidizing agent is normally used in at least equimolar amounts, based on the starting compound. In general, an excess of oxidizing agent has proven to be particularly advantageous.
- the substituted 2-phenylpyridines I can normally be prepared by one of the synthesis processes mentioned above. For economic or procedural reasons, however, it may be more expedient to prepare some compounds I from similar 2-phenylpyridines, but which differ in the meaning of a radical.
- the diazotization can also take place in the presence of disulfide VII.
- mineral oil fractions of medium to high boiling point such as
- Kerosene and diesel oil also coal tarols and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, 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, e.g. Amines such as N-methylpyrrolidone and water.
- Paraffins etrahydronaphthalene
- 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 e.g.
- Granules e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.
- Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as corn flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
- mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium s
- the active ingredients I or the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less compatible for certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck wherever possible, while the active ingredients on the leaves underneath are growing undesirably Plants or the uncovered floor area (post-directed, lay-by).
- the substituted 2-phenylpyridines I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
- 1,2,4-thiazadiols, 1,3,4-thiadiazoles, amide, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy- / heteroaryloxyalkanoic acids and their derivatives, benzoic acid and their derivatives, benzo come as mixing partners - thiadiazinone, 2 - (hetaroyl / aroyl) - 1, 3 -cyclohexanedione, heteroaryl-aryl-ke one, benzylisoxazolidinones, meta-CF-phenyl derivatives, carbamates, quinoline carboxylic acid and their derivatives, chloroacetanilides, cyclohexane-1, 3 -dione derivatives, diazines, dichlor
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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Abstract
The present invention pertains to substituted 2-phenylpyridine I and the salts thereof of formula (I), where R1 = SH, SO¿2?NH2, C1-C2-alkylthio, C1-C6-alkyl-sulfinyl, C1-C6-akylsulfonyl, C1-C6alkylaminosulfonyl, Di-(C1-C6alkyl)aminosulfonyl; R?1, R3¿ = H, halogen; R4 = CN, OH, halogen, C¿1?-C6-alkoxy, possibly substituted OCH2-phenyl and R?5¿ have the meanings given in the description. The invention also relates to: the use of compounds (I) as herbicides or as plant dessicating/defoliating agents, the herbicides and the plant dessicating/defoliating agents containing compounds (I) as actives substances, the processes for controlling undesirable plant growth and for dessicating/defoliating plants using compounds (I), the processes for producing compounds (I), herbicides and plant dessicating/defoliating agents by compounds (I), as well as the intermerdiate products of formulae (IIa, V and VI).
Description
SUBSTITUIERTE 2-PHENYLPYRIDINE ALS HERBIZIDESUBSTITUTED 2-PHENYLPYRIDINE AS HERBICIDE
Beschreibungdescription
Die vorliegende Erfindung betrifft neue substituierte 2-Phenyl- pyridine der Formel IThe present invention relates to new substituted 2-phenylpyridines of the formula I.
R5 in der die Variablen folgende Bedeutungen haben:R5 in which the variables have the following meanings:
n Null oder 1;n zero or 1;
R1 ercapto, Hydroxysulfonyl, Chlorsulfonyl , Aminosulfonyl , Cι-C6-Alkylthio, Ci -C6 -Alkylsulf inyl, Ci -C6 -Alkylsulfonyl,R 1 ercapto, hydroxysulfonyl, chlorosulfonyl, aminosulfonyl, C 1 -C 6 -alkylthio, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -alkylsulfonyl,
Ci-Cö-Alkylaminosulfonyl oder Di - (Ci -C6 -alkyl) aminosulfonyl ;Ci-Cö-alkylaminosulfonyl or di - (Ci -C 6 alkyl) aminosulfonyl;
R2,R3 unabhängig voneinander Wasserstoff oder Halogen;R 2 , R 3 independently of one another are hydrogen or halogen;
R4 Cyano, Hydroxy, Halogen, Cι-C6 -Alkoxy oder Phenylmethoxy, wobei der Phenylring unsubstituiert sein oder ein bis drei Substituenten tragen kann, jeweils ausgewählt aus der Gruppe bestehend aus Hydroxy, Halogen, Ci-Cg -Alkyl, Cχ-C6 -Halogenalkyl, Cι-C6-Alkoxy, Ci-Cβ -Halogenalkoxy, Hydroxycarbonyl, (Cχ-C6 -Alkoxy) carbonyl und (Cχ-C6 -Alkoxy) - carbonyl -Cι-C6- alkoxy;R 4 cyano, hydroxy, halogen, -CC 6 alkoxy or phenylmethoxy, where the phenyl ring can be unsubstituted or can carry one to three substituents, each selected from the group consisting of hydroxy, halogen, Ci-Cg-alkyl, Cχ-C 6 -haloalkyl, -C-C6-alkoxy, Ci-Cβ -haloalkoxy, hydroxycarbonyl, (Cχ-C 6 -alkoxy) carbonyl and (Cχ-C 6 -alkoxy) - carbonyl -Cι-C 6 - alkoxy;
R5 Wasserstoff, Nitro, Cyano, Hydroxyla ino, Halogen, Cι-C6-Alkyl, Cι-C6 -Halogenalkyl, -COC1, -CO-OR6, -CO-N(R7)R8, -CO-O- (Cι-C4-Alkylen) -CO-OR6,R 5 is hydrogen, nitro, cyano, hydroxylamine ino, halogen, Cι-C 6 -alkyl, C 6 haloalkyl, -COC1, -CO-OR 6, -CO-N (R 7) R 8, -CO O- (-C 4 alkylene) -CO-OR 6 ,
-CO-O- (Cι-C4-Alkylen) -CO-N(R7) R8, -χl- (C!-C4 -Alkylen) -CO-R6,-CO-O- (-CC 4 alkylene) -CO-N (R 7 ) R 8 , -χ l - (C ! -C 4 alkylene) -CO-R 6 ,
-X1- (Cι-C -Alkylen) -CO-OR6,-X 1 - (-C-alkylene) -CO-OR 6 ,
-X1- (Ci-Cj-Alkylen) -CO-O- (Cχ-C -Alkylen) -CO-OR6,-X 1 - (Ci-Cj-alkylene) -CO-O- (Cχ-C-alkylene) -CO-OR 6 ,
-X1- (Cι-C4 -Alkylen) -CO-N(R7) R8, -χl-R9, -CH=C (R10) -CO-OR6 , -CH=C(R10) -CO-O- (Cι-C4 -Alkylen) -CO-OR6, -CH=C(R10) -CO-N(R7)R8, Formyl , -CO-R6,-X 1 - (-CC 4 alkylene) -CO-N (R 7 ) R 8 , -χ l -R 9 , -CH = C (R 10 ) -CO-OR 6 , -CH = C (R 10 ) -CO-O- (-CC 4 alkylene) -CO-OR 6 , -CH = C (R 10 ) -CO-N (R 7 ) R 8 , formyl, -CO-R 6 ,
-C(R8)=N-OR15, -X1- (C1-C4 -Alkylen) -C (R8) =N-OR15, -CH=C(R10) -C(R8)=N-OR15, -CH (Ci -C6 -Alkoxy) 2 , -N(R16)Rl7, -N(R16) -SO2- (Cι-C6-Alkyl) , -N(Rlfe) -CO- (C± -C6 -Alkyl) , Chlorsulfonyl, Hydroxysulfonyl oder - S02 -N (R18) R19 ; -C (R 8 ) = N-OR 15 , -X 1 - (C 1 -C 4 alkylene) -C (R 8 ) = N-OR 15 , -CH = C (R 10 ) -C (R 8 ) = N-OR 15 , -CH (Ci -C 6 alkoxy) 2 , -N (R 16 ) R 17 , -N (R 16 ) -SO 2 - (-C-C 6 alkyl), -N ( R lfe ) -CO- (C ± -C 6 alkyl), chlorosulfonyl, hydroxysulfonyl or - S0 2 -N (R 18 ) R 19 ;
R6 Wasserstoff, Cχ-C6 -Alkyl, Cι-C6 -Halogenalkyl , C3 -C6 -Alkenyl , C3-C6-Alkinyl, C3 -C6 -Cycloalkyl , Ci -C6 -Alkoxy - Cλ -C6 - alkyl oder 3-Oxetanyl;R 6 is hydrogen, Cχ-C6 alkyl, Cι-C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, Ci -C 6 alkoxy - C λ -C 6 alkyl or 3-oxetanyl;
R7 Wasserstoff oder Cχ-C6- Alkyl ;R 7 is hydrogen or Cχ-C 6 alkyl;
R8 Wasserstoff, Hydroxy, Cι-C6-Alkyl, Hydroxycarbonyl -Ci -Cβ - alkyl, (Ci -C6 -Alkoxy) carbonyl -Ci -C6 - alkyl , Ci -C6- Alkoxy, Cι-C6-Halogenalkoxy, Phenyl -Cι-C6 -alkoxy, C3 -Cg -Alkenyloxy oder C3 -C6 -Alkinyloxy oderR 8 is hydrogen, hydroxy, Cι-C6 alkyl, hydroxycarbonyl -C -Cβ - alkyl, (Ci -C 6 -alkoxy) carbonyl -C -C 6 - alkyl, Ci-C6 - alkoxy, Cι-C 6 - Halogenalkoxy, phenyl -C-C 6 alkoxy, C 3 -Cg -alkenyloxy or C 3 -C 6 -alkynyloxy or
R7 und R8 zusammen eine Tetra- oder Pentamethylenkette, die einen (Ci-Cβ -Alkoxy) carbonylrest tragen kann;R 7 and R 8 together form a tetra or pentamethylene chain which can carry a (Ci-Cβ-alkoxy) carbonyl radical;
R9 Wasserstoff, Cι-C6-Alkyl, Ci -C6 -Halogenalkyl, C3 -C6-Alkenyl,- C3-C6-Alkinyl, C3 -C6 -Cycloalkyl oder Cι-C6 -Alkoxy-Cχ -C6 - alkyl;R 9 are hydrogen, C 6 alkyl, Ci -C 6 haloalkyl, C 3 -C 6 alkenyl, - C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl or Cι-C 6 alkoxy Cχ -C 6 alkyl;
R10 Wasserstoff, Halogen oder Ci-Cβ-Alkyl;R 10 is hydrogen, halogen or Ci-Cβ-alkyl;
R1X-R14 unabhängig voneinander Wasserstoff, Ci-Cg -Alkyl oder (Ci-Cβ -Alkoxy) carbonyl;R 1X -R 14 independently of one another are hydrogen, Ci-Cg-alkyl or (Ci-Cβ-alkoxy) carbonyl;
R15 Wasserstoff, Cι-C6-Alkyl, Phenyl -Ci -C6 -alkyl , (Cι-C6-Alkoxy)carbonyl-Cι-C6-alkyl, C3 -C6-Alkenyl oder C3 -C6-Alkinyl ;R 15 are hydrogen, C 6 alkyl, phenyl -C -C 6 alkyl, (Cι-C 6 -alkoxy) carbonyl-Cι-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 Alkynyl;
R16 Wasserstoff oder Cι-C6-Alkyl;R 16 is hydrogen or -CC 6 alkyl;
R17 Wasserstoff, Ci-Cβ-Al yl, Hydroxycarbonyl -Ci -C6- alkyl, (Ci -Cδ -Alkoxy) carbonyl -Cι-C6- alkyl oder Cι-C6 -Alkoxy;R 17 is hydrogen, Ci-Cβ-Al yl, hydroxycarbonyl -Ci -C 6 - alkyl, (Ci -C δ alkoxy) carbonyl -Cι-C 6 - alkyl or -CC 6 alkoxy;
R18 Wasserstoff oder Cx -C6 -Alkyl;R 18 is hydrogen or C x -C 6 alkyl;
R19 Wasserstoff, Cι-C6 -Alkyl, Hydroxycarbonyl -Cι-C6-alkyl,R 19 is hydrogen, -CC 6 alkyl, hydroxycarbonyl -C-C 6 alkyl,
(Ci-Ce-AlkoxyJcarbonyl-Ci-Cβ-alkyl oder Cι-C6-Alkoxy oder(Ci-Ce-AlkoxyJcarbonyl-Ci-Cβ-alkyl or -CC 6 alkoxy or
R18 und R19 zusammen eine Tetra- oder Pentamethylenkette, die einen (Cι-C6 -Alkoxy) carbonylrest tragen kann;R 18 and R 19 together form a tetra or pentamethylene chain, which can carry a (-C 6 alkoxy) carbonyl radical;
X1-X3 unabhängig voneinander Sauerstoff oder Schwefel,
sowie die landwirtschaftlich brauchbaren Salze der Verbindungen I mit R6 = Wasserstoff.X 1 -X 3 independently of one another oxygen or sulfur, and the agriculturally useful salts of the compounds I with R 6 = hydrogen.
Außerdem betrifft die Erfindung - die Verwendung der Verbindungen I als Herbizide oder zurThe invention also relates to the use of the compounds I as herbicides or for
Desikkation/Defoliation von Pflanzen, herbizide Mittel und Mittel zur Desikkation und/oderDesiccation / defoliation of plants, herbicidal agents and agents for desiccation and / or
Defoliation von Pflanzen, welche die Verbindungen I als wirksame Substanzen enthalten, - Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs und zur Desikkation und/oder Defoliation von Pflanzen mit denDefoliation of plants which contain the compounds I as active substances, - methods for combating undesired plant growth and for desiccating and / or defoliation of plants with the
Verbindungen I,Connections I,
Verfahren zur Herstellung der Verbindungen I und von herbiziden Mitteln und Mitteln zur Desikkation und/oder Defoliation von Pflanzen unter Verwendung der Verbindungen I sowieProcess for the preparation of the compounds I and herbicidal agents and agents for the desiccation and / or defoliation of plants using the compounds I and
Zwischenprodukte der Formeln Ha, V und VI.Intermediate products of the formulas Ha, V and VI.
In der WO 95/02580 wird eine Vielzahl von herbidzid wirksamen 2 -Phenylpyridinen beschrieben. Unter die dortige allgemeine Formel fallen auch einige der vorliegenden Verbindungen I mit R1 = Cι-C4-Alkylthio.WO 95/02580 describes a large number of herbicidally active 2-phenylpyridines. Some of the present compounds I with R 1 = C 1 -C 4 -alkylthio also fall under the general formula there.
Gegenstand der WO 94/05153 sind herbizid wirksame Benzolverbin- düngen, die u.a. auch einen durch Halogen und Methylthio substituierten Pyridinring tragen können. Das spezielle Substitutionsmuster der vorliegenden 2 - Phenylpyridine ist dieser Druckschrift jedoch nicht zu entnehmen.WO 94/05153 relates to herbicidally active benzene compounds which, inter alia, can also carry a pyridine ring substituted by halogen and methylthio. The specific substitution pattern of the present 2-phenylpyridines, however, cannot be found in this publication.
In DE-A 19 500 760, DE-A 19 500 758 und DE-A 19 500 911 werden bereits bestimmte substituierte 2 -Phenylpyridine vom Typ der Verbindungen I mit Mercapto, Ci -C4 -Alkylthio, Ci -C -Alkylsulf inyl oder C1-C4 -Alkylsulfonyl in 5 -Position des Pyridinringes als herbizide und desikkante/defoliante Wirkstoffe beschrieben.DE-A 19 500 760, DE-A 19 500 758 and DE-A 19 500 911 already describe certain substituted 2-phenylpyridines of the type of the compounds I with mercapto, C 1 -C 4 -alkylthio, C 1 -C -alkylsulfinyl or C 1 -C 4 alkylsulfonyl in the 5 position of the pyridine ring as herbicidal and desiccant / defoliant active ingredients.
Die herbizide Wirkung der bekannten Verbindungen bezüglich der Schadpflanzen ist jedoch nicht immer voll befriedigend. Aufgabe der vorliegenden Erfindung war es demnach, neue herbizid wirksame Verbindungen bereitzustellen, mit denen sich unerwünschte Pflanzen besser als bisher gezielt bekämpfen lassen. Die Aufgabe erstreckt sich auch auf die Bereitstellung neuer desikkant/ defoliant wirksamer Verbindungen.However, the herbicidal activity of the known compounds with regard to the harmful plants is not always completely satisfactory. The object of the present invention was therefore to provide new herbicidally active compounds which can be used to control undesirable plants better than before. The task also extends to the provision of new desiccant / defoliant connections.
Demgemäß wurden die eingangs definierten substituierten 2-Phenyl- pyridine der Formel I mit herbizider Wirkung sowie neue Zwischenprodukte V und VI zu deren Herstellung gefunden.
Ferner wurden herbizide Mittel gefunden, die die Verbindungen I enthalten und eine sehr gute herbizide Wirkung besitzen. Außerdem wurden Verfahren zur Herstellung dieser Mittel und Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs mit den Verbindungen I gefunden.Accordingly, the substituted 2-phenylpyridines of the formula I defined at the outset with herbicidal activity and new intermediates V and VI for their preparation have been found. Furthermore, herbicidal compositions have been found which contain the compounds I and have a very good herbicidal action. In addition, processes for the preparation of these compositions and processes for controlling unwanted vegetation using the compounds I have been found.
Des weiteren wurde gefunden, daß die Verbindungen I auch zur Defoliation/Desikkation von Pflanzenteilen geeignet sind, wofür Kulturpflanzen wie Baumwolle, Kartoffel, Raps, Sonnenblume, So a- bohne oder Ackerbohnen, insbesondere Baumwolle und Kartoffel, in Betracht kommen. Diesbezüglich wurden Mittel zur Desikkation und/ oder Defoliation von Pflanzen, Verfahren zur Herstellung dieser Mittel und Verfahren zur Desikkation und/oder Defoliation von Pflanzen mit den Verbindungen I gefunden.Furthermore, it was found that the compounds I are also suitable for defoliation / desiccation of parts of plants, for which crop plants such as cotton, potatoes, rapeseed, sunflower, bean beans or field beans, in particular cotton and potatoes, are suitable. In this regard, agents for the desiccation and / or defoliation of plants, methods for producing these agents and methods for the desiccation and / or defoliation of plants with the compounds I have been found.
Die Verbindungen der Formel I können je nach Substitutionsmuster ein oder mehrere Chiralitatszentren enthalten und liegen dann als Enantio eren- oder Diastereomerengemische vor. Gegenstand der Erfindung sind sowohl die reinen Enantio ere oder Diastereomere als auch deren Gemische.Depending on the substitution pattern, the compounds of the formula I can contain one or more chiral centers and are then present as enantiomer or diastereomer mixtures. The invention relates both to the pure enantiomers or diastereomers and to mixtures thereof.
Die substituierten 2-Phenylpyridme I mit R6 = Wasserstoff können in Form ihrer landwirtschaftlich brauchbaren Salze vorliegen, wobei es auf die Art des Salzes m der Regel nicht ankommt. Im allgemeinen kommen die Salze von solchen Basen in Betracht, bei denen die herbizide Wirkung im Vergleich zu der freien Verbindung I nicht negativ beeinträchtigt ist.The substituted 2-phenylpyrids I with R 6 = hydrogen can be present in the form of their agriculturally useful salts, the type of salt generally not being important. In general, the salts of such bases come into consideration in which the herbicidal action is not adversely affected in comparison with the free compound I.
Als Salze eignen sich besonders diejenigen der Alkalimetalle, vorzugsweise Natrium- und Kaliumsalze, der Erdalkalimetalle, vorzugsweise Calcium- und Magnesiumsalze, die der Übergangs - etalle, vorzugsweise Zink- und Eisensalze, sowie Ammoniumsalze, bei denen das Ammoniumion gewunschtenfalls ein bis vier Cι-C4-Alkyl-, Hydroxy-Cι-C4-alkylsubstituenten und/oder einen Phenyl- oder Benzylsubstituenten tragen kann, vorzugsweise Diiso- propyla rnonium-, Tetramethylammonium-, Tetrabutylammonium-, Tri- methylbenzylammonium- und Trimethyl- (2-hydroxyethyl) -ammoniumsalze, des weiteren Phosphoniumsalze, Sulfomumsalze wie vorzugsweise Tri- (Cι-C4-alkyl) sulfonium-salze, und Sulfoxoniumsalze wie vorzugsweise Tri- (Cχ-C4-alkyl ) sulfoxoniumsalze.Particularly suitable salts are those of the alkali metals, preferably sodium and potassium salts, of the alkaline earth metals, preferably calcium and magnesium salts, those of the transition metals, preferably zinc and iron salts, and also ammonium salts in which the ammonium ion, if desired, one to four C 1 -C 4 -Alkyl-, Hydroxy-Cι-C 4 alkyl substituents and / or a phenyl or benzyl substituent can wear, preferably diisopropyl ammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium and trimethyl (2-hydroxyethyl) - ammonium salts, furthermore phosphonium salts, sulfomum salts such as preferably tri- (C 1 -C 4 -alkyl) sulfonium salts, and sulfoxonium salts such as preferably tri- (Cχ-C 4 -alkyl) sulfoxonium salts.
Die für die Substituenten R1 und R4 bis R19 oder als Reste an einem Phenylring oder an Tetra- oder Pentamethylen genannten organischen Molekulteile stellen Sammelbegriffe für individuelle Aufzählungen der einzelnen Gruppenmitglieder dar. SamtlicheThe organic molecule parts mentioned for the substituents R 1 and R 4 to R 19 or as residues on a phenyl ring or on tetra- or pentamethylene represent collective terms for individual lists of the individual group members
Kohlenstoffketten, also alle Alkyl-, Halogenalkyl-, Phenylalkyl - , Alkylen-, Alkoxy-, Halogenalkoxy-, Phenylalkoxy- , Alkylthio-,
Alkylsulfinyl- , Alkylsulfonyl- , Hydroxycarbonylalkyl-, Alkoxy- carbonyl-, Alkylamino-, Alkenyl-, Alkinyl - , Alkenyloxy- und Alkinyloxy-Teile können geradkettig oder verzweigt sein. Halogenierte Substituenten tragen vorzugsweise ein bis fünf gleiche oder verschiedene Halogenatome.Carbon chains, i.e. all alkyl, haloalkyl, phenylalkyl, alkylene, alkoxy, haloalkoxy, phenylalkoxy, alkylthio, Alkylsulfinyl, alkylsulfonyl, hydroxycarbonylalkyl, alkoxycarbonyl, alkylamino, alkenyl, alkynyl, alkenyloxy and alkynyloxy parts can be straight-chain or branched. Halogenated substituents preferably carry one to five identical or different halogen atoms.
Die Bedeutung Halogen steht jeweils für Fluor, Chlor, Brom oder Iod, insbesondere für Fluor oder Chlor.Halogen is fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine.
Ferner stehen beispielsweise:Furthermore, for example:
C!-C6-Alkyl für: Cx- -Alkyl wie CH3, C2H5, n-Propyl, CH(CH3)2, n-Butyl, CH (CH3) -C2H5, CH2-CH(CH3)2 und C(CH3)3, oder z.B. n-Pentyl, 1-Methylbutyl, 2-Methylbutyl, 3-Methylbutyl, 2, 2-Dimethylpropyl, 1-Ethylpropyl , n-Hexyl, 1 , 1-Dimethyl - propyl , 1, 2-Dimethylpropyl , 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1, 1-Dimethylbutyl , 1,2-Di- ethylbutyl, 1 , 3-Dimethylbutyl , 2 , 2-Dimethylbutyl , 2,3-Dι- methylbutyl, 3 , 3-Dimethylbutyl , 1-Ethylbutyl, 2-Ethylbutyl, 1, 1, 2-Tnmethylpropyl, 1, 2 , 2-Trimethylpropyl, 1-Ethyl-C ! -C 6 alkyl for: Cx- alkyl such as CH 3 , C 2 H 5 , n-propyl, CH (CH 3 ) 2 , n-butyl, CH (CH 3 ) -C 2 H 5 , CH 2 -CH (CH 3 ) 2 and C (CH 3 ) 3 , or, for example, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethyl - Propyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-diethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl , 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-tnmethylpropyl, 1, 2, 2-trimethylpropyl, 1-ethyl-
1-methylpropyl oder l-Ethyl-2-methylpropyl , insbesondere für CH3, C2H5, n-Propyl, CH(CH3)2, n-Butyl, C(CH3)3, n-Pentyl oder n-Hexyl;1-methylpropyl or l-ethyl-2-methylpropyl, in particular for CH 3 , C 2 H 5 , n-propyl, CH (CH 3 ) 2 , n-butyl, C (CH 3 ) 3 , n-pentyl or n- Hexyl;
- Cι-C6-Halogenalkyl für: einen Cι-C6-Alkylrest wie vorstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder Iod substituiert ist, also z.B. CH2F, CHF2, CF3, CH2C1, CH(C1)2, C(C1)3, CHFC1, CF(C1)2, CF2C1, CF2Br, 1-Fluor- ethyl, 2-Fluorethyl, 2-Chlorethyl , 2-Bromethyl, 2-Iodethyl, 2, 2-Difluorethyl, 2, 2, 2-Trifluorethyl, 2-Chlor-2-fluorethyl , 2-Chlor-2, 2-difluorethyl, 2 , 2-Dichlor-2-f luorethyl , 1,2-Di- chlorethyl, 2 , 2 , 2-Trichlorethyl , C2F5, 2-Fluorpropyl, 3-Fluor- propyl , 2 , 2-Difluorpropyl, 2 , 3-Difluorpropyl , 2-Chlorpropyl , 3-Chlorpropyl, 2 , -Dichlorpropyl , 2-Brompropyl, 3-Brompropyl, 3, 3, 3-Trif luorpropyl, 3, 3 , 3-Trichlorpropyl, 2 , 2 , 3 , 3 , 3-Penta- fluorpropyl, CF2-C2F5, 1- (Fluormethyl) -2-fluorethyl, 1- (Chlormethyl ) -2-chlorethyl, 1- (Brommethyl) -2-bromethyl, 4-Fluorbutyl , 4-Chlorbutyl, 4-Brombutyl, Nonafluorbutyl , 5-Fluorpentyl, 5-Chlorpentyl, 5-Brompentyl, 5-Iodpentyl, 5, 5, 5-Trichlorpentyl, Undecafluorpentyl, 6-Fluorhexyl,A Cι-6 alkyl C as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, eg CH 2 F, CHF 2, CF 3, CH: - Cι-C 6 -haloalkyl 2 C1, CH (C1) 2 , C (C1) 3 , CHFC1, CF (C1) 2 , CF 2 C1, CF 2 Br, 1-fluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2 -Iodethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 1,2- Dechloroethyl, 2, 2, 2-trichloroethyl, C 2 F 5 , 2-fluoropropyl, 3-fluoropropyl, 2, 2-difluoropropyl, 2, 3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2, - Dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl, 3, 3, 3-trichloropropyl, 2, 2, 3, 3, 3-pentafluoropropyl, CF 2 -C 2 F 5 , 1 - (Fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, nonafluorobutyl, 5-fluoropentyl, 5-chloropentyl , 5-bromopentyl, 5-iodopentyl, 5, 5, 5-trichlorpe ntyl, undecafluoropentyl, 6-fluorohexyl,
6-Chlorhexyl, 6-Bromhexyl, 6-Iodhexyl, 6, 6, 6-Trichlorhexyl oder Dodecafluorhexyl, insbesondere für CH2F, CHF2, CF3, CH2C1, 2-Fluorethyl, 2-Chlorethyl, 1, 2 -Dichlorethyl , 2, 2, 2-Trifluorethyl oder C2F5; ϊ
Phenyl-Cι-C6-alkyl für: z.B. Benzyl, 1-Phenylethyl , 2-Phenyl- ethyl, 1-Phenylprop-l-yl , 2-Phenylprop-l-yl , 3-Phenylprop- 1-yl, 1-Phenylbut-l-yl, 2-Phenylbut-l-yl , 3-Phenylbut-l-yl, 4-Phenylbut-l-yl, l-Phenylbut-2-yl , 2-Phenylbut-2-yl , 3-Phenylbut-2-yl, 4-Phenylbut-2-yl , 1- (Benzyl ) -eth-l-yl , 1- (Benzyl) -1- (methyl) -eth-l-yl , 1- (Benzyl ) -prop-1-yl oder 2-Phenyl-hex-6-yl, insbesondere für Benzyl oder 2-Phenyl- ethyl;6-chlorohexyl, 6-bromohexyl, 6-iodohexyl, 6, 6, 6-trichlorohexyl or dodecafluorohexyl, especially for CH 2 F, CHF 2 , CF 3 , CH 2 C1, 2-fluoroethyl, 2-chloroethyl, 1, 2 - Dichloroethyl, 2, 2, 2-trifluoroethyl or C 2 F 5 ; ϊ Phenyl-C 6 -C 6 alkyl for: for example benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-l-yl, 2-phenylprop-l-yl, 3-phenylprop-1-yl, 1-phenylbut -l-yl, 2-phenylbut-l-yl, 3-phenylbut-l-yl, 4-phenylbut-l-yl, l-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, 1- (benzyl) -prop-1 -yl or 2-phenyl-hex-6-yl, especially for benzyl or 2-phenyl-ethyl;
C3-C6-Cycloalkyl für: Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl, insbesondere für Cyclopentyl oder Cyclo- hexyl ;C 3 -C 6 cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, in particular for cyclopentyl or cyclohexyl;
Cι-C -Alkylen für: -CH2-, -CH(CH3)-, 1,2-Ethylen, 1, 1-Propylen, 1 , 2-Propylen, 1, 3-Propylen, -C(CH3)2-, 1,1-Butylen, 1,2-Butylen, 1,3-Butylen, 1,4-Butylen, 2,2-Butylen, 2,3-Butylen, 2-Methyl-l , 1-propylen, 2-Methyl-l, 2-propylen oder 2-Methyl-l , 3-propylen, vorzugsweise für Methylen, 1,1-Ethylen, 1,2-Ethylen, 1,1-Propylen oder 2, 2-Propylen;-C -C alkylene for: -CH 2 -, -CH (CH 3 ) -, 1,2-ethylene, 1, 1-propylene, 1, 2-propylene, 1, 3-propylene, -C (CH 3 ) 2 -, 1,1-butylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 2,2-butylene, 2,3-butylene, 2-methyl-l, 1-propylene, 2 -Methyl-1,2-propylene or 2-methyl-1,3-propylene, preferably for methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene or 2,2-propylene;
Cx-Cδ-Alkoxy für: z.B. OCH3, OC2H5, n-Propoxy, OCH(CH3)2, n-Butoxy, 0CH(CH3) -C2H5, OCH2 -CH (CH3) 2 , OC(CH3)3, n-Pentoxy, 1-Methylbutoxy, 2-Methylbutoxy, 3-Methylbutoxy, 1 , 1-Dimethyl - propoxy, 1, 2-Dimethylpropoxy, 2 , 2-Dimethylpropoxy, 1-Ethyl- propoxy, n-Hexoxy, 1-Methylpentoxy, 2-Methylpentoxy, 3-Methylpentoxy, 4-Methylpentoxy, 1, 1-Dimethylbutoxy,Cx-C δ alkoxy for: e.g. OCH 3 , OC 2 H 5 , n-propoxy, OCH (CH 3 ) 2 , n-butoxy, 0CH (CH 3 ) -C 2 H 5 , OCH 2 -CH (CH 3 ) 2 , OC (CH 3 ) 3 , n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2, 2-dimethylpropoxy, 1-ethyl- propoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy,
1, 2-Dimethylbutoxy, 1 , 3-Dimethylbutoxy, 2 , 2-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-Trimethylprop- oxy, 1-Ethyl-l-methylpropoxy oder l-Ethyl-2-methylpropoxy, insbesondere OCH3, OC2H5, OCH(CH3)2 oder OC(CH3)3;2, 3-dimethylbutoxy, 3, 3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2, 2-trimethylpropoxy, 1-ethyl-l-methylpropoxy or l-ethyl- 2-methylpropoxy, especially OCH 3 , OC 2 H 5 , OCH (CH 3 ) 2 or OC (CH 3 ) 3 ;
Ci-Cε-Halogenalkoxy für: Cι-C6-Alkoxy wie vorstehend genannt, das partiell oder vollständig durch Fluor, Chlor, Brom und/oder Iod substituiert ist, also z.B. OCH2F, OCHF2, OCF3, 0CH2C1, OCH (CD 2. 0C(C1)3, OCHFC1, 0CF(C1)2, 0CF2C1, OCF2Br, 1-Fluorethoxy, 2-Fluorethoxy, 2-Bromethoxy, 2-Iodethoxy, 2, 2-Difluorethoxy, 2 , 2 , 2-Trif luorethoxy, 2-Chlor-2-fluor- ethoxy, 2-Chlor-2, 2-difluorethoxy, 2 , 2-Dichlor-2-f luorethoxy, 2, 2, 2-Trichlorethoxy, OC2F5, 2-Fluorpropoxy, 3-Fluorpropoxy, 2-Chlorpropoxy, 3-Chlorpropoxy, 2-Brompropoxy, 3-Brompropoxy,Ci-Cε-haloalkoxy for: -C-C 6 alkoxy as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example OCH 2 F, OCHF 2 , OCF 3 , 0CH 2 C1, OCH (CD. 2 0C (C1) 3, OCHFC1, 0CF (C1) 2 0CF 2 C1, OCF 2 Br, 1-fluoroethoxy, 2-fluoroethoxy, 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, OC 2 F 5 , 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy,
2, 2-Difluorpropoxy, 2 , 3-Difluorpropoxy, 2 , 3-Dichlorpropoxy,2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy,
3, 3, 3-Trif luorpropoxy, 3, 3 , 3-Trichlorpropoxy, 2,2,3,3,3-Pentafluorpropoxy, OCF2-C2F5, 1- (CH2F) -2-f luorethoxy, 1- (CHCl)-2-chlorethoxy, 1- (CH2Br) -2-bromethoxy, 4-Fluorbutoxy, 4-Chlorbutoxy, 4-Brombutoxy, Nonaf luorbutoxy,
5-Fluorpentoxy, 5-Chlorpentoxy, 5-Brompentoxy, 5-Iodpentoxy, Undecaf luorpentoxy , 6-Fluorhexoxy, 6-Chlorhexoxy, 6-Brom- hexoxy oder Dodecafluorhexoxy;3, 3, 3-trifluoropropoxy, 3, 3, 3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, OCF 2 -C 2 F 5 , 1- (CH 2 F) -2-f luorethoxy, 1- (CHCl) -2-chloroethoxy, 1- (CH 2 Br) -2-bromethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy, nonafluorobutoxy, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy or dodecafluorohexoxy;
Phenyl-Cχ-C6-alkoxy für: z.B. Benzyloxy, 1-Phenylethoxy,Phenyl-Cχ-C 6 -alkoxy for: e.g. benzyloxy, 1-phenylethoxy,
2-Phenylethoxy, 1-Phenylprop-l-yloxy, 2-Phenylprop-l-yloxy, 3-Phenylprop-l-yloxy, 1-Phenylbut-l-yloxy, 2-Phenylbut-l-yl - oxy, 3-Phenylbut-l-yloxy , 4-Phenylbut-l-yloxy, 1-Phenylbut- 2-yloxy, 2-Phenylbut-2-yloxy, 3-Phenylbut-2-yloxy, 4-Phenyl- but-2-yloxy, 1- (Benzyl) -eth-1-yloxy, 1- (Benzyl) -1- (methyl) - eth-1-yloxy, 1- (Benzyl) -prop-1-yloxy oder 2-Phenyl-hex-6-yl - oxy, insbesondere für Benzyloxy oder 2-Phenylethoxy;2-phenylethoxy, 1-phenylprop-l-yloxy, 2-phenylprop-l-yloxy, 3-phenylprop-l-yloxy, 1-phenylbut-l-yloxy, 2-phenylbut-l-yl - oxy, 3-phenylbut- l-yloxy, 4-phenylbut-l-yloxy, 1-phenylbut-2-yloxy, 2-phenylbut-2-yloxy, 3-phenylbut-2-yloxy, 4-phenylbut-2-yloxy, 1- (benzyl ) -eth-1-yloxy, 1- (benzyl) -1- (methyl) - eth-1-yloxy, 1- (benzyl) prop-1-yloxy or 2-phenyl-hex-6-yl - oxy, especially for benzyloxy or 2-phenylethoxy;
Cχ-C6-Alkoxy-Cχ-C6-alkyl für: durch Cχ-C6-Alkoxy wie vor- stehend genannt substituiertes Cχ-C6~Alkyl, also z.B. fürCχ-C 6 -alkoxy-Cχ-C 6 -alkyl for: substituted by Cχ-C 6 -alkoxy as mentioned above Cχ-C 6 ~ alkyl, so for example for
CH2OCH3, CH2OC2H5, CH2OCH2-C2H5, CH2OCH (CH3 ) 2 , CH2OCH CH2-C2H5 , (1-Methylpropoxy) methyl, (2-Methylpropoxy) methyl, CH2OC(CH3)3, CH20(CH2)3-C2H5, CH20(CH2)4-C2H5, CH(CH3)OCH3, CH (CH3 ) OC2H5 , CH2CH2OCH3, CH2CH2OC2H5, CH2CH2OCH2-C2H5 , CH2CHOCH (CH3 ) , CH2CH2OCH2CH2-C2H5, 2- (1-Methylpropoxy) ethyl, 2-(2-Methyl- propoxy)ethyl, CH2CH2OC (CH3) 3, CH2CH20 (CH2) 3-C2H5, CH2CH20(CH2)4-C2H5, 2-(0CH3) propyl, 2- (OC2H5) propyl , 2- (OCH2-C2H5) propyl, 2- [OCH (CH3) 2] propyl, 2- (OCH2CH2-C2H5) - propyl, 2- (1-Methylpropoxy) propyl, 2- (2-Methylpropoxy) propyl , 2- [OC(CH3)3] propyl, 3- (OCH3) propyl, 3- (OC2H5) propyl ,CH 2 OCH 3 , CH 2 OC 2 H 5 , CH 2 OCH 2 -C 2 H 5 , CH 2 OCH (CH 3 ) 2 , CH 2 OCH CH 2 -C 2 H 5 , (1-methylpropoxy) methyl, ( 2-methylpropoxy) methyl, CH 2 OC (CH 3 ) 3 , CH 2 0 (CH 2 ) 3 -C 2 H 5 , CH 2 0 (CH 2 ) 4 -C 2 H 5 , CH (CH 3 ) OCH 3 , CH (CH 3 ) OC 2 H 5 , CH 2 CH 2 OCH 3 , CH 2 CH 2 OC 2 H 5 , CH 2 CH 2 OCH 2 -C 2 H 5 , CH 2 CHOCH (CH 3 ), CH 2 CH 2 OCH 2 CH 2 -C 2 H 5 , 2- (1-methylpropoxy) ethyl, 2- (2-methylpropoxy) ethyl, CH 2 CH 2 OC (CH 3 ) 3 , CH 2 CH 2 0 (CH 2 ) 3 -C 2 H 5 , CH 2 CH 2 0 (CH 2 ) 4 -C 2 H 5 , 2- (0CH 3 ) propyl, 2- (OC 2 H 5 ) propyl, 2- (OCH 2 -C 2 H 5 ) propyl, 2- [OCH (CH 3 ) 2 ] propyl, 2- (OCH 2 CH 2 -C 2 H 5 ) propyl, 2- (1-methylpropoxy) propyl, 2- (2-methylpropoxy) propyl , 2- [OC (CH 3 ) 3 ] propyl, 3- (OCH 3 ) propyl, 3- (OC 2 H 5 ) propyl,
3- (OCH -C2H5) propyl, 3- [OCH (CH3) 2] propyl , 3- (OCH2CH2-C2H5) - propyl, 3- (1-Methylpropoxy) propyl , 3- (2-Methylpropoxy) - propyl, 3- [OC (CH3) 3] propyl , 3- [0(CH2) 3-C2H5] propyl, 3- [0(CH2)4-C2H5] propyl, 2- (0CH3)butyl, 2- (OC2H5)butyl, 2-(OCH2-C2H5)butyl, 2- [OCH (CH3) 2] butyl, 2- (OCH2CH2-C2H5) - butyl, 2- (1-Methylpropoxy) butyl, 2- (2-Methylpropoxy) butyl, 2- [OC(CH3)3]butyl, 3- (OCH3)butyl, 3- (OC2H5)butyl, 3-(OCH2-C2H5)butyl, 3- [OCH (CH3) 2] butyl , 3- (OCH2CH2-C2H5) - butyl, 3- (1-Methylpropoxy) butyl, 3- (2-Methylpropoxy)butyl , 3-[OC(CH3)3]butyl, 4- (OCH3)butyl, 4- (OC2H5) butyl,3- (OCH -C 2 H 5 ) propyl, 3- [OCH (CH 3 ) 2 ] propyl, 3- (OCH 2 CH 2 -C 2 H 5 ) propyl, 3- (1-methylpropoxy) propyl, 3 - (2-Methylpropoxy) propyl, 3- [OC (CH 3 ) 3 ] propyl, 3- [0 (CH 2 ) 3 -C 2 H 5 ] propyl, 3- [0 (CH 2 ) 4 -C 2 H 5 ] propyl, 2- (0CH 3 ) butyl, 2- (OC 2 H 5 ) butyl, 2- (OCH 2 -C 2 H 5 ) butyl, 2- [OCH (CH 3 ) 2 ] butyl, 2- (OCH 2 CH 2 -C 2 H 5 ) - butyl, 2- (1-methylpropoxy) butyl, 2- (2-methylpropoxy) butyl, 2- [OC (CH 3 ) 3 ] butyl, 3- (OCH 3 ) butyl, 3- (OC 2 H 5 ) butyl, 3- (OCH 2 -C 2 H 5 ) butyl, 3- [OCH (CH 3 ) 2 ] butyl, 3- (OCH 2 CH 2 -C 2 H 5 ) - butyl, 3- (1-methylpropoxy) butyl, 3- (2-methylpropoxy) butyl, 3- [OC (CH 3 ) 3 ] butyl, 4- (OCH 3 ) butyl, 4- (OC 2 H 5 ) butyl ,
4-(OCH2-C2H5)butyl, 4-[OCH(CH3)2]butyl, 4- (OCH2CH2-C2H5) - butyl, 4- (1-Methylpropoxy) butyl, 4- (2-Methylpropoxy) butyl, 4-[OC(CH3)3]butyl, 4- [0 (CH2) 3-C2H5] butyl , 4- [0 (CH2) 4-C2H5] - butyl, 5- (0CH3) pentyl, 5- (OC2H5) pentyl, 5- (OCH2-C2H5)pentyl, 5- [OCH (CH3)2] pentyl, 5- (OCH2CH2-C2H5) pentyl, 5- (1-Methyl- propoxy) pentyl, 5- (2-Methylpropoxy) pentyl, 5- [OC (CH3) 3] pentyl , 5- [0(CH2)3-C2H5] pentyl, 5- [0(CH2) 4-C2H5] pentyl , 6- (OCH3) hexyl , 6-(OC2H5)hexyl, 6- (OCH2-C2H5) hexyl, 6- [OCH(CH3) 2] hexyl , 6-(OCH2CH2-C2H5)hexyl, 6- (1-Methylpropoxy) hexyl, 6-(2-Methyl- propoxy) hexyl , 6- [OC (CH3) 3] hexyl, 6- [0 (CH2) 3-C2H5] hexyl oder4- (OCH 2 -C 2 H 5 ) butyl, 4- [OCH (CH 3 ) 2 ] butyl, 4- (OCH 2 CH 2 -C 2 H 5 ) butyl, 4- (1-methylpropoxy) butyl, 4- (2-methylpropoxy) butyl, 4- [OC (CH 3 ) 3 ] butyl, 4- [0 (CH 2 ) 3 -C 2 H 5 ] butyl, 4- [0 (CH 2 ) 4 -C 2 H 5 ] - butyl, 5- (0CH 3 ) pentyl, 5- (OC 2 H 5 ) pentyl, 5- (OCH 2 -C 2 H 5 ) pentyl, 5- [OCH (CH 3 ) 2 ] pentyl, 5 - (OCH 2 CH 2 -C 2 H 5 ) pentyl, 5- (1-methylpropoxy) pentyl, 5- (2-methylpropoxy) pentyl, 5- [OC (CH 3 ) 3 ] pentyl, 5- [0 (CH 2 ) 3 -C 2 H 5 ] pentyl, 5- [0 (CH 2 ) 4 -C 2 H 5 ] pentyl, 6- (OCH 3 ) hexyl, 6- (OC 2 H 5 ) hexyl, 6- (OCH 2 -C 2 H 5 ) hexyl, 6- [OCH (CH 3 ) 2 ] hexyl, 6- (OCH 2 CH 2 -C 2 H 5 ) hexyl, 6- (1-methylpropoxy) hexyl, 6- ( 2-methyl-propoxy) hexyl, 6- [OC (CH 3 ) 3 ] hexyl, 6- [0 (CH 2 ) 3 -C 2 H 5 ] hexyl or
6- [0(CH2)4-C H5] hexyl, insbesondere für CH20CH3, CH(CH3)OCH3, CH3CH2OCH3 oder CH (CH3) CH2OCH3;6- [0 (CH 2 ) 4 -CH 5 ] hexyl, especially for CH 2 0CH 3 , CH (CH 3 ) OCH 3 , CH 3 CH 2 OCH 3 or CH (CH 3 ) CH 2 OCH 3 ;
?
Hydroxycarbonyl-C -C6-alkyl für: z.B. CH2COOH, CH(CH3)C00H, CH2CH2COOH, l-(COOH)prop-l-yl, 2- (COOH) prop-1-yl , 3- (COOH)prop-l-yl, 1- (COOH)but-l-yl , 2- (COOH)but-l-yl, 3- (COOH)but-l-yl, 4-(COOH)but-l-yl, 1- (COOH) but-2-yl , 2- (COOH)but-2-yl, 3- (COOH)but-2-yl , 4- (COOH) but-2-yl , 1- (CH2COOH) eth-l-yl, 1- (CH2COOH) -1- (CH3) -eth-l-yl, 1- (CH2COOH)prop-l-yl, 5- (COOH) ent-1-yl oder 6- (COOH) hex- 1-yl;? Hydroxycarbonyl-C -C 6 -alkyl for: for example CH 2 COOH, CH (CH 3 ) C00H, CH 2 CH 2 COOH, l- (COOH) prop-l-yl, 2- (COOH) prop-1-yl, 3- (COOH) prop-l-yl, 1- (COOH) but-l-yl, 2- (COOH) but-l-yl, 3- (COOH) but-l-yl, 4- (COOH) but -l-yl, 1- (COOH) but-2-yl, 2- (COOH) but-2-yl, 3- (COOH) but-2-yl, 4- (COOH) but-2-yl, 1 - (CH 2 COOH) eth-l-yl, 1- (CH 2 COOH) -1- (CH 3 ) -eth-l-yl, 1- (CH 2 COOH) prop-l-yl, 5- (COOH ) ent-1-yl or 6- (COOH) hex-1-yl;
(Cχ-C6-Alkoxy) carbonyl für: COOCH3, COOC2H5, n-Propoxy- carbonyl, OCH(CH3)2, n-Butoxycarbonyl, 1-Methylpropoxy- carbonyl, 2-Methylpropoxycarbonyl, OC(CH3)3, n-Pentoxy- carbonyl , 1-Methylbutoxycarbonyl, 2-Methylbutoxycarbonyl, 3-Methylbutoxycarbonyl , 2, 2-Dimethylpropoxycarbonyl , 1-Ethyl- propoxycarbonyl, n-Hexoxycarbonyl, 1 , 1-Dimethylpropoxy- carbonyl, 1 , 2-Dimethylpropoxycarbonyl , 1-Methylpentoxy- carbonyl, 2-Methylpentoxycarbonyl, 3-Methylpentoxycarbonyl , 4-Methylpentoxycarbonyl, 1, 1-Dimethylbutoxycarbonyl , 1,2-Di- methylbutoxycarbonyl , 1 , 3-Dimethylbutoxycarbonyl , 2,2-Di- methylbutoxycarbonyl , 2 , 3-Dimethylbutoxycarbonyl , 3,3-Di- methylbutoxycarbonyl, 1-Ethylbutoxycarbonyl , 2-Ethylbutoxy- carbonyl, 1 , 1 , 2-Trimethylpropoxycarbonyl, 1 , 2 , 2-Trimethyl - propoxycarbonyl, l-C2Hs-l-CH3-propoxycarbonyl oder l-C2H5-2-CH -propoxycarbonyl, insbesondere für COOCH3, COOC2H5 oder COOC(CH3)3;(Cχ-C 6 -alkoxy) carbonyl for: COOCH 3 , COOC 2 H 5 , n-propoxycarbonyl, OCH (CH 3 ) 2 , n-butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl, OC (CH 3 ) 3 , n-Pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2, 2-dimethylpropoxycarbonyl, 1-ethyl-propoxycarbonyl, n-hexoxycarbonyl, 1, 1-dimethylpropoxycarbonyl, 1, 2-dimethylpropoxycarbonyl , 1-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 1, 1-dimethylbutoxycarbonyl, 1,2-dimethylbutoxycarbonyl, 1, 3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 2, 3 -Dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1, 1, 2-trimethylpropoxycarbonyl, 1, 2, 2-trimethylpropoxycarbonyl, 1C 2 Hs-1-CH 3 -propoxycarbonyl or IC 2 H 5 -2-CH-propoxycarbonyl, in particular for COOCH 3 , COOC 2 H 5 or COOC (CH 3 ) 3 ;
(Cχ-C6-Alkoxy) carbonyl-Ci-Cβ-alkyl für: durch (Cχ-C6~Alkoxy) - carbonyl wie vorstehend genannt substituiertes Cχ-Ce-Alkyl, also z.B. für CH2COOCH3, CH2COOC2H5, CH2COOCH2-C2H5, CH2COOCH(CH3)2, CH2COOCH2CH2-C2H5, ( 1-Methylpropoxycarbonyl) - methyl, (2-Methylpropoxycarbonyl) methyl, CH2COOC (CH3) 3, CH2COO(CH2)3-C2H5, CH2COO(CH2)4-C2H5, CH (CH3 ) COOCH3 , CH(CH3)COOC2H5, CH2CH2COOCH3 , CH2CH2COOC2H5, CH2CH2COOCH2-C2H5 , CH2CH2COOCH(CH3)2, CH2CH2COOCH2CH2-C2H5 , 2- (1-Methylpropoxy- carbonyl )ethyl, 2- (2-Methylpropoxycarbonyl) ethyl,(Cχ-C 6 -alkoxy) carbonyl-Ci-Cβ-alkyl for: C (-Ce-alkyl substituted by (Cχ-C 6 ~ alkoxy) carbonyl as mentioned above, e.g. for CH 2 COOCH 3 , CH 2 COOC 2 H 5 , CH 2 COOCH 2 -C 2 H 5 , CH 2 COOCH (CH 3 ) 2 , CH 2 COOCH 2 CH 2 -C 2 H 5 , (1-methylpropoxycarbonyl) methyl, (2-methylpropoxycarbonyl) methyl, CH 2 COOC (CH 3 ) 3 , CH 2 COO (CH 2 ) 3 -C 2 H 5 , CH 2 COO (CH 2 ) 4 -C 2 H 5 , CH (CH 3 ) COOCH 3 , CH (CH 3 ) COOC 2 H 5 , CH 2 CH 2 COOCH 3 , CH 2 CH 2 COOC 2 H 5 , CH 2 CH 2 COOCH 2 -C 2 H 5 , CH 2 CH 2 COOCH (CH 3 ) 2 , CH 2 CH 2 COOCH 2 CH 2 -C 2 H 5 , 2- (1-methylpropoxycarbonyl) ethyl, 2- (2-methylpropoxycarbonyl) ethyl,
CH2CH2COOC(CH3)3, CH2CH2COO(CH2)3-C2H5 CH2CH2COO (CH2) 4-C2H5, 2- (COOCH3) propyl, 2- (COOC2H5) propyl , 2- (COOCH2-C2H5) propyl , 2- [COOCH(CH3)2] propyl, 2- (COOCH2CH2-C2H5) propyl, 2-(l-Methyl- propoxycarbonyl ) propyl , 2- ( 2-Methylpropoxycarbony1) propyl , 2- [COOC(CH3)3] propyl, 3- (COOCH3) propyl , 3- (COOC2H5) propyl, 3- (COOCH2-C2H5) propyl, 3- [COOCH(CH3) 2] propyl, 3- (COOCH2CH2-C2H5) propyl, 3- (1-Methylpropoxycarbonyl) ropyl , 3- (2 -Methylpropoxycarbonyl) propyl, 3- [COOC (CH3) 3] propyl, 3- [COO (CH2) 3-C2H5] propyl, 3- [COO (CH2) 4-C2H5] propyl, 2-(COOCH3)butyl, 2- (COOC2H5)butyl , 2- (COOCH2-C2H5) butyl,CH 2 CH 2 COOC (CH 3 ) 3 , CH 2 CH 2 COO (CH 2 ) 3 -C 2 H 5 CH 2 CH 2 COO (CH 2 ) 4 -C 2 H 5 , 2- (COOCH 3 ) propyl, 2- (COOC 2 H 5 ) propyl, 2- (COOCH 2 -C 2 H 5 ) propyl, 2- [COOCH (CH 3 ) 2 ] propyl, 2- (COOCH 2 CH 2 -C 2 H 5 ) propyl, 2- (l-methylpropoxycarbonyl) propyl, 2- (2-methylpropoxycarbonyl) propyl, 2- [COOC (CH 3 ) 3 ] propyl, 3- (COOCH 3 ) propyl, 3- (COOC 2 H 5 ) propyl, 3- (COOCH 2 -C 2 H 5 ) propyl, 3- [COOCH (CH 3 ) 2 ] propyl, 3- (COOCH 2 CH 2 -C 2 H 5 ) propyl, 3- (1-methylpropoxycarbonyl) ropyl, 3 - (2-Methylpropoxycarbonyl) propyl, 3- [COOC (CH 3 ) 3 ] propyl, 3- [COO (CH 2 ) 3 -C 2 H 5 ] propyl, 3- [COO (CH 2 ) 4 -C 2 H 5 ] propyl, 2- (COOCH 3 ) butyl, 2- (COOC 2 H 5 ) butyl, 2- (COOCH 2 -C 2 H 5 ) butyl,
2-[COOCH(CH3)2]butyl, 2- (COOCH2CH2-C2H5) butyl , 2-(l-Methyl- propoxycarbonyl) butyl, 2- (2-Methylpropoxycarbonyl ) butyl ,2- [COOCH (CH 3 ) 2 ] butyl, 2- (COOCH 2 CH 2 -C 2 H 5 ) butyl, 2- (l-methylpropoxycarbonyl) butyl, 2- (2-methylpropoxycarbonyl) butyl,
β
2- [COOC(CH3)3] butyl, 3- (COOCH3)butyl , 3- (COOC2H5) butyl , 3- (COOCH2-C2H5)butyl, 3- [COOCH (CH3 ) 2] butyl ,β 2- [COOC (CH 3 ) 3 ] butyl, 3- (COOCH 3 ) butyl, 3- (COOC 2 H 5 ) butyl, 3- (COOCH 2 -C 2 H 5 ) butyl, 3- [COOCH (CH 3 ) 2 ] butyl,
3- (COOCH2CH2-C2H5)butyl, 3- (1-Methylpropoxycarbonyl) butyl, 3- (2 -Methylpropoxycarbonyl) butyl, 3- [COOC (CH3) 3] butyl, 4- (COOCH3) butyl, 4- (COOC2H5) butyl , 4- (COOCH2-C2H5) butyl ,3- (COOCH 2 CH 2 -C 2 H 5 ) butyl, 3- (1-methylpropoxycarbonyl) butyl, 3- (2-methylpropoxycarbonyl) butyl, 3- [COOC (CH 3 ) 3 ] butyl, 4- (COOCH 3 ) butyl, 4- (COOC 2 H 5 ) butyl, 4- (COOCH 2 -C 2 H 5 ) butyl,
4- [COOCH (CH3)2] butyl, 4- (COOCH2CH2-C2H5) butyl , 4-(l-Methyl- propoxycarbonyl) butyl, 4- (2-Methylpropoxycarbonyl) butyl ,4- [COOCH (CH 3 ) 2 ] butyl, 4- (COOCH 2 CH 2 -C 2 H 5 ) butyl, 4- (l-methylpropoxycarbonyl) butyl, 4- (2-methylpropoxycarbonyl) butyl,
4- [COOC (CH3)3] butyl, 4- [COO (CH2) 3-C2H5] butyl ,4- [COOC (CH 3 ) 3 ] butyl, 4- [COO (CH 2 ) 3 -C 2 H 5 ] butyl,
4- [COO (CH2)4-C2H5] butyl, 5- (COOCH3 ) pentyl , 5- (COOC2H5)pentyl, 5- (COOCH -C2H5)pentyl, 5- [COOCH (CH3) ] pentyl ,4- [COO (CH 2 ) 4 -C 2 H 5 ] butyl, 5- (COOCH 3 ) pentyl, 5- (COOC 2 H 5 ) pentyl, 5- (COOCH -C 2 H 5 ) pentyl, 5- [ COOCH (CH 3 )] pentyl,
5- (COOCH2CH2-C2H5) pentyl, 5- (1-Methylpropoxycarbonyl) pentyl , 5- (2 -Methylpropoxycarbonyl) pentyl, 5- [COOC(CH3)3] pentyl,5- (COOCH 2 CH 2 -C 2 H 5 ) pentyl, 5- (1-methylpropoxycarbonyl) pentyl, 5- (2-methylpropoxycarbonyl) pentyl, 5- [COOC (CH 3 ) 3 ] pentyl,
5- [COO(CH2) 3-C2H5] pentyl, 5- [COO (CH2) 4-C2H5] pentyl ,5- [COO (CH 2 ) 3 -C 2 H 5 ] pentyl, 5- [COO (CH 2 ) 4 -C 2 H 5 ] pentyl,
6- (COOCH3) hexyl, 6- (COOC2H5) hexyl, 6- (COOCH2-C2H5) hexyl , 6- [COOCH (CH3)2] hexyl, 6- (COOCH2CH2-C2H5) hexyl , 6-(l-Methyl- propoxycarbonyl) hexyl, 6- (2 -Methylpropoxycarbonyl) hexyl , 6- [COOC (CH3) 3] hexyl, 6- [COO (CH2) 3-C2H5] hexyl oder 6- [COO(CH2) -C2H5] hexyl, insbesondere für CH2COOCH3, CH2COOCH(CH3)2 oder CH (CH3 ) COOCH3;6- (COOCH 3 ) hexyl, 6- (COOC 2 H 5 ) hexyl, 6- (COOCH 2 -C 2 H 5 ) hexyl, 6- [COOCH (CH 3 ) 2 ] hexyl, 6- (COOCH 2 CH 2 -C 2 H 5 ) hexyl, 6- (l-methylpropoxycarbonyl) hexyl, 6- (2-methylpropoxycarbonyl) hexyl, 6- [COOC (CH 3 ) 3 ] hexyl, 6- [COO (CH 2 ) 3 - C 2 H 5 ] hexyl or 6- [COO (CH 2 ) -C 2 H 5 ] hexyl, in particular for CH 2 COOCH 3 , CH 2 COOCH (CH 3 ) 2 or CH (CH 3 ) COOCH 3 ;
(Cχ-C6-Alkoxy) carbonyl-Cχ-C6-alkoxy für: durch (Cχ-C6-Alkoxy) - carbonyl wie vorstehend genannt substituiertes Cχ-C6-Alkoxy, also z.B. für OCH2COOCH3, OCH2COOC2H5, OCH2COOCH2-C2H5, OCH COOCH(CH3)2, OCH COOCH2CH2-C2H5, ( 1-Methylpropoxycarbonyl ) - methoxy, (2-Methylpropoxycarbonyl)methoxy, OCH2COOC (CH3) 3 ,(Cχ-C 6 alkoxy) carbonyl-Cχ-C 6 -alkoxy of: by (Cχ-C 6 alkoxy) - carbonyl as mentioned above substituted Cχ-C6 alkoxy, eg for OCH 2 COOCH 3, OCH 2 COOC 2 H 5 , OCH 2 COOCH 2 -C 2 H 5 , OCH COOCH (CH 3 ) 2 , OCH COOCH 2 CH 2 -C 2 H 5 , (1-methylpropoxycarbonyl) methoxy, (2-methylpropoxycarbonyl) methoxy, OCH 2 COOC (CH 3 ) 3 ,
OCH2COO(CH2)3-C2H5, OCH COO(CH2)4-C H5, OCH (CH3 ) COOCH3 , OCH(CH3)COOC2H5, OCH2CH2COOCH3 , OCH2CH2COOC2H5,OCH 2 COO (CH 2 ) 3 -C 2 H 5 , OCH COO (CH 2 ) 4 -CH 5 , OCH (CH 3 ) COOCH 3 , OCH (CH 3 ) COOC 2 H 5 , OCH 2 CH 2 COOCH 3 , OCH 2 CH 2 COOC 2 H 5 ,
OCH2CH2COOCH2-C2H5, OCH2CH2COOCH (CH3 ) 2 , OCH2CH2COOCH CH2-C2H5 , 2- ( 1 -Methylpropoxycarbonyl ) ethoxy, 2- (2-Methylpropoxy- carbonyl) ethoxy, OCH2CH2COOC (CH3) 3, OCH2CH2COO (CH2) 3-C2H5,OCH 2 CH 2 COOCH 2 -C 2 H 5 , OCH 2 CH 2 COOCH (CH 3 ) 2 , OCH 2 CH 2 COOCH CH 2 -C 2 H 5 , 2- (1-methylpropoxycarbonyl) ethoxy, 2- (2- Methylpropoxycarbonyl) ethoxy, OCH 2 CH 2 COOC (CH 3 ) 3 , OCH 2 CH 2 COO (CH 2 ) 3 -C 2 H 5 ,
OCH2CH2COO(CH2)4-C2H5, 2- (COOCH3) propoxy, 2- (COOC H5) propoxy,OCH 2 CH 2 COO (CH 2 ) 4 -C 2 H 5 , 2- (COOCH 3 ) propoxy, 2- (COOC H 5 ) propoxy,
2- (COOCH2-C2H5) propoxy, 2- [COOCH (CH3) 2] propoxy,2- (COOCH 2 -C 2 H 5 ) propoxy, 2- [COOCH (CH 3 ) 2 ] propoxy,
2- (COOCH2CH2-C2H5) propoxy, 2- (1-Methylpropoxycarbonyl ) propoxy,2- (COOCH 2 CH 2 -C 2 H 5 ) propoxy, 2- (1-methylpropoxycarbonyl) propoxy,
2- (2 -Methylpropoxycarbonyl) propoxy, 2- [COOC (CH3) 3] propoxy, 3- (COOCH3) propoxy, 3- (COOC2H5) propoxy , 3- (COOCH2-C H5) propoxy,2- (2-methylpropoxycarbonyl) propoxy, 2- [COOC (CH 3 ) 3 ] propoxy, 3- (COOCH 3 ) propoxy, 3- (COOC 2 H 5 ) propoxy, 3- (COOCH 2 -CH 5 ) propoxy,
3- [COOCH (CH3)2] propoxy, 3- (COOCH2CH2-C2H5) propoxy,3- [COOCH (CH 3 ) 2 ] propoxy, 3- (COOCH 2 CH 2 -C 2 H 5 ) propoxy,
3- (1 -Methylpropoxycarbonyl) propoxy, 3- (2-Methylpropoxy- carbonyl) propoxy, 3- [COOC (CH )3] propoxy,3- (1-methylpropoxycarbonyl) propoxy, 3- (2-methylpropoxycarbonyl) propoxy, 3- [COOC (CH) 3 ] propoxy,
3- [COO (CH2)3-C2H5] propoxy, 3- [COO(CH2) -C H5] propoxy, 2- (COOCH3)butoxy, 2- (COOC2H5)butoxy, 2- (COOCH2-C2H5)butoxy,3- [COO (CH 2 ) 3 -C 2 H 5 ] propoxy, 3- [COO (CH 2 ) -CH 5 ] propoxy, 2- (COOCH 3 ) butoxy, 2- (COOC 2 H 5 ) butoxy, 2 - (COOCH 2 -C 2 H 5 ) butoxy,
2- [COOCH (CH3)2]butoxy, 2- (COOCH2CH2-C2H5)butoxy, 2-(l-Methyl- propoxycarbonyDbutoxy, 2- (2-Methylpropoxycarbonyl)butoxy, 2- [COOC(CH3)3]butoxy, 3-(COOCH3)butoxy, 3- (COOC2H5)butoxy, 3- (COOCH2-C2H5)butoxy, 3- [COOCH (CH3) 2] butoxy, 3- (COOCH2CH2-C H5) butoxy, 3- (1-Methylpropoxycarbonyl) butoxy,2- [COOCH (CH 3 ) 2 ] butoxy, 2- (COOCH 2 CH 2 -C 2 H 5 ) butoxy, 2- (l-methylpropoxycarbonyldbutoxy, 2- (2-methylpropoxycarbonyl) butoxy, 2- [COOC ( CH 3 ) 3 ] butoxy, 3- (COOCH 3 ) butoxy, 3- (COOC 2 H 5 ) butoxy, 3- (COOCH 2 -C 2 H 5 ) butoxy, 3- [COOCH (CH 3 ) 2 ] butoxy, 3- (COOCH 2 CH 2 -CH 5 ) butoxy, 3- (1-methylpropoxycarbonyl) butoxy,
3- (2 -Methylpropoxycarbonyl) utoxy, 3- [COOC (CH3) 3] butoxy, 4- (COOCH3) butoxy, 4- (COOC2H5) butoxy, 4- (COOCH -C2H5) butoxy,3- (2-Methylpropoxycarbonyl) utoxy, 3- [COOC (CH 3 ) 3 ] butoxy, 4- (COOCH 3 ) butoxy, 4- (COOC 2 H 5 ) butoxy, 4- (COOCH -C 2 H 5 ) butoxy ,
J
4- [COOCH (CH3)2] butoxy, 4- (COOCH2CH2-C2H5)butoχy, 4- (1 -Methylpropoxycarbonyl) butoxy, 4- (2-Methyl ropoxycarbonyl) butoxy,J 4- [COOCH (CH 3 ) 2 ] butoxy, 4- (COOCH 2 CH 2 -C 2 H 5 ) butoxy, 4- (1-methylpropoxycarbonyl) butoxy, 4- (2-methyl ropoxycarbonyl) butoxy,
4- [COOC (CH3)3] butoxy, 4- [COO (CH2)3-C2H5] butoxy,4- [COOC (CH 3 ) 3 ] butoxy, 4- [COO (CH 2 ) 3 -C 2 H 5 ] butoxy,
4- [COO (CH2) -C2H5] butoxy, 5- (COOCH3) pentoxy, 5- (COOC2H5) - pentoxy, 5- (COOCH2-C2H5) pentoxy, 5- [COOCH (CH3) 2] pentoxy,4- [COO (CH 2 ) -C 2 H 5 ] butoxy, 5- (COOCH 3 ) pentoxy, 5- (COOC 2 H 5 ) pentoxy, 5- (COOCH 2 -C 2 H 5 ) pentoxy, 5- [COOCH (CH 3 ) 2 ] pentoxy,
5- (COOCH2CH2-CH5) pentoxy, 5- (1-Methylpropoxycarbonyl ) pentoxy, 5- (2-Methylpropoxycarbonyl) pentoxy, 5- [COOC (CH3) 3] pentoxy,5- (COOCH 2 CH 2 -CH 5 ) pentoxy, 5- (1-methylpropoxycarbonyl) pentoxy, 5- (2-methylpropoxycarbonyl) pentoxy, 5- [COOC (CH 3 ) 3 ] pentoxy,
5- [COO(CH2) 3-C2H5] pentoxy, 5- [COO (CH2) 4-C2H5] pentoxy,5- [COO (CH 2 ) 3 -C 2 H 5 ] pentoxy, 5- [COO (CH 2 ) 4-C2H5] pentoxy,
6- (COOCH3)hexoxy, 6- (COOC2H5) hexoxy, 6- (COOCH2-C2H5) hexoxy, 6- [COOCH (CH3)2] hexoxy, 6- {COOCH2CH2-C2H5 ) hexoxy, 6-(l-Methyl- propoxycarbony1) hexoxy, 6- ( 2-Methylpropoxycarbony1 ) hexoxy, 6- [COOC (CH3) 3] hexoxy, 6- [COO (CH2) 3-C2H5] hexoxy oder 6- [COO (CH2)4-C2H5] hexoxy, insbesondere für OCH2COOCH3, OCH2COOCH(CH3)2, OCH(CH3)COOCH3 oder OCH2CH2COOCH3 ;6- (COOCH 3 ) hexoxy, 6- (COOC 2 H 5 ) hexoxy, 6- (COOCH 2 -C 2 H 5 ) hexoxy, 6- [COOCH (CH 3 ) 2 ] hexoxy, 6- {COOCH 2 CH 2 -C 2 H 5 ) hexoxy, 6- (l-methylpropoxycarbony1) hexoxy, 6- (2-methylpropoxycarbony1) hexoxy, 6- [COOC (CH 3 ) 3 ] hexoxy, 6- [COO (CH 2 ) 3 - C 2 H 5 ] hexoxy or 6- [COO (CH 2 ) 4 -C 2 H 5 ] hexoxy, in particular for OCH 2 COOCH 3 , OCH 2 COOCH (CH 3 ) 2 , OCH (CH 3 ) COOCH 3 or OCH 2 CH 2 COOCH 3 ;
Cι-C6-Alkylthio für: z.B. SCH3 , SC2H5, n-Propylthio, SCH(CH3)2, n-Butylthio, 1-Methylpropylthio, 2-Methylpropylthio, SC(CH3)3, n-Pentylthio, 1-Methylbutylthio, 2-Methylbutylthio, 3-Methyl- butylthio, 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-Dimethylbutyl - thio, 1, 3-Dimethylbutylthio, 2 , 2-Dimethylbutylthio, 2,3-Di- methylbutylthio, 3, 3-Dimethylbutylthio, 1-Ethylbutylthio, 2-Ethylbutylthio, 1, 1, 2-Trimethylpropylthio, 1, 2 , 2-Trimethyl- propylthio, 1-Ethyl-l-methylpropylthio oder l-Ethyl-2-methyl- propylthio, insbesondere für SCH3 oder SC2H5;Cι-C 6 alkylthio for: for example SCH 3 , SC 2 H 5 , n-propylthio, SCH (CH 3 ) 2 , n-butylthio, 1-methylpropylthio, 2-methylpropylthio, SC (CH 3 ) 3 , 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 -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-l-methylpropylthio or l-ethyl-2-methylpropylthio, in particular for SCH 3 or SC 2 H 5 ;
Cχ-C6~Halogenalkylthio für: einen Cχ-C6-Alkylthiorest wie vor- stehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder Iod substituiert ist, also z.B. für SCH2F, SCHF2, SCF3, SCH2C1, SCH(C1)2, SC(C1)3, SCHFC1, SCF(C1)2, SCF2C1, SCF2Br, 2-Fluorethylthio, 2-Chlorethylthio, 2-Bromethylthio, 2-Iodethylthio, 2 , 2-Dif luorethylthio, 2,2, 2-Trifluorethylthio, 2 , 2 , 2-Trichlorethylthio, 2-Chlor-2- fluorethylthio, 2-Chlor-2, 2-difluorethylthio, 2 , 2-Dichlor-2- fluorethylthio, SC2F5, 2-Fluorpropylthio, 3-Fluorpropylthio, 2-Chlorpropylthio, 3-Chlorpropylthio, 2-Brompropylthio, 3-Brompropylthio, 2 , 2-Difluorpropylthio, 2, 3-Dif luorpropyl - thio, 2,3-Dichlorpropylthio, 3 , 3 , 3-Trifluorpropylthio,Cχ-C 6 ~ haloalkylthio for: a Cχ-C 6 alkylthio radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example for SCH 2 F, SCHF 2 , SCF 3 , SCH 2 C1, SCH (C1) 2 , SC (C1) 3 , SCHFC1, SCF (C1) 2 , SCF 2 C1, SCF 2 Br, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2 , 2-difluoroethylthio, 2,2, 2-trifluoroethylthio, 2, 2, 2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2, 2-difluoroethylthio, 2, 2-dichloro-2-fluoroethylthio, SC 2 F 5 , 2-fluoropropylthio, 3-fluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 2, 2-difluoropropylthio, 2, 3-difluoropropylthio, 2,3-dichloropropylthio 3, 3, 3-trifluoropropylthio,
3,3, 3-Trichlorpropylthio, 2,2,3,3, 3-Pentafluorpropylthio, Heptafluorpropylthio, 1- (CH2F) -2-fluorethylthio, 1- (CH2Cl)-2-chlorethylthio, 1- (CH2Br) -2-bromethylthio, 4-Fluorbutylthio, 4-Chlorbutylthio, 4-Brombutylthio, 5-Fluor- pentylthio, 5-Chlorpentylthio, 5-Brompentoxy, 5-Iodpentoxy, Undecafluorpentoxy, 6-Fluorhexylthio oder 6-Chlorhexylthio, insbesondere für SCHF2, SCF3 oder SC(C1)3;
Cχ-C6-Alkylsulf inyl für: z.B. SOCH , SOC2H5, n-Propylsulf inyl , SOCH(CH3)2, n-Butylsulfinyl, 1-Methylpropylsulf inyl, 2-Methyl- propylsulf inyl, SOC(CH3)3, n-Pentylsulf inyl , 1-Methylbutyl - sulfinyl, 2-Methylbutylsulf inyl , 3-Methylbutylsulf inyl , 2, 2-Dimethylpropylsulf inyl , 1-Ethylpropylsulf inyl , n-Hexyl - sulfinyl, 1 , 1-Dimethylpropylsulfinyl , 1 , 2-Dimethylpropyl - sulfinyl, 1-Methylpentylsulfinyl, 2-Methylpentylsulf inyl, 3-Methylpentylsulf inyl, 4-Methylpentylsulf inyl , 1 , 1-Dimethyl - butylsulf inyl, 1, 2-Dimethylbutylsulf inyl , 1 , 3-Dimethylbutyl - sulfinyl, 2 , 2-Dimethylbutylsulf inyl , 2 , 3-Dimethylbutyl - sulfinyl, 3 , 3-Dimethylbutylsulf inyl , 1-Ethylbutylsulf inyl , 2-Ethylbutylsulf inyl , 1,1, 2-Trimethylpropylsulf inyl, 1,2, 2-Trimethylpropylsulf inyl, 1-Ethyl-l-methylpropylsulf inyl oder l-Ethyl-2-methylpropylsulf inyl , insbesondere für SOCH3 oder SOC2H5;3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio, heptafluoropropylthio, 1- (CH 2 F) -2-fluoroethylthio, 1- (CH 2 Cl) -2-chloroethylthio, 1- (CH 2 Br) -2-bromethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio, 5-fluoropentylthio, 5-chloropentylthio, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorhexylthio or 6-chlorohexylthio, in particular for SCHF 2 , SCF 3 or SC (C1) 3 ; Cχ-C 6 alkylsulf inyl for: e.g. SOCH, SOC 2 H 5 , n-propylsulf inyl, SOCH (CH 3 ) 2 , n-butylsulfinyl, 1-methylpropylsulf inyl, 2-methylpropylsulfinyl, SOC (CH 3 ) 3 , n-pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2, 2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, n-hexylsulfinyl, 1, 1-dimethylpropylsulfinyl, 1, 2 -Dimethylpropyl - sulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfyl, 3-methylpentylsulfyl, 4-methylpentylsulfyl, 1, 1-dimethylbutylsulfyl, 1, 2-dimethylbutylsulfyl, 1, 3-dimethylbutylsulfinyl, 2, 2-Dimethylbutylsulf inyl, 2, 3-Dimethylbutylsulfinyl, 3, 3-Dimethylbutylsulf inyl, 1-Ethylbutylsulf inyl, 2-Ethylbutylsulf inyl, 1,1, 2-Trimethylpropylsulf inyl, 1,2, 2-Trimethylpropylsulf inyl, 1- Ethyl-l-methylpropylsulfinyl or l-ethyl-2-methylpropylsulfinyl, in particular for SOCH 3 or SOC 2 H 5 ;
C -C6-Alkylsulfonyl für: z.B. S02CH3, S02C2H5, n-Propylsulfonyl, S0 CH(CH3)2, n-Butylsulfonyl, 1-Methylpropyl - sulfonyl, 2-Methylpropylsulfonyl, S02C(CH3)3, n-Pentyl - sulfonyl, 1-Methylbutylsulfonyl, 2-Methylbutylsulfonyl,C -C 6 alkylsulfonyl for: e.g. S0 2 CH 3 , S0 2 C 2 H 5 , n-propylsulfonyl, S0 CH (CH 3 ) 2 , n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, S0 2 C (CH 3 ) 3 , n-pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl,
3-Methylbutylsulfonyl, 2 , 2-Dimethylpropylsulfonyl , 1-Ethyl- propylsulfonyl, n-Hexylsulfonyl, 1 , 1-Dimethylpropylsulfonyl , 1, 2-Dimethylpropylsulfonyl, 1-Methylpentylsulfonyl, 2-Methyl- pentylsulfonyl , 3-Methylpentylsulfonyl, 4-Methylpentyl - sulfonyl, 1 , 1-Dimethylbutylsulfonyl , 1 , 2-Dimethylbutyl - sulfonyl, 1 , 3-Dimethylbutylsulfonyl , 2 , 2-Dimethylbutyl - sulfonyl, 2 , 3-Dimethylbutylsulfonyl, 3, 3-Dimethylbutyl - sulfonyl, 1-Ethylbutylsulfonyl, 2-Ethylbutylsulfonyl, 1,1, 2-Trimethylpropylsulfonyl, 1,2, 2-Trimethylpropylsulfonyl , 1-Ethyl-l-methylpropylsulfonyl oder l-Ethyl-2-methylpropyl - sulfonyl, insbesondere für S02CH3 oder S02CHs;3-methylbutylsulfonyl, 2, 2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, n-hexylsulfonyl, 1, 1-dimethylpropylsulfonyl, 1, 2-dimethylpropylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentyl-pentylsulfonylsulfonyl, 3 sulfonyl, 1, 1-dimethylbutylsulfonyl, 1, 2-dimethylbutyl - sulfonyl, 1, 3-dimethylbutylsulfonyl, 2, 2-dimethylbutyl - sulfonyl, 2, 3-dimethylbutylsulfonyl, 3, 3-dimethylbutyl - sulfonyl, 1-ethylbutylsulfonyl Ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-l-methylpropylsulfonyl or l-ethyl-2-methylpropylsulfonyl, in particular for S0 2 CH 3 or S0 2 CHs;
Cι-C6-Alkylaminosulfonyl für: z.B. H3C-NHS02-, H5C2-NHS02-, n-Propyl-NHS02-, (CH3) 2CH-NHS02-, n-Butyl-NHS0 - , 1-Methyl- propyl-NHS02-, 2-Methylpropyl-NHS02-, (CH3) 3C-NHS02- , n-Pentyl-NHS02-, 1-Methylbutyl-NHS02- , 2-Methylbutyl-NHS02-, 3-Methylbutyl-NHS02-, 2 , 2-Dimethylpropyl-NHS02- , 1-Ethyl- propyl-NHS02-, n-Hexyl-NHS02-, 1, 1-Dimethylpropyl-NHS02-, 1, 2-Dimethylpropyl-NHS02-, 1-Methylpentyl-NHS02- , 2-Methyl- pentyl-NHS02-, 3-Methylpentyl-NHS02-, 4-Methylpentyl-NHS02- , 1, 1-Dimethylbutyl-NHS02-, 1, 2-Dimethylbutyl-NHS02-, 1,3-Di- methylbutyl-NHS02-, 2 , 2-Dimethylbutyl-NHS02-, 2 , 3-Dimethyl - butyl-NHS02-, 3 , 3-Dimethylbutyl-NHS02- , 1-Ethylbutyl-NHS02-, 2-Ethylbutyl-NHS02-, 1 , 1 , 2-Trimethylpropyl-NHS02-, 1,2,2-Tri- methylpropyl-NHS02-, l-Ethyl-l-methylpropyl-NHS02- oder l-Ethyl-2-methylpropyl-NHS02-, insbesondere für H3C-NHS02- oder H5C -NHS02-;-C-C 6 -Alkylaminosulfonyl for: for example H 3 C-NHS0 2 -, H 5 C 2 -NHS0 2 -, n-propyl-NHS0 2 -, (CH 3 ) 2 CH-NHS0 2 -, n-butyl-NHS0 -, 1-methyl-propyl-NHS0 2 -, 2-methylpropyl-NHS0 2 -, (CH 3 ) 3 C-NHS0 2 -, n-pentyl-NHS0 2 -, 1-methylbutyl-NHS0 2 -, 2-methylbutyl -NHS0 2 -, 3-methylbutyl-NHS0 2 -, 2, 2-dimethylpropyl-NHS0 2 -, 1-ethyl-propyl-NHS0 2 -, n-hexyl-NHS0 2 -, 1, 1-dimethylpropyl-NHS0 2 - , 1, 2-Dimethylpropyl-NHS0 2 -, 1-methylpentyl-NHS0 2 -, 2-methylpentyl-NHS0 2 -, 3-methylpentyl-NHS0 2 -, 4-methylpentyl-NHS0 2 -, 1, 1-dimethylbutyl -NHS0 2 -, 1, 2-dimethylbutyl-NHS0 2 -, 1,3-dimethylbutyl-NHS0 2 -, 2, 2-dimethylbutyl-NHS0 2 -, 2, 3-dimethylbutyl-NHS0 2 -, 3 , 3-dimethylbutyl-NHS0 2 -, 1-ethylbutyl-NHS0 2 -, 2-ethylbutyl-NHS0 2 -, 1, 1, 2-trimethylpropyl-NHS0 2 -, 1,2,2-trimethylpropyl-NHS0 2 - , l-ethyl-l-methylpropyl-NHS0 2 - or l-ethyl-2-methylpropyl-NHS0 2 -, in particular for H 3 C-NHS0 2 - or H 5 C -NHS0 2 -;
//
Di - (Cχ-C6-alkyl) aminosulfonyl für: z.B. (CH3 ) 2N-S02- , (C2H5) 2N-S02-, N,N-Dipropylamino-S02-, N, N-Di (1-methylethyl) amino-S02-, N,N-Dibutylamino-S02-, N, -Di ( 1-methyl - propyl) amino-S02-, N, N-Di (2-methylpropyl ) amino-S0 -, N,N-Di (1, l-dimethylethyl)amino-S0-, N-Ethyl-N-methyl - amino-S02-, N-Methyl-N-propylamino-S0 - , N-Methyl-N- (1- methylethyl) amino-S02-, N-Butyl-N-methylamino-S0 - , N-Methyl-N- (1-methylpropyl) amino-S02-, N-Methyl-N- (2-methyl - propyl ) amino-S0 - , N- { 1 , 1-Dimethylethyl ) -N-methylamino-S02- , N-Ethyl-N-propylamino-S02-, N-Ethyl-N- (1-methylethyl) amino- S02-, N-Butyl-N-ethylamino-S02-, N-Ethyl-N- (1-methylpropyl ) - amino-S02-, N-Ethyl-N- (2-methylpropyl) amino-S02- , N-Ethyl-N- (1, l-dimethylethyl)amino-S02-, N- (1-Methylethyl ) -N-propyl- amino-S02-, N-Butyl-N-propylamino-S02- , N- (1-Methylpropyl) -N- propylamino-S02- , N- ( 2-Methylpropyl ) -N-propylamino-S02- , N- (1 , 1-Dimethylethyl) -N-propylamino-S02-, N-Butyl-N- (1- methylethyl) amino-S02-, N- (1-Methylethyl) -N- (1-methyl - propyl) amino-S02-, N- ( 1-Methylethyl) -N- (2-methylpropyl) - amino-S02-, N- (1, 1-Dimethylethyl) -N- (1-methylethyl) amino-S02-, N-Butyl-N- (l-methylpropyl)amino-S02-, N-Butyl-N- (2-methyl - propyl) amino-S02-, N-Butyl-N- ( 1, 1-dimethylethyl) amino-S02- , N- (1-Methylpropyl) -N- (2-methylpropyl ) a ino-SC^-, N- (1, 1-Di - methylethyl) -N- ( 1-methylpropyl ) amino-S02- oder N- (1, 1-Dimethylethyl) -N- (2-methylpropyl ) amino-S02- , insbesondere für (CH3)2N-S02- , (C2H5)2N-S02- oder N-Ethyl -N-methylamino-S02 - ;// Di - (Cχ-C 6 -alkyl) aminosulfonyl for: e.g. (CH 3 ) 2 N-S0 2 -, (C 2 H 5 ) 2 N-S0 2 -, N, N-Dipropylamino-S0 2 -, N, N-Di (1-methylethyl) amino-S0 2 -, N, N-dibutylamino-S0 2 -, N, -Di (1-methyl-propyl) amino-S0 2 -, N, N-Di (2-methylpropyl ) amino-S0 -, N, N-Di (1, l-dimethylethyl) amino-S0-, N-ethyl-N-methyl - amino-S0 2 -, N-methyl-N-propylamino-S0 -, N- Methyl-N- (1-methylethyl) amino-S0 2 -, N-butyl-N-methylamino-S0 -, N-methyl-N- (1-methylpropyl) amino-S0 2 -, N-methyl-N- ( 2-methyl-propyl) amino-S0 -, N- {1, 1-dimethylethyl) -N-methylamino-S0 2 -, N-ethyl-N-propylamino-S0 2 -, N-ethyl-N- (1- methylethyl) amino-S0 2 -, N-butyl-N-ethylamino-S0 2 -, N-ethyl-N- (1-methylpropyl) - amino-S0 2 -, N-ethyl-N- (2-methylpropyl) amino -S0 2 -, N-ethyl-N- (1, l-dimethylethyl) amino-S0 2 -, N- (1-methylethyl) -N-propyl-amino-S0 2 -, N-butyl-N-propylamino- S0 2 -, N- (1-methylpropyl) -N-propylamino-S0 2 -, N- (2-methylpropyl) -N-propylamino-S0 2 -, N- (1, 1-dimethylethyl) -N- propylamino-S0 2 -, N-butyl-N- (1-methylethyl) amino-S0 2 -, N- (1-methylethyl) -N- (1-methyl-propyl) amino-S0 2 -, N- (1 -Methylethyl) -N- (2-methylpropyl) - amino-S0 2 -, N- (1, 1-dimethylethyl) -N- (1-methylethyl) amino-S0 2 -, N-butyl-N- (l- methylpropyl) amino-S0 2 -, N-butyl-N- (2-methyl-propyl) amino-S0 2 -, N-butyl-N- (1, 1-dimethylethyl) amino-S0 2 -, N- (1 -Methylpropyl) -N- (2-methylpropyl) a ino-SC ^ -, N- (1, 1-dimethylethyl) -N- (1-methylpropyl) amino-S0 2 - or N- (1, 1- Dimethylethyl) -N- (2-methylpropyl) amino-S0 2 -, especially for (CH 3 ) 2 N-S0 2 -, (C 2 H 5 ) 2 N-S0 2 - or N-ethyl -N-methylamino- S0 2 -;
C3-C6-Alkenyl für: z.B. Prop-1-en-l-yl , Allyl, 1-Methyl- ethenyl, n-Buten-1-yl , n-Buten-2-yl, n-Buten-3-yl, 1-Methyl- prop-1-en-l-yl , 2-Methylprop-l-en-l-yl , l-Methylprop-2-en- 1-yl, 2-Methylprop-2-en-l-yl, n-Penten-1-yl , n-Penten-2-yl , n-Penten-3-yl, n-Penten-4-yl, 1-Methylbut-l-en-l-yl, 2-Methylbut-l-en-l-yl, 3-Methylbut-l-en-l-yl, 1-Methyl- but-2-en-l-yl, 2-Methylbut-2-en-l-yl, 3-Methylbut-2-en-l-yl , l-Methylbut-3-en-l-yl, 2-Methylbut-3-en-l-yl, 3-Methyl- but-3-en-l-yl, 1, l-Dimethyl-prop-2-en-l-yl, 1, 2-Dimethyl- prop-1-en-l-yl, 1 , 2-Dimethyl-prop-2-en-l-yl , 1-Ethyl- prop-l-en-2-yl, l-Ethylprop-2-en-l-yl , n-Hex-1-en-l-yl, n-Hex-2-en-l-yl, n-Hex-3-en-l-yl, n-Hex-4-en-l-yl, n-Hex-5- en-l-yl, 1-Methyl-pent-l-en-l-yl, 2-Methylpent-l-en-l-yl, 3-Methylpent-l-en-l-yl, 4-Methylpent-l-en-l-yl , 1-Methyl - pent-2-en-l-yl, 2-Methylpent-2-en-l-yl, 3-Methylpent-2-en- 1-yl, 4-Methylpent-2-en-l-yl, l-Methylpent-3-en-l-yl, 2-Methylpent-3-en-l-yl, 3-Methylpent-3-en-l-yl, 4-Methyl - pent-3-en-l-yl, l-Methylpent-4-en-l-yl, 2-Methylpent-4-en- 1-yl, 3-Methylpent-4-en-l-yl, 4-Methylpent-4-en-l-yl , 1,1-Di- methyl-but-2-en-l-yl, 1, l-Dimethyl-but-3-en-l-yl, 1,2-Di- methyl-but-1-en-l-yl, 1, 2-Dimethyl-but-2-en-l-yl, 1,2-Di-C 3 -C 6 alkenyl for: for example prop-1-en-l-yl, allyl, 1-methylethenyl, n-buten-1-yl, n-buten-2-yl, n-buten-3- yl, 1-methylprop-1-en-l-yl, 2-methylprop-l-en-l-yl, l-methylprop-2-en- 1-yl, 2-methylprop-2-en-l- yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methylbut-l-en-l-yl, 2-methylbut- l-en-l-yl, 3-methylbut-l-en-l-yl, 1-methylbut-2-en-l-yl, 2-methylbut-2-en-l-yl, 3-methylbut- 2-en-l-yl, l-methylbut-3-en-l-yl, 2-methylbut-3-en-l-yl, 3-methylbut-3-en-l-yl, 1, l- Dimethyl-prop-2-en-l-yl, 1, 2-dimethyl-prop-1-en-l-yl, 1, 2-dimethyl-prop-2-en-l-yl, 1-ethyl-prop- l-en-2-yl, l-ethylprop-2-en-l-yl, n-hex-1-en-l-yl, n-hex-2-en-l-yl, n-hex-3- en-l-yl, n-hex-4-en-l-yl, n-hex-5- en-l-yl, 1-methyl-pent-l-en-l-yl, 2-methylpent-l- en-l-yl, 3-methylpent-l-en-l-yl, 4-methylpent-l-en-l-yl, 1-methyl-pent-2-en-l-yl, 2-methylpent-2- en-l-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-l-yl, l-methylpent-3-en-l-yl, 2-methylpent-3-en- l-yl, 3-methylpent-3-en-l-yl, 4-methyl-pen t-3-en-l-yl, l-methylpent-4-en-l-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-l-yl, 4-methylpent- 4-en-1-yl, 1,1-dimethyl-but-2-en-1-yl, 1, l-dimethyl-but-3-en-1-yl, 1,2-dimethyl but-1-en-l-yl, 1,2-dimethyl-but-2-en-l-yl, 1,2-di-
II
methyl-but-3-en-l-yl, 1 , 3-Dimethyl-but-l-en-l-yl , 1,3-Di- methyl-but-2-en-l-yl, 1 , 3-Dimethyl-but-3-en-l-yl , 2,2-Di- methyl-but-3-en-l-yl , 2 , 3-Dimethyl-but-l-en-l-yl , 2,3-Di- methyl-but-2-en-l-yl, 2 , 3-Dimethyl-but-3-en-l-yl, 3,3-Di- methyl-but-1-en-l-yl, 3 , 3-Dimethyl-but-2-en-l-yl, 1-Ethyl- but-1-en-l-yl, l-Ethylbut-2-en-l-yl , l-Ethylbut-3-en-l-yl , 2-Ethylbut-l-en-l-yl, 2-Ethylbut-2-en-l-yl , 2-Ethylbut-3- en-l-yl, 1, 1 , 2-Trimethyl-prop-2-en-l-yl, 1-Ethyl-l-methyl- prop-2-en-l-yl, l-Ethyl-2-methyl-prop-l-en-l-yl oder l-Ethyl-2-methyl-prop-2-en-l-yl, insbesondere für Allyl;II methyl-but-3-en-l-yl, 1, 3-dimethyl-but-l-en-l-yl, 1,3-dimethyl-but-2-en-l-yl, 1, 3- Dimethyl-but-3-en-l-yl, 2,2-dimethyl-but-3-en-l-yl, 2,3-dimethyl-but-l-en-l-yl, 2,3- Dimethyl-but-2-en-1-yl, 2, 3-dimethyl-but-3-en-1-yl, 3,3-dimethyl-but-1-en-1-yl, 3, 3-dimethyl-but-2-en-l-yl, 1-ethyl-but-1-en-l-yl, l-ethylbut-2-en-l-yl, l-ethylbut-3-en-l- yl, 2-ethylbut-l-en-l-yl, 2-ethylbut-2-en-l-yl, 2-ethylbut-3- en-l-yl, 1, 1, 2-trimethyl-prop-2- en-l-yl, 1-ethyl-l-methyl-prop-2-en-l-yl, l-ethyl-2-methyl-prop-l-en-l-yl or l-ethyl-2-methyl prop-2-en-l-yl, especially for allyl;
C3-C6-Alkinyl für: z.B. Prop-1-in-l-yl , Propargyl, n-But-1- in-l-yl, n-But-l-in-3-yl , n-But-l-in-4-yl , n-But-2-in-l-yl , n-Pent-1-in-l-yl , n-Pent-l-in-3-yl , n-Pent-l-in-4-yl , n-Pent- l-in-5-yl, n-Pent-2-in-l-yl, n-Pent-2-in-4-yl , n-Pent-2-in-C 3 -C 6 alkynyl for: for example prop-1-in-1-yl, propargyl, n-but-1-in-1-yl, n-but-1-in-3-yl, n-but- l-in-4-yl, n-but-2-in-l-yl, n-pent-1-in-l-yl, n-pent-l-in-3-yl, n-pent-l- in-4-yl, n-pent-1-in-5-yl, n-pent-2-in-1-yl, n-pent-2-in-4-yl, n-pent-2-in
5-yl, 3-Methyl-but-l-in-3-yl, 3-Methyl-but-l-in-4-yl , n-Hex- 1-in-l-yl, n-Hex-l-in-3-yl , n-Hex-l-in-4-yl, n-Hex-l-in-5-yl , n-Hex-l-in-6-yl, n-Hex-2-in-l-yl , n-Hex-2-in-4-yl , n-Hex-2- in-5-yl, n-Hex-2-in-6-yl , n-Hex-3-in-l-yl , n-Hex-3-in-2-yl , 3-Methyl-pent-l-in-l-yl, 3-Methyl-pent-l-in-3-yl, 3-Methyl- pent-l-in-4-yl , 3-Methyl-pent-l-in-5-yl, 4-Methyl-pent-l- in-l-yl, 4-Methyl-pent-2-in-4-yl oder 4-Methyl-pent-2-in- 5-yl, insbesondere für Propargyl;5-yl, 3-methyl-but-l-in-3-yl, 3-methyl-but-l-in-4-yl, n-hex-1-in-l-yl, n-hex-l- in-3-yl, n-hex-1-in-4-yl, n-hex-1-in-5-yl, n-hex-1-in-6-yl, n-hex-2-in l-yl, n-hex-2-in-4-yl, n-hex-2-in-5-yl, n-hex-2-in-6-yl, n-hex-3-in-l- yl, n-hex-3-in-2-yl, 3-methyl-pent-l-in-l-yl, 3-methyl-pent-l-in-3-yl, 3-methyl-pent-l- in-4-yl, 3-methyl-pent-1-in-5-yl, 4-methyl-pent-1-in-1-yl, 4-methyl-pent-2-in-4-yl or 4- Methyl-pent-2-in-5-yl, especially for propargyl;
C3-C6-Alkenyloxy für: z.B. Prop-1-en-l-yloxy, Allyloxy, 1-Methylethenyloxy, n-Buten-1-yloxy, n-Buten-2-yloxy, n-Buten-3-yloxy, 1-Methylprop-l-en-l-yloxy, 2-Methylprop-l- en-1-yloxy, l-Methylprop-2-en-l-yloxy, 2-Methylprop-2-en- 1-yloxy, n-Penten-1-yloxy, n-Penten-2-yloxy, n-Penten-3-yl - oxy, n-Penten-4-yloxy, 1-Methylbut-l-en-l-yloxy, 2-Methyl- but-1-en-l-yloxy, 3-Methylbut-l-en-l-yloxy, l-Methylbut-2- en-1-yloxy, 2-Methylbut-2-en-l-yloxy, 3-Methylbut-2-en-l-yl - oxy, l-Methylbut-3-en-l-yloxy, 2-Methylbut-3-en-l-yloxy, 3-Methylbut-3-en-l-yloxy, 1, l-Dimethyl-prop-2-en-l-yloxy, 1, 2-Dimethyl-prop-l-en-l-yloxy, 1 , 2-Dimethyl-prop-2-en-l-yl - oxy, l-Ethylprop-l-en-2-yloxy, l-Ethylprop-2-en-l-yloxy, n-Hex-1-en-l-yloxy, n-Hex-2-en-l-yloxy, n-Hex-3-en-l-yloxy, n-Hex-4-en-l-yloxy, n-Hex-5-en-l-yloxy, 1-Methyl-pent-l-en- 1-yloxy, 2-Methylpent-l-en-l-yloxy, 3-Methylpent-l-en-l-yl - oxy, 4-Methylpent-l-en-l-yloxy, l-Methylpent-2-en-l-yloxy, 2-Methylpent-2-en-l-yloxy, 3-Methylpent-2-en-l-yloxy, 4-Methylpent-2-en-l-yloxy, l-Methylpent-3-en-l-yloxy, 2-Methylpent-3-en-l-yloxy, 3-Methylpent-3-en-l-yloxy, 4-Methylpent-3-en-l-yloxy, l-Methylpent-4-en-l-yloxy, 2-Methylpent-4-en-l-yloxy, 3-Methylpent-4-en-l-yloxy,C 3 -C 6 alkenyloxy for: for example prop-1-en-l-yloxy, allyloxy, 1-methylethenyloxy, n-buten-1-yloxy, n-buten-2-yloxy, n-buten-3-yloxy, 1-methylprop-l-en-l-yloxy, 2-methylprop-l-en-1-yloxy, l-methylprop-2-en-l-yloxy, 2-methylprop-2-en- 1-yloxy, n- Penten-1-yloxy, n-penten-2-yloxy, n-penten-3-yl - oxy, n-penten-4-yloxy, 1-methylbut-l-en-l-yloxy, 2-methyl-but- 1-en-l-yloxy, 3-methylbut-l-en-l-yloxy, l-methylbut-2-en-1-yloxy, 2-methylbut-2-en-l-yloxy, 3-methylbut-2- en-l-yl-oxy, l-methylbut-3-en-l-yloxy, 2-methylbut-3-en-l-yloxy, 3-methylbut-3-en-l-yloxy, 1, l-dimethyl- prop-2-en-l-yloxy, 1, 2-dimethyl-prop-l-en-l-yloxy, 1, 2-dimethyl-prop-2-en-l-yl - oxy, l-ethylprop-l- en-2-yloxy, l-ethylprop-2-en-l-yloxy, n-hex-1-en-l-yloxy, n-hex-2-en-l-yloxy, n-hex-3-en- l-yloxy, n-hex-4-en-l-yloxy, n-hex-5-en-l-yloxy, 1-methyl-pent-l-en-1-yloxy, 2-methylpent-l-en- l-yloxy, 3-methylpent-l-en-l-yloxy, 4-methylpent-l-en-l-yloxy, l-methylpent-2-en-l-yloxy, 2-methylpent-2-en- l-yloxy, 3-methylpent-2-en-l-ylo xy, 4-methylpent-2-en-l-yloxy, l-methylpent-3-en-l-yloxy, 2-methylpent-3-en-l-yloxy, 3-methylpent-3-en-l-yloxy, 4-methylpent-3-en-l-yloxy, l-methylpent-4-en-l-yloxy, 2-methylpent-4-en-l-yloxy, 3-methylpent-4-en-l-yloxy,
4-Methylpent-4-en-l-yloxy, 1 , l-Dimethyl-but-2-en-l-yloxy,4-methylpent-4-en-l-yloxy, 1, l-dimethyl-but-2-en-l-yloxy,
1, l-Dimethyl-but-3-en-l-yloxy, 1, 2-Dimethyl-but-l-en-l-yloxy,
1 , 2 -Dimethyl-but-2 -en- l-yloxy, 1 , 2 -Dimethyl -but- 3-en-l -yloxy ,1, l-dimethyl-but-3-en-l-yloxy, 1, 2-dimethyl-but-l-en-l-yloxy, 1,2-dimethyl-but-2-en-l-yloxy, 1,2-dimethyl-but-3-en-1-yloxy,
1 , 3-Dimethyl-but-l -en- l-yloxy, 1 , 3 -Dimethyl-but-2-en- l -yloxy ,1,3-dimethyl-but-1-en-1-yloxy, 1,3-dimethyl-but-2-en-1-yloxy,
1 , 3-Dimethyl-but-3 -en-l-yloxy, 2 , 2-Dimethyl-but-3-en-l-yloxy,1,3-dimethyl-but-3-en-l-yloxy, 2,2-dimethyl-but-3-en-l-yloxy,
2 , 3-Dimethyl-but-l-en-l-yloxy, 2 , 3-Dimethyl-but- 2-en-l-yloxy, 2 , -Dimethyl-but-3 -en-l-yloxy, 3 , 3-Dimethyl-but- l-en- l -yloxy,2,3-dimethyl-but-l-en-l-yloxy, 2,3-dimethyl-but-2-en-l-yloxy, 2,3-dimethyl-but-3-en-l-yloxy, 3,3 -Dimethyl-but-l-en-l -yloxy,
3 , 3-Dimethyl-but-2-en-l-yloxy, 1-Ethylbut-l-en-l-yloxy, l-Ethylbut-2-en-l-yloxy, l-Ethylbut-3-en-l-yloxy, 2-Ethyl- but-1-en-l-yloxy, 2-Ethylbut-2-en-l-yloxy, 2-Ethylbut-3- en-1-yloxy, 1 , 1 , 2-Trimethyl-prop-2-en-l-yloxy, 1-Ethyl-l- methyl-prop-2-en-l-yloxy, l-Ethyl-2-methyl-prop-l-en-l-yloxy oder l-Ethyl-2-methyl-prop-2-en-l-yloxy, insbesondere für Allyloxy;3,3-dimethyl-but-2-en-l-yloxy, 1-ethylbut-l-en-l-yloxy, l-ethylbut-2-en-l-yloxy, l-ethylbut-3-en-l- yloxy, 2-ethyl-but-1-en-1-yloxy, 2-ethylbut-2-en-1-yloxy, 2-ethylbut-3-en-1-yloxy, 1, 1, 2-trimethyl-prop- 2-en-l-yloxy, 1-ethyl-l-methyl-prop-2-en-l-yloxy, l-ethyl-2-methyl-prop-l-en-l-yloxy or l-ethyl-2- methyl-prop-2-en-l-yloxy, especially for allyloxy;
C3~C6-Alkinyloxy für: z.B. Prop-1-in-l-yloxy, Propargyloxy, n-But-1-in-l-yloxy, n-But-l-in-3-yloxy, n-But-l-in-4-yloxy, n-But-2-in-l-yloxy, n-Pent-1-in-l-yloxy, n-Pent-l-in-3-yloxy, n-Pent-l-in-4-yloxy, n-Pent-l-in-5-yloxy, n-Pent-2-in-l-yl - oxy, n-Pent-2-in-4-yloxy, n-Pent-2-in-5-yloxy, 3-Methyl-but- l-in-3-yloxy, 3-Methyl-but-l-in-4-yloxy, n-Hex-1-in-l-yloxy, n-Hex-l-in-3-yloxy, n-Hex-l-in-4-yloxy, n-Hex-l-in-5-yloxy, n-Hex-l-in-6-yloxy, n-Hex-2-in-l-yloxy, n-Hex-2-in-4-yloxy, n-Hex-2-in-5-yloxy, n-Hex-2-in-6-yloxy, n-Hex-3-in-l-yloxy, n-Hex-3-in-2-yloxy, 3-Methyl-pent-l-in-l-yloxy, 3-Methyl- pent-l-in-3-yloxy, 3-Methyl-pent-l-in-4-yloxy, 3-Methyl- pent-l-in-5-yloxy, 4-Methyl-pent-l-ιn-l-yloxy, 4-Methyl- pent-2-in-4-yloxy oder 4-Methyl-pent-2-in-5-yloxy, insbesondere für Propargyloxy.C 3 ~ C 6 -alkynyloxy for: e.g. prop-1-in-l-yloxy, propargyloxy, n-but-1-in-l-yloxy, n-but-l-in-3-yloxy, n-but- l-in-4-yloxy, n-but-2-in-l-yloxy, n-pent-1-in-l-yloxy, n-pent-l-in-3-yloxy, n-pent-l- in-4-yloxy, n-pent-1-in-5-yloxy, n-pent-2-in-1-yl-oxy, n-pent-2-in-4-yloxy, n-pent-2- in-5-yloxy, 3-methyl-but-l-in-3-yloxy, 3-methyl-but-l-in-4-yloxy, n-hex-1-in-l-yloxy, n-hex l-in-3-yloxy, n-hex-l-in-4-yloxy, n-hex-l-in-5-yloxy, n-hex-l-in-6-yloxy, n-hex-2- in-1-yloxy, n-hex-2-in-4-yloxy, n-hex-2-in-5-yloxy, n-hex-2-in-6-yloxy, n-hex-3-in l-yloxy, n-hex-3-in-2-yloxy, 3-methyl-pent-l-in-l-yloxy, 3-methyl-pent-l-in-3-yloxy, 3-methyl-pent- l-in-4-yloxy, 3-methyl-pent-l-in-5-yloxy, 4-methyl-pent-l-ιn-l-yloxy, 4-methyl-pent-2-in-4-yloxy or 4-methyl-pent-2-yn-5-yloxy, especially for propargyloxy.
Im Hinblick auf die Verwendung der substituierten 2-Phenyl- pyridine I als Herbizide und/oder als desikkant/defoliant wirksame Verbindungen haben die Variablen vorzugsweise folgende Bedeutungen, und zwar jeweils für sich allein oder in Kombination:With regard to the use of the substituted 2-phenylpyridines I as herbicides and / or as desiccant / defoliant compounds, the variables preferably have the following meanings, individually or in combination:
n Null;n zero;
R1 Cχ-C6-Alkylsulfonyl, insbesondere S02CH3;R 1 Cχ-C 6 alkylsulfonyl, in particular S0 2 CH 3 ;
R2 Halogen, insbesondere Chlor;R 2 halogen, especially chlorine;
R3 Wasserstoff, Fluor oder Chlor, besonders bevorzugt Fluor oder Chlor, insbesondere Fluor;R 3 is hydrogen, fluorine or chlorine, particularly preferably fluorine or chlorine, in particular fluorine;
R4 Cyano oder Halogen, besonders bevorzugt Cyano oder Chlor, insbesondere Chlor;R 4 cyano or halogen, particularly preferably cyano or chlorine, especially chlorine;
/,
R5 Wasserstoff, Nitro, Cyano, Hydroxylamino, Cχ-C6-Alkyl/, R 5 is hydrogen, nitro, cyano, hydroxylamino, Cχ-C 6 alkyl
(insbesondere CH3) , Cχ-C6-Halogenalkyl (insbesondere Halogen - methyl), -COC1 , -CO-OR6, -CO-O- (Cχ-C4-Alkylen) -CO-OR6 , -0- (Cχ-C4-Alkylen) -CO-OR6 , -0- (Cχ-C -Alkylen) -CO-O- (Cχ-C4- Alkylen) -CO-OR6, -OR9 , For yl, -CH=N-OR15 oder -NH2 ;(in particular CH 3 ), Cχ-C 6 -haloalkyl (especially halogen - methyl), -COC1, -CO-OR 6 , -CO-O- (Cχ-C 4 -alkylene) -CO-OR 6 , -0- (Cχ-C 4 -alkylene) -CO-OR 6 , -0- (Cχ-C -alkylene) -CO-O- (Cχ-C 4 - alkylene) -CO-OR 6 , -OR 9 , for yl, -CH = N-OR 15 or -NH 2 ;
R6 Wasserstoff, Cχ-C6-Alkyl, C3-C6-Alkenyl , C3-C6-Alkinyl oder Cι-C6-Alkoxy-C -C6-alkyl ;R 6 is hydrogen, Cχ-C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or -C-C 6 alkoxy-C -C 6 alkyl;
R9 Wasserstoff, Cχ-C6-Alkyl, C3-C6-Alkenyl oder C3-C6-Alkinyl ;R 9 is hydrogen, Cχ-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
R15 Cχ-C6-Alkyl.R 15 Cχ-C 6 alkyl.
l
Ganz besonders bevorzugt sind die Verbindungen der Formel Ia (^ I mit n = Null; R1 = Methylsulfonyl ; R2 und R4 = Chlor; R3 = Fluor), insbesondere die Verbindungen der Tabelle 1:l The compounds of the formula Ia (I with n = zero; R 1 = methylsulfonyl; R 2 and R 4 = chlorine; R 3 = fluorine) are very particularly preferred, in particular the compounds of Table 1:
Tabelle 1Table 1
l o
lo
7
7
/δ
/ δ
2Ό
2Ό
2ι
2ι
U
U
22»
22 »
2«f
2 «f
2t
2t
1
1
78
78
1Λ
1Λ
ID
ID
3ι
3ι
31
31
Des weiteren sind die substituierten 2 - Phenylpyridine der Formeln Ib, Ic, Id, Ie und If ganz besonders bevorzugt, insbesondereFurthermore, the substituted 2-phenylpyridines of the formulas Ib, Ic, Id, Ie and If are very particularly preferred, in particular
die Verbindungen Ib.l bis Ib.662, die sich von den entsprechenden Verbindungen la.l bis Ia.662 lediglich dadurch unterscheiden, daß R3 für Chlor steht:the compounds Ib.l to Ib.662, which differ from the corresponding compounds la.l to Ia.662 only in that R 3 is chlorine:
die Verbindungen Ic.l bis Ic.662, die sich von den entsprechenden Verbindungen la.l bis Ia.662 lediglich dadurch unterscheiden, daß R3 für Wasserstoff steht:the compounds Ic.l to Ic.662, which differ from the corresponding compounds la.l to Ia.662 only in that R 3 is hydrogen:
die Verbindungen Id.l bis Id.662, die sich von den entsprechenden Verbindungen la.l bis Ia.662 lediglich dadurch unterscheiden, daß R4 für Cyano steht: the compounds Id.l to Id.662, which differ from the corresponding compounds la.l to Ia.662 only in that R 4 is cyano:
die Verbindungen Ie.l bis Ie.662, die sich von den entsprechenden Verbindungen la.l bis Ia.662 lediglich dadurch unterscheiden, daß R3 für Chlor und R4 für Cyano stehen:the compounds Ie.l to Ie.662, which differ from the corresponding compounds la.l to Ia.662 only in that R 3 is chlorine and R 4 is cyano:
die Verbindungen If.l bis If .662, die sich von den entsprechenden Verbindungen la.l bis Ia.662 lediglich dadurch unterscheiden, daß R3 für Wasserstoff und R4 für Cyano stehen:the compounds If.l to If .662, which differ from the corresponding compounds la.l to Ia.662 only in that R 3 is hydrogen and R 4 is cyano:
3*1
Die substituierten 2 -Phenylpyridine der Formel I sind auf verschiedene Weise erhältlich, beispielsweise nach einem der folgenden Verfahren:3 * 1 The substituted 2-phenylpyridines of the formula I can be obtained in various ways, for example by one of the following processes:
Verfahren AjAj method
Oxidation von substituierten 2-Phenylpyridinen der Formel I, bei denen n Null bedeutet und R1 und R5 keinen oxidierbaren Schwefel enthalten, auf an sich bekannte Weise {vgl. z.B. A. Albini & S. Pietra, Heterocyclic N-Oxides, CRC-Press Inc., Boca Raton, USA 1991; H.S. Mosher et al., Org. Synth. Coll. Vol. IV 1963, Seite 828; E.C. Taylor et al., Org. Synth. Coll. Vol. IV 1963, Seite 704; T.W. Bell et. al . , Org. Synth. ü_9_, Seite 226 (1990)}:Oxidation of substituted 2-phenylpyridines of the formula I, in which n is zero and R 1 and R 5 contain no oxidizable sulfur, in a manner known per se {cf. e.g. A. Albini & S. Pietra, Heterocyclic N-Oxides, CRC-Press Inc., Boca Raton, USA 1991; HS Mosher et al., Org. Synth. Coll. Vol. IV 1963, page 828; EC Taylor et al., Org. Synth. Coll. Vol. IV 1963, page 704; TW Bell et. al. , Org. Synth. ü_9_, page 226 (1990)}:
Oxidationoxidation
I(n=0) ► I (n=l)I (n = 0) ► I (n = l)
Unter den zur Oxidation des Pyridinrings üblichen Oxidations- mitteln sei beispielhaft auf Peressigsäure, Trifluorperessig- säure, Perbenzoesäure, m-Chlorperbenzoesäure, Monopermalein- säure, Magnesiummonoperphthalat, Natriumperborat, Oxone® (enthält Peroxidisulfat) , Perwolframsäure und Wasserstoffperoxid verwiesen.Among the conventionally used for the oxidation of the pyridine oxidizing agents is exemplified on peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, Monopermalein- acid, magnesium monoperphthalate, sodium perborate, oxone ® (contains peroxydisulfate), pertungstic acid and hydrogen peroxide, referred.
Geeignete Lösungsmittel sind z.B. Wasser, Schwefelsäure, Carbonsäuren wie Essigsäure und Trifluoressigsäure sowie halogenierte Kohlenwasserstoffe wie Dichlormethan und Chloroform.Suitable solvents are e.g. Water, sulfuric acid, carboxylic acids such as acetic acid and trifluoroacetic acid and halogenated hydrocarbons such as dichloromethane and chloroform.
Normalerweise gelingt die Oxidation bei Temperaturen von 0°C bis Siedetemperatur des Reaktionsgemisches.The oxidation is usually successful at temperatures from 0 ° C to the boiling point of the reaction mixture.
Das Oxidationsmittel wird normalerweise in mindestens äuquimolaren Mengen, bezogen auf die Ausgangsverbindung, eingesetzt. Im allgemeinen hat sich ein Überschuß an Oxidationsmittel als besonders vorteilhaft erwiesen.The oxidizing agent is normally used in at least equimolar amounts, based on the starting compound. In general, an excess of oxidizing agent has proven to be particularly advantageous.
Verfahren B>Procedure B>
Oxidation von substituierten 2-Phenylpyridinen der Formel I, bei denen R1 für Cχ-C6-Alkylthio oder Cχ-C6 -Alkylsulfinyl steht und der Substituent R5 keinen oxidierbaren Schwefel enthält, auf an sich bekannte Weise {vgl. z.B. C.S. Giam et al., Org. Prep. Proced. Int. 11(2), S. 137 (1981); S.G. Woods et al., J. Hetero- cycl. Chem. ZI, 97-101 (1984); S.G. Woods, U.S. 4,616,087; N. Finch et al., J. Med. Chem. 21(12), 1269-1274 (1978); H. Ban- Oganowska, Pd. J. Chem. £1(9), 1609-1613 (1993); A.D. Dünn & R. Norrie, J. Prakt. Chem. /Chem. -Ztg. 3_3>, 269-272 (1993)}:
Oxidation of substituted 2-phenylpyridines of the formula I in which R 1 is Cχ-C 6 -alkylthio or Cχ-C 6 -alkylsulfinyl and the substituent R 5 contains no oxidizable sulfur, in a manner known per se {cf. e.g. CS Giam et al., Org. Prep. Proced. Int. 11 (2), p. 137 (1981); SG Woods et al., J. Heterocycl. Chem. ZI, 97-101 (1984); SG Woods, U.S. 4,616,087; N. Finch et al., J. Med. Chem. 21 (12), 1269-1274 (1978); H. Ban Oganowska, Pd. J. Chem. £ 1 (9), 1609-1613 (1993); AD Dünn & R. Norrie, J. Prakt. Chem. / Chem. - Currently 3_3>, 269-272 (1993)}:
I (R1 = Alkylthio) KR' -^ Alkylsulfinyl)I (R 1 = alkylthio) KR '- ^ alkylsulfinyl)
R = Cι-Cfi-AlkylR = Cι-C alkyl fi
I (R' = Alkylsulfonyl)I (R '= alkylsulfonyl)
Bezüglich geeigneter Lösungsmittel und Reaktionstemperaturen sei auf die Angaben bei Verfahren A> verwiesen. Neben den bei Verfahren A) genannten Oxidationsmitteln kommen hier auch Alkali - metallhypohalogenide wie Natrium- und Kaliumhypochlorid in Betracht .With regard to suitable solvents and reaction temperatures, reference is made to the information given in process A>. In addition to the oxidizing agents mentioned in process A), alkali metal hypohalides such as sodium and potassium hypochlorite are also suitable here.
Zur Herstellung von Wertprodukten I mit R1 = Alkylsulfinyl empfiehlt es sich, nicht mehr als ca. 1,1 Äquivalente des Oxidationsmittels einzusetzen. Zur Herstellung von I mit R1 = Alkylsulfonyl ist es notwendig, mindestens ein Äquivalent oder mindestens zwei Äquivalente des Oxidationsmittels einzusetzen, je nachdem, ob man von den entsprechenden Verbindungen I mit R1 = Alkylthio oder mit R1 = Alkylsulfinyl ausgeht.For the production of valuable products I with R 1 = alkylsulfinyl, it is advisable not to use more than about 1.1 equivalents of the oxidizing agent. To prepare I with R 1 = alkylsulfonyl, it is necessary to use at least one equivalent or at least two equivalents of the oxidizing agent, depending on whether one starts from the corresponding compounds I with R 1 = alkylthio or with R 1 = alkylsulfinyl.
Verfahren C)Process C)
Übergangsmetall -katalysierte Kreuzkupplungsreaktion von 2-Halogenpyridinen II (Hai = Chlor oder Brom) mit metall- organischen Verbindungen der Formel III auf an sich bekannte Weise {vgl. z.B. WO 95/02580 und die dort auf den Seiten 21 und 22 zitierte Literatur}:Transition metal-catalyzed cross-coupling reaction of 2-halopyridines II (Hai = chlorine or bromine) with organometallic compounds of the formula III in a manner known per se {cf. e.g. WO 95/02580 and the literature cited there on pages 21 and 22}:
ή
M1 steht für B(OH)2, Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br, Zn-J, Lithium, Kupfer oder Zinntri (Cx -C -alkyl) , vorzugsweise für B(OH)2, Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br oder Zn-J.ή M 1 stands for B (OH) 2 , Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br, Zn-J, lithium, copper or tin tri (Cx-C -alkyl), preferably for B. (OH) 2 , Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br or Zn-J.
Alternativ können statt der Boronsäuren III {M1 B(OH)2} auch die Boroxine IV eingesetzt werden.Alternatively, the boroxins IV can also be used instead of the boronic acids III {M 1 B (OH) 2 }.
Als Katalysatoren kommen insbesondere Palladiumkatalysatoren wie Tetrakis- (triphenylphosphin) -palladium (0) , Bis- (triphenyl - phosphin) -palladium (II) -chlorid, 1,4 -Bis- (diphenylphosphino) - butan-palladium(II) -chlorid, 1,2 -Bis- (diphenylphosphino) -ethan- palladiu dl ) -chlorid, Palladium (II) -acetat + Triphenylphosphin, Palladiumdl) -acetat + Tri - (o- tolyl) -phosphin oder Palladium auf Aktivkohle, und Nickelkatalysatoren wie Bis- (triphenyl - phosphin) -nickel (II) -chlorid, 1,3 -Bis- (diphenylphosphino) -propan- nickel (II) -chlorid oder Nickel (II) -acetylacetonat in Betracht.Palladium catalysts such as tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) chloride and 1,4-bis (diphenylphosphino) butane-palladium (II) chloride come in particular as catalysts , 1,2 -Bis (diphenylphosphino) ethane palladiu dl) chloride, palladium (II) acetate + triphenylphosphine, palladium dl) acetate + tri - (o-tolyl) phosphine or palladium on activated carbon, and nickel catalysts such as Bis- (triphenyl-phosphine) -nickel (II) chloride, 1,3-bis (diphenylphosphino) propane-nickel (II) chloride or nickel (II) acetylacetonate.
Verfahren D)Procedure D)
Reduktion von 5-Nitro-2 -phenylpyridinen der Formel V zu 5-Amino- 2 -phenylpyridinen VI, Diazotierung der Aminogruppe und Umsetzung der Diazoniumsalze mit einem symmetrischen aliphati- schen Disulfid der Formel VII auf an sich bekannte Weise:Reduction of 5-nitro-2-phenylpyridines of the formula V to 5-amino-2-phenylpyridines VI, diazotization of the amino group and reaction of the diazonium salts with a symmetrical aliphatic disulfide of the formula VII in a manner known per se:
5 }
Umsetzungen dieser Art sind allgemein bekannt, beispielsweise aus den folgenden Veröffentlichungen:5} Implementations of this type are generally known, for example from the following publications:
- Reduktion von Nitropyridinen mit Wasserstoff: F. Janssens et al., J. Med. Chem. 2.(12), S. 1943 (1985);- Reduction of nitropyridines with hydrogen: F. Janssens et al., J. Med. Chem. 2. (12), p. 1943 (1985);
- Reduktion von Nitropyridinen mit Eisen:- Reduction of nitropyridines with iron:
B.A. Fox et al., Org. Synth. ., S. 34 (1964);B.A. Fox et al., Org. Synth. ., P. 34 (1964);
- Reduktion von Nitropyridinen mit Zinn (II) chlorid:- Reduction of nitropyridines with tin (II) chloride:
L.A. Perez-Medina et al . , J. Am. Chem. Soc . 6__, S. 2574 (1947); - Reduktion von Nitropyridinen mit Hydrazin:L.A. Perez-Medina et al. , J. Am. Chem. Soc. 6__, p. 2574 (1947); - Reduction of nitropyridines with hydrazine:
G. J. Clark et al . , Aust. J. Chem. M, S. 927 (1981);G. J. Clark et al. , Aust. J. Chem. M, p. 927 (1981);
- Reduktion von Nitropyridinen mit Zinn:- Reduction of nitropyridines with tin:
K. Wojciechowski et al . , Synthesis , 651-653 (1986);K. Wojciechowski et al. , Synthesis, 651-653 (1986);
- Reduktion von Nitropyridinen mit niedervalenten Titanverbin- düngen: M. Malinowski, B. Soc. Chim. Belg. 9_7(1), 51-53 (1988);- Reduction of nitropyridines with low-valent titanium compounds: M. Malinowski, B. Soc. Chim. Belg. 9_7 (1), 51-53 (1988);
- Reduktion von Nitropyridinen mit Bäckerhefe:- Reduction of nitropyridines with baker's yeast:
M. Takeshita et al . , Heterocycles 11(12), 2201-2204 (1990);M. Takeshita et al. , Heterocycles 11 (12), 2201-2204 (1990);
- Reduktion von Nitropyridinen mit Zink:- Reduction of nitropyridines with zinc:
K. Goerlitzer et al., Arch. Phar . 121(10), 785-796 (1991); - Reduktion von Nitropyridinen mit Natriumdithionit : F.G. Fischer et al., Ann. Chem. £5_1, S. 49 (1962);K. Goerlitzer et al., Arch. Phar. 121 (10), 785-796 (1991); - Reduction of nitropyridines with sodium dithionite: F.G. Fischer et al., Ann. Chem. £ 5_1, p. 49 (1962);
- Diazotierung von Aminopyridinen mit Isoamylnitrit und Umsetzung der Diazoniumsalze mit Dimethyldisulf id oder Diphenyldisulfid: C.S. Giam et al., J. Chem. Soc, Chem. Commun. 1£, S. 756 (1980);- Diazotization of aminopyridines with isoamyl nitrite and reaction of the diazonium salts with dimethyl disulfide or diphenyl disulfide: C.S. Giam et al., J. Chem. Soc, Chem. Commun. £ 1, p. 756 (1980);
T. Yasumitsu et al., J. Org. Chem. 4£., 3564-3567 (1981).T. Yasumitsu et al., J. Org. Chem. 4 £., 3564-3567 (1981).
2- (4 -Chlor -3 -methoxyphenyl) - 5-nitropyridin, 2- (4 -Chlor -3 -methoxyphenyl) -3-chlor-5-nitropyridin, 5-Amino-2- (4 -chlor -3 -methoxy- phenyl) -pyridin und 5 -Amino-2 - (4 -chlor -3 -methoxyphenyl) - 3 -chlor- pyridin sind bereits aus der WO 95/02580 bekannt. Von diesen Verbindungen abgesehen sind die 5 -Nitro- 2 -phenylpyridine V und die 5 -Amino- 2 -phenylpyridine VI neu. Die Herstellung von V erfolgt zweckmäßigerweise analog Verfahren C> durch Übergangsmetall - katalysierte Kreuzkupplungsreaktion von 2 -Halogen- 5 -nitropyridinen der Formel VIII (Hai = Chlor oder Brom) mit metallorganischen Verbindungen der Formel IX {vgl. z.B. M.B. Mitchell et al . , Tetrahedron Lett. 21. 2273-2276 (1991)}:2- (4-Chloro-3-methoxyphenyl) -5-nitropyridine, 2- (4-Chloro-3-methoxyphenyl) -3-chloro-5-nitropyridine, 5-amino-2- (4-chloro-3-methoxy - Phenyl) pyridine and 5-amino-2 - (4-chloro-3-methoxyphenyl) -3-chloro-pyridine are already known from WO 95/02580. Apart from these compounds, the 5 -nitro-2-phenylpyridines V and the 5 -amino-2 -phenylpyridines VI are new. V is expediently prepared analogously to process C> by transition metal-catalyzed cross-coupling reaction of 2 -halogen-5-nitropyridines of the formula VIII (Hai = chlorine or bromine) with organometallic compounds of the formula IX {cf. e.g. M.B. Mitchell et al. , Tetrahedron Lett. 21. 2273-2276 (1991)}:
3S
M2 steht für B(OH) , Zn-Cl, Zn-Br, Zn-J, Kupfer oder Zinn- tri (Cχ-C4-alkyl) .3S M 2 stands for B (OH), Zn-Cl, Zn-Br, Zn-J, copper or tin tri (Cχ-C 4 alkyl).
Die unter Verfahren C) angegebenen Katalysatoren kommen auch hier in Betracht.The catalysts specified under process C) are also suitable here.
Verfahren E>Procedure E>
Diazotierung von 5 -Amino- 2 -phenylpyridinen der Formel VI und Umsetzung der Diazoniumsalze mit S02 in Gegenwart von Kupfer (II)- chlorid {vgl. z.B. US 4,784,684 und Gilbert in Synthesis 1969,Diazotization of 5-amino-2-phenylpyridines of the formula VI and reaction of the diazonium salts with S0 2 in the presence of copper (II) chloride {cf. e.g. US 4,784,684 and Gilbert in Synthesis 1969,
Reaktion von I (R1 = S02C1) mit Ammoniak, primären oder sekundären Aminen führt zu den entsprechenden Verbindungen I mit Rl = H2N-S02, Alkyl-NH-S02 oder (Alkyl)2N-S02 {vgl. z.B. C. Naegeli et al., Helv. Chim. Acta 21, 1485 (1942); M. Yasuhiro et al., J. Med. Chem. 21, 1376-1380 (1980); J.F. Liegeois et al . , Helv. Chim. Acta IA, 8, 1764-1772 (1991) und P. De Tullio et al., Tetrahedron H, 11, 3221-3234 (1995} Reaction of I (R 1 = S0 2 C1) with ammonia, primary or secondary amines leads to the corresponding compounds I with R l = H 2 N-S0 2 , alkyl-NH-S0 2 or (alkyl) 2 N-S0 2 {see. e.g. C. Naegeli et al., Helv. Chim. Acta 21, 1485 (1942); M. Yasuhiro et al., J. Med. Chem. 21, 1376-1380 (1980); JF Liegeois et al. , Helv. Chim. Acta IA, 8, 1764-1772 (1991) and P. De Tullio et al., Tetrahedron H, 11, 3221-3234 (1995}
I (Cχ-C6-Alkyl)NH2 I (Cχ-C 6 alkyl) NH 2
(R1 Cl- S02) I {R1 = (Cχ-C6-Alkyl) -NH-S02}(R 1 Cl- S0 2 ) I {R 1 = (Cχ-C 6 alkyl) -NH-S0 2 }
I {R1 = (C -C6-Alkyl)2N-S02} I {R 1 = (C -C 6 alkyl) 2 N-S0 2 }
(Cχ-C6-Alkyl)2NH(Cχ-C 6 alkyl) 2 NH
Die substituierten 2 -Phenylpyridine I mit R1 = Chlorsulfonyl können außerdem auch zu den entsprechenden Verbindungen I mit R1 = Hydroxysulfonyl hydrolysiert werden.The substituted 2 -phenylpyridines I with R 1 = chlorosulfonyl can also be hydrolyzed to the corresponding compounds I with R 1 = hydroxysulfonyl.
Normalerweise sind die substituierten 2-Phenylpyridine I nach einem der vorstehend genannten Syntheseverfahren herstellbar. Aus wirtschaftlichen oder verfahrenstechnischen Gründen kann es jedoch zweckmäßiger sein, einige Verbindungen I aus ähnlichen 2-Phenylpyridinen, die sich jedoch in der Bedeutung eines Restes unterscheiden, herzustellen.The substituted 2-phenylpyridines I can normally be prepared by one of the synthesis processes mentioned above. For economic or procedural reasons, however, it may be more expedient to prepare some compounds I from similar 2-phenylpyridines, but which differ in the meaning of a radical.
3 1
Die Verbindungen der Formel Ha3 1 The compounds of the formula Ha
sind neu. 2 -Chlor - 5 -methylthiopyridm ist z.B. aus J. Med. are new. 2 -Chlor - 5 -methylthiopyridm is for example from J. Med.
Chem. 16., 319-327 (1973) bekannt. Bezuglich 2 -Chlor- 5-methyl - sulfinyl- und 2 -Chlor- 5 -methylsulfonylpyridin vgl. J. Med.Chem. 16., 319-327 (1973). For 2-chloro-5-methyl-sulfinyl and 2-chloro-5-methylsulfonylpyridine see. J. Med.
Chem. 2i< 427-433 (1986); bezuglich 2 -Brom- 5 - ter . -butyl thio- pyridin sei auf Bull. Soc. Chim. Belg. 9_5_, 1009-1020 (1986) verwiesen.Chem. 2i <427-433 (1986); regarding 2 -Brom- 5 - ter. -butyl thiopyridine is on Bull. Soc. Chim. Belg. 9_5_, 1009-1020 (1986).
Allgemein kann die Herstellung der 2 -Halogenpyridine II z.B. durch Diazotierung der entsprechenden 5 -Am opyridme X 1 ] - vor- zugsweise mit einem Salpetrigsäureester wie tert . -Butylnitrit und Isopentylnitrit - und anschließender Umsetzung des Diazonium- salzes mit einem symmetrischen aliphatischen Disulfid VII erfolgen {vgl. z.B. J. Chem. Soc, Chem. Commun. 1980, S. 756/757}: 1. Diazotierung 2 (Cι,C6,Alkyl),s"
(C,-C6-Alkyl)-SIn general, the preparation of the 2 -halopyridines II can be carried out, for example, by diazotizing the corresponding 5 -Am opyridme X 1] - preferably with a nitrous acid ester such as tert. -Butyl nitrite and isopentyl nitrite - and subsequent reaction of the diazonium salt with a symmetrical aliphatic disulfide VII {see. e.g. J. Chem. Soc, Chem. Commun. 1980, pp. 756/757}: 1. Diazotization 2 (Cι, C6, alkyl), s " (C, -C 6 alkyl) -S
X VIIX VII
Die Diazotierung kann auch in Gegenwart des Disulfids VII stattfinden.The diazotization can also take place in the presence of disulfide VII.
Vorzugsweise arbeitet man in einem wasserfreien System, beispielsweise in Eisessig, der Chlorwasserstoff enthalt, in Dioxan, absolutem Ethanol, Tetrahydrofuran, Acetonitril oder in Aceton.It is preferable to work in an anhydrous system, for example in glacial acetic acid which contains hydrogen chloride, in dioxane, absolute ethanol, tetrahydrofuran, acetonitrile or in acetone.
Die Reaktionstemperatur liegt normalerweise bei (-30) bis 80°C.The reaction temperature is usually (-30) to 80 ° C.
Üblicherweise werden die Komponenten der Diazotierungsreaktion in etwa stochiometrischem Verhältnis eingesetzt, jedoch kann auch ein Überschuß einer der Komponenten, z.B. im Hinblick auf eine möglichst vollständige Umsetzung der anderen Komponente, vorteilhaft sein. Bevorzugt verwendet man das Nitrit im Überschuß, bis etwa zur 2fachen molaren Menge, bezogen auf die Menge an X.The components of the diazotization reaction are usually used in an approximately stochiometric ratio, but an excess of one of the components, e.g. with a view to implementing the other component as completely as possible. The nitrite is preferably used in excess, up to about 2 times the molar amount, based on the amount of X.
Das Disulfid VII wird zweckmäßig in ca. äqui olaren Mengen oder im Überschuß, bezogen auf das Diazoniumsalz , eingesetzt. Im allgemeinen hat sich ein großer Überschuß an Disulfid VII (bis etwa zur 5fachen molaren Menge) , bezogen auf die Menge an Diazoniumsalz, als besonders vorteilhaft erwiesen.The disulfide VII is expediently used in approximately equi olar amounts or in excess, based on the diazonium salt. In general, a large excess of disulfide VII (up to about 5 times the molar amount), based on the amount of diazonium salt, has proven to be particularly advantageous.
-) zu deren Herstellung siehe J Med. Chem.16, 319-327 (1973)
Die 2 -Halogenpyridine II mit R1 = Cx -Cβ-Alkylthio können anschließend zu den entsprechenden Verbindungen mit R1 = Cχ-C6-Alkylsulfinyl oder Cx -C6 -Alkylsulfonyl oxidiert werden, wie es unter Verfahren B> für die Verbindungen I mit R1 = Ci -C6 -Alkylthio beschrieben wurde.- ) for their production see J Med. Chem. 16, 319-327 (1973) The 2 -halopyridines II with R 1 = Cx-Cβ-alkylthio can then be oxidized to the corresponding compounds with R 1 = Cχ-C 6 -alkylsulfinyl or Cx -C 6 -alkylsulfonyl, as described under process B> for the compounds I with R 1 = Ci -C 6 alkylthio has been described.
Sofern nicht anders angegeben werden alle vorstehend beschriebenen Verfahren zweckmäßigerweise bei Atmosphärendruck oder unter dem Eigendruck des jeweiligen Reaktionsgemisches vorgenommen.Unless otherwise stated, all of the processes described above are expediently carried out at atmospheric pressure or under the autogenous pressure of the respective reaction mixture.
Die Aufarbeitung der Reaktionsgemische erfolgt in der Regel nach an sich bekannten Methoden, beispielsweise durch Verdünnen der Reaktionslösung mit Wasser und anschließender Isolierung des Produktes mittels Filtration, Kristallisation oder Lösungsmittelextraktion, oder durch Entfernen des Lösungsmittels, Verteilen des Rückstandes in einem Gemisch aus Wasser und einem geeigneten organischen Lösungsmittel und Aufarbeiten der organischen Phase auf das Produkt hin.The reaction mixtures are generally worked up by methods known per se, for example by diluting the reaction solution with water and then isolating the product by means of filtration, crystallization or solvent extraction, or by removing the solvent, distributing the residue in a mixture of water and a suitable one organic solvents and working up the organic phase towards the product.
Die substituierten 2-Phenylpyridine I können bei der Herstellung als Isomerengemische anfallen, die jedoch gewünschtenfalls nach den hierfür üblichen Methoden wie Kristallisation oder Chromatographie, auch an einem optisch aktiven Adsorbat, in die weit- gehend reinen Isomeren getrennt werden können. Reine optisch aktive Isomere lassen sich vorteilhaft aus entsprechenden optisch aktiven Ausgangsprodukten herstellen.The substituted 2-phenylpyridines I can be obtained in the preparation as isomer mixtures, which, however, if desired, can be separated into the largely pure isomers by the customary methods such as crystallization or chromatography, including on an optically active adsorbate. Pure optically active isomers can advantageously be prepared from corresponding optically active starting products.
Landwirtschaftlich brauchbare Salze der Verbindungen I können durch Reaktion mit einer Base des entsprechenden Kations, vorzugsweise einem Alkalimetallhydroxid oder -hydrid, gebildet werden.Agricultural salts of the compounds I can be formed by reaction with a base of the corresponding cation, preferably an alkali metal hydroxide or hydride.
Salze von I, deren Metallion kein Alkalimetallion ist, können auch durch Umsalzen des entsprechenden Alkalimetallsalzes in üblicher Weise hergestellt werden, ebenso Ammonium-, Phosphonium-, Sulfonium- und Sulfoxoniumsalze mittels Ammoniak, Phosphonium-, Sulfonium- oder Sulfoxoniumhydroxiden.Salts of I, the metal ion of which is not an alkali metal ion, can also be prepared in a conventional manner by salting the corresponding alkali metal salt, as can ammonium, phosphonium, sulfonium and sulfoxonium salts using ammonia, phosphonium, sulfonium or sulfoxonium hydroxides.
Die Verbindungen I und deren landwirtschaftlich brauchbaren Salze eignen sich - sowohl als Isomerengemische als auch in Form der reinen Isomeren - als Herbizide. Die I enthaltenden herbiziden Mittel bekämpfen Pflanzenwuchs auf Nichtkulturflächen sehr gut, besonders bei hohen Aufwandmengen. In Kulturen wie Weizen, Reis, Mais, Soja und Baumwolle wirken sie gegen Unkräuter und Schad-The compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides. The herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and harmful
hι
gräser, ohne die Kulturpflanzen nennenswert zu schädigen. Dieser Effekt tritt vor allem bei niedrigen Aufwandmengen auf.hι grasses without significantly damaging the crops. This effect occurs especially at low application rates.
In Abhängigkeit von der jeweiligen Applikationsmethode können die Verbindungen I bzw. sie enthaltenden herbiziden Mittel noch in einer weiteren Zahl von Kulturpflanzen zur Beseitigung unerw nschter Pflanzen eingesetzt werden. In Betracht kommen beispielsweise folgende Kulturen: Alliu cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var . napus, Brassica napus var. napobrassica, Brassica rapa 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, (Gossypiu arboreum, Gossypium herbaceu , Gossypium vitifolium) , Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicu , Malus spec, Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa , Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pisu sativ m, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgäre), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera und Zea mays .Depending on the particular application method, the compounds I or herbicidal compositions comprising them can also be used in a further number of crop plants for removing undesired plants. The following crops are possible, for example: Alliu cepa, pineapple comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodonine dactis , Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypiu arboreum, Gossypium herbaceu, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culitaticonersusum, lens culitatissusum , Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pisu sativ m, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (see vulgar), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triti cum durum, Vicia faba, Vitis vinifera and Zea mays.
Darüber hinaus können die Verbindungen I auch in Kulturen, die durch Züchtung einschließlich gentechnischer Methoden gegen die Wirkung von Herbiziden tolerant sind, verwandt werden.In addition, the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
Des weiteren eignen sich die substituierten 2-Phenylpyridine I auch zur Desikkation und/oder Defoliation von Pflanzen.Furthermore, the substituted 2-phenylpyridines I are also suitable for the desiccation and / or defoliation of plants.
Als Desikkantien eignen sie sich insbesondere zur Austrocknung der oberirdischen Teile von Kulturpflanzen wie Kartoffel, Raps, Sonnenblume und Sojabohne. Damit wird ein vollständig mechani- sches Beernten dieser wichtigen Kulturpflanzen ermöglicht.As desiccants, they are particularly suitable for drying out the above-ground parts of crops such as potatoes, rapeseed, sunflower and soybeans. This enables fully mechanical harvesting of these important crops.
Von wirtschaf lichem Interesse ist ferner die Ernteerleichterung, die durch das zeitlich konzentrierte Abfallen oder Vermindern der Haftfestigkeit am Baum bei Zitrusfruchten, Oliven oder bei ande- ren Arten und Sorten von Kern-, Stein- und Schalenobst ermöglicht wird. Derselbe Mechanismus, das heißt die Förderung der Ausbildung von Trenngewebe zwischen Frucht- oder Blatt- und Sproßteil l
der Pflanzen ist auch für ein gut kontrollierbares Entblättern von Nutzpflanzen, insbesondere Baumwolle, wesentlich.Also of economic interest is the ease of harvesting, which is made possible by the temporally concentrated drop or decrease in the adhesive strength on the tree for citrus fruits, olives or other types and varieties of pome, stone and nuts. The same mechanism, that is, the promotion of the formation of separating tissue between the fruit or leaf and sprout part l of the plants is also essential for a well controllable defoliation of useful plants, especially cotton.
Außerdem führt die Verkürzung des Zeitintervalls, in dem die einzelnen Baumwollpflanzen reif werden, zu einer erhöhten Faser- qualitat nach der Ernte.In addition, the shortening of the time interval in which the individual cotton plants ripen leads to an increased fiber quality after the harvest.
Die Verbindungen I bzw. die sie enthaltenden Mittel können beispielsweise in Form von direkt verspruhbaren wäßrigen Losun- gen, Pulvern, Suspensionen, auch hochprozentigen wäßrigen, öligen oder sonstigen Suspensionen oder Dispersionen, Emulsionen, Oldispersionen, Pasten, Stäubemitteln, Streumitteln oder Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfindungsgemäßen Wirkstoffe gewahr - leisten.The compounds I or the compositions comprising them can be sprayed, for example in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, old-dispersions, pastes, dusts, sprays or granules. Nebulization, dusting, scattering or pouring can be used. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
Als inerte Hilfsstoffe kommen im wesentlichen in Betracht: Mineralölfraktionen von mittlerem bis hohem Siedepunkt wieThe following are essentially considered as inert auxiliaries: mineral oil fractions of medium to high boiling point such as
Kerosin und Dieselöl, ferner Kohlenteerole sowie Ole pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Paraffine, Tetrahydronaphthalin, alkylierte Naphthaline und deren Derivate, alkylierte Benzole und deren Derivate, Alkohole wie Methanol, Ethanol, Propanol, Butanol und Cyclohexanol, Ketone wie Cyclohexanon, stark polare Lösungsmittel, z.B. Amine wie N-Methylpyrrolidon und Wasser.Kerosene and diesel oil, also coal tarols and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, 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, e.g. Amines such as N-methylpyrrolidone and water.
Wäßrige Anwendungsformen können aus Emulsionskonzentraten, Suspensionen, Pasten, netzbaren Pulvern oder wasserdispergier- baren Granulaten durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Oldispersionen können die Substrate als solche oder in einem 01 oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermittel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz, Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Losungsmittel oder 01 bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind.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 oldispersions, the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare active substances, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or existing concentrates which are suitable for dilution with water.
Als oberflächenaktive Stoffe (Adjuvantien) kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsäuren, z.B. Lignin-, Phenol-, Naphthalin- und Dibutylnaphthalinsulfonsäure, sowie von Fettsäuren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Laurylether- und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta- und Octadecanolen sowie von Fettalkoholglykolether, Kondensationsprodukte von sulfoniertem Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des NaphthalinsThe surfactants (adjuvants) are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene
<ι3
bzw. der Naphthalinsulfonsauren mit Phenol und Formaldehyd, Poly- oxyethylenoctylphenolether , ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Alkylphenyl-, Tributylphenylpolyglykolether , Alkyl - arylpolyetheralkohole, Isotridecylalkohol , Fettalkoholethylen- oxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylen- oder Polyoxypropylenalkylether, Laurylalkoholpolyglykoletheracetat, Sorbitester, Lignin-Sulfitablaugen oder Methylcellulose in Betracht .<ι3 or the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensate oil, polyoxyethylene ethoxylated alcohol ethoxylated ethoxylated alcohol ethoxylated ethylene glycol ethoxylated ethylene glycol ethoxylated ethylene glycol ethoxylated ethylene glycol ethoxylated ethylene glycol ethoxylated ethoxylated ethylene glycol ethoxylated alkoxylated ethoxylated ethoxylated ethoxylated ethoxylated ethoxylated alcohol, , Lignin sulfite liquor or methyl cellulose.
Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden.Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
Granulate, z.B. Umhullungs-, Imprägnierungs- und Homogengranulate können durch Bindung der Wirkstoffe an feste Tragerstoffe hergestellt werden. Feste Trägerstoffe sind Mineralerden wie Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Loß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Dunge- mittel, wie Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver oder andere feste Trägerstoffe.Granules, e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as corn flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
Die Konzentrationen der Wirkstoffe I in den anwendungsfertigen Zubereitungen können in weiten Bereichen variiert werden. Im allgemeinen enthalten die Formulierungen etwa von 0,001 bis 98 Gew.-%, vorzugsweise 0,01 bis 95 Gew.-%, mindestens eines Wirkstoffs. Die Wirkstoffe werden dabei in einer Reinheit von 90% bis 100%, vorzugsweise 95% bis 100% (nach NMR-Spektrum) eingesetzt .The concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range. In general, the formulations contain from about 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
Die folgenden Formulierungsbeispiele verdeutlichen die Herstellung solcher Zubereitungen:The following formulation examples illustrate the preparation of such preparations:
I. 20 Gewichtsteile der Verbindung Nr. Ia.181 werden in einer Mischung gelöst, die aus 80 Gewichtsteilen alkylierte Benzol, 10 Gewichtsteilen des Anlagerungsproduktes von 8 bis 10 Mol Ethylenoxid an 1 Mol Ölsäure-N-monoethanolamid, 5 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsäure und 5 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Rizinusöl besteht. Durch Ausgießen und feines Verteilen der Lösung in 100000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.-% des Wirkstoffs enthält.
II. 20 Gewichtsteile der Verbindung Nr. Ia.384 werden in einer Mischung gelöst, die aus 40 Gewichtsteilen Cyclohexanon,I. 20 parts by weight of compound no. Ia.181 are dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 Parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient. II. 20 parts by weight of compound no. Ia.384 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone,
30 Gewichtsteilen Isobutanol, 20 Gewichtsteilen des Anlagerungsproduktes von 7 Mol Ethylenoxid an 1 Mol Isooctyl- phenol und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Rizinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.-% des Wirkstoffs enthält.30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the additive of 40 moles of ethylene oxide with 1 mole 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.
III. 20 Gewichtsteile des Wirkstoffs Nr. Ia.402 werden in einer Mischung gelöst, die aus 25 Gewichtsteilen Cyclohexanon, 65 Gewichtsteilen einer Mineralölfraktion vom Siedepunkt 210 bis 280°C und 10 Gewichtsteilen des Anlagerungs- Produktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.-% des Wirkstoffs enthält.III. 20 parts by weight of active ingredient No. Ia.402 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole 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.
IV. 20 Gewichtsteile des Wirkstoffs Nr. 2 werden mitIV. 20 parts by weight of active ingredient No. 2 are with
3 Gewichtsteilen des Natriumsalzes der Diisobutyl- naphthalin-α-sulfonsäure, 17 Gewichtsteilen des Natriumsalzes einer Ligninsulfonsäure aus einer Sulfit-Ablauge und 60 Gewichtsteilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermählen. Durch feines Verteilen der Mischung in 20000 Gewichtsteilen Wasser erhält man eine Spritzbrühe, die 0,1 Gew.-% des Wirkstoffs enthält.3 parts by weight of the sodium salt of diisobutyl-naphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel are mixed well and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient.
V. 3 Gewichtsteile des Wirkstoffs Nr. 3 werden mitV. 3 parts by weight of active ingredient No. 3 are with
97 Gewichtsteilen feinteiligem Kaolin vermischt. Man erhält auf diese Weise ein Stäubemittel, das 3 Gew.-% des Wirkstoffs enthält.97 parts by weight of finely divided kaolin mixed. In this way, a dust is obtained which contains 3% by weight of the active ingredient.
VI. 20 Gewichtsteile des Wirkstoffs Nr. 7 werden mitVI. 20 parts by weight of active ingredient No. 7 are with
2 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsäure, 8 Gewichtsteilen Fettalkohol-polyglykolether, 2 Gewichtsteilen Natriumsalz eines Phenol-Harnstoff-Formaldehyd- Kondensates und 68 Gewichtsteilen eines paraffinischen Mineralöls innig vermischt. Man erhält eine stabile ölige Dispersion.2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
VII. 1 Gewichtsteil des Wirkstoffs Nr. 10 wird in einerVII. 1 part by weight of active ingredient No. 10 is in a
Mischung gelöst, die aus 70 Gewichtsteilen Cyclohexanon, 20 Gewichtsteilen ethoxyliertem Isooctylphenol undDissolved mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and
10 Gewichtsteilen ethoxyliertem Rizinusöl besteht. Man erhält ein stabiles Emulsionskonzentrat. T
VIII. 1 Gewichtsteil des Wirkstoffs Nr. 13 wird in einerThere are 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained. T VIII. 1 part by weight of active ingredient No. 13 is in a
Mischung gelost, die aus 80 Gewichtsteilen Cyclohexanon undMixture made up of 80 parts by weight of cyclohexanone and
(fr(fr
20 Gewichtsteilen Wettol J EM 31 (= nichtionischer Emulgator auf der Basis von ethoxyliertem Rizinusöl; BASF AG) besteht. Man erhält ein stabiles Emulsionskonzentrat.20 parts by weight of Wettol J EM 31 (= nonionic emulsifier based on ethoxylated castor oil; BASF AG). A stable emulsion concentrate is obtained.
Die Applikation der Wirkstoffe I bzw. der herbiziden Mittel kann im Vorauflauf- oder im Nachauflaufverfahren erfolgen. Sind die Wirkstoffe für gewisse Kulturpflanzen weniger verträglich, so können Ausbringungstechniken angewandt werden, bei welchen die herbiziden Mittel mit Hilfe der Spritzgerate so gespritzt werden, daß die Blätter der empfindlichen Kulturpflanzen nach Möglichkeit nicht getroffen werden, während die Wirkstoffe auf die Blatter darunter wachsender unerw nschter Pflanzen oder die unbedeckte Bodenfläche gelangen (post-directed, lay-by) .The active ingredients I or the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less compatible for certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck wherever possible, while the active ingredients on the leaves underneath are growing undesirably Plants or the uncovered floor area (post-directed, lay-by).
Die Aufwandmengen an Wirkstoff I betragen je nach Bekämpfungs- ziel, Jahreszeit, Zielpflanzen und Wachstumsstadium 0,001 bis 3,0, vorzugsweise 0,01 bis 1,0 kg/ha aktive Substanz (a.S.).The application rates of active ingredient I are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a.S.) depending on the control target, the season, the target plants and the growth stage.
Zur Verbreiterung des Wirkungsspektrums und zur Erzielung synergistischer Effekte können die substituierten 2-Phenylpyridιne I mit zahlreichen Vertretern anderer herbizider oder Wachstums - regulierender Wirkstoffgruppen gemischt und gemeinsam ausgebracht werden. Beispielsweise kommen als Mischungspartner 1,2,4-Thia- diazole, 1 , 3 , 4-Thiadiazole, A ide, Aminophosphorsäure und deren Derivate, Aminotriazole, Anilide, Aryloxy-/Heteroaryloxyalkan- säuren und deren Derivate, Benzoesäure und deren Derivate, Benzo- thiadiazinone, 2 - (Hetaroyl/Aroyl) - 1, 3 -cyclohexandione, Hetero- aryl-Aryl-Ke one, Benzylisoxazolidinone, meta-CF-Phenylderivate, Carbamate, Chinolincarbonsäure und deren Derivate, Chloracet- anilide, Cyclohexan-1, 3-dionderivate, Diazine, Dichlorpropion- säure und deren Derivate, Dihydrobenzofurane, Dihydrofuran-3-one, Dinitroaniline, Dinitrophenole, Diphenylether , Dipyridyle, Halogencarbonsäuren und deren Derivate, Harnstoffe, 3-Phenyl- uracile, Imidazole, Imidazolinone, N-Phenyl-3, 4 , 5, 6-tetrahydro- phthalimide, Oxadiazole, Oxirane, Phenole, Aryloxy- und Hetero- aryloxyphenoxypropionsäureester, Phenylessigsäure und deren Derivate, 2-Phenylpropionsäure und deren Derivate, Pyrazole, Phenylpyrazole, Pyridazine, Pyridincarbonsäure und deren Derivate, Pyrimidylether, Sulfonamide, Sulfonylharnstoffe, Triazine, Triazinone, Triazolinone, Triazolcarboxamide und Uracile in Betracht.To broaden the spectrum of activity and to achieve synergistic effects, the substituted 2-phenylpyridines I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together. For example, 1,2,4-thiazadiols, 1,3,4-thiadiazoles, amide, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy- / heteroaryloxyalkanoic acids and their derivatives, benzoic acid and their derivatives, benzo, come as mixing partners - thiadiazinone, 2 - (hetaroyl / aroyl) - 1, 3 -cyclohexanedione, heteroaryl-aryl-ke one, benzylisoxazolidinones, meta-CF-phenyl derivatives, carbamates, quinoline carboxylic acid and their derivatives, chloroacetanilides, cyclohexane-1, 3 -dione derivatives, diazines, dichloropropionic acid and their derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyl-uracils, imidazoles, imidazylones, 3-one , 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, pyridine car bonic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.
Außerdem kann es von Nutzen sein, die Verbindungen I allein oder in Kombination mit anderen Herbiziden auch noch mit weiteren Pflanzenschutzmitteln gemischt, gemeinsam auszubringen, bei-
spielsweise mit Mitteln zur Bekämpfung von Schädlingen oder phytopathogenen Pilzen bzw. Bakterien. Von Interesse ist ferner die Mischbarkeit mit Mineralsalzlösungen, welche zur Behebung von Ernährungs- und Spurenelementmängeln eingesetzt werden. Es können auch nichtphytotoxische Öle und Ölkonzentrate zugesetzt werden.It can also be useful to apply the compounds I alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.
HerstellungsbeispieleManufacturing examples
Beispiel 1 (Verbindung Ia.384 in Tabelle 1):Example 1 (Compound Ia.384 in Table 1):
12,1 g (2 , 3 -Dichlor-5-mechylsulfonylpyridin, 11,05 g 4-Chlor-2- fluor- 5-methoxybenzolboronsäure, 13,6 g Natriumhydrogencarbonat und 2,0 g Tetrakis (triphenylphosphin) -palladiu (0) wurden in 360 ml einer Tetrahydrof ran/Wasser-Mischung (1:1) 120 Stunden auf Rückflußtemperatur erhitzt. Nach Abkühlen auf Raumtemperatur extrahierte man dreimal mit je 200 ml Methyl - tert . -butylether (MTB) . Die vereinigten organischen Phasen wurden mit 100 ml Wasser gewaschen, dann über Natriumsulfat getrocknet und schließlich eingeengt. Die Reinigung des Rohproduktes erfolgte mittels Säulenchromatographie an Kieselgel (Laufmittel: Cyclohexan/MTB = ■ 10:1 → 7:3 → 1:1). Die erhaltenen weißen Kristalle (5,8 g) wurden durch Ausrühren mit MTB/Petrolether (1:1) weiter gereinigt. Ausbeute: 5,2 g (27 %) ; Smp. : 184-185°C.12.1 g (2,3-dichloro-5-mechylsulfonylpyridine, 11.05 g 4-chloro-2-fluoro-5-methoxybenzeneboronic acid, 13.6 g sodium hydrogen carbonate and 2.0 g tetrakis (triphenylphosphine) palladiu (0) were heated to reflux temperature for 120 hours in 360 ml of a tetrahydrofuran / water mixture (1: 1). After cooling to room temperature, the mixture was extracted three times with 200 ml each of methyl tert-butyl ether (MTB) ml of water, then dried over sodium sulfate and finally evaporated in. The crude product was purified by column chromatography on silica gel (mobile phase: cyclohexane / MTB = 10: 1 → 7: 3 → 1: 1). The white crystals obtained (5.8 g) were further purified by stirring with MTB / petroleum ether (1: 1) Yield: 5.2 g (27%), mp: 184-185 ° C.
Vorstufe α: 2 , 3 -Dichlor- 5 - ethylthio-pyridinPrecursor α: 2,3-dichloro-5-ethylthio-pyridine
Zu einer Lösung von 56,6 g (0,6 mol) Dimethyldisulfid und 46,7 g (0,45 mol) tert . -Butylnitrit in 320 ml trockenem Methylenchlorid tropfte man langsam bei 40°C eine Lösung von 50,6 g (0,3 mol) 3 -Amino- 5, 6 -dichlorpyridin in 700 ml Methylenchlorid. Dann wurde die Mischung 1 Std. bei 40°C und anschließend noch etwa 15 Std. bei ca. 20°C gerührt, wonach man 500 ml Eiswasser zum Reaktionsgemisch gab. Die abgetrennte organische Phase wurde einmal mit 1 N Salzsäure und einmal mit Wasser gewaschen, über Natriumsulfat getrocknet und schließlich eingeengt. Nach Verrühren des Rohprodukts mit n-Hexan erhielt man 21 g eines dunklen Feststoffs (94 % Reinheit nach GC) . Nach Einengen der Hexanlösung verblieben noch 21,3 g Wertprodukt mit einer Reinheit von 77 % (nach GC) . Gesamtausbeute: 62 %; Fp. : 66-67°C; 1H-NMR (in d6-Dimethyl- sulfoxid) : δ [ppm] = 2,6 (s,CH3); 8,1 und 8,3 (2xd,Pyr-H).To a solution of 56.6 g (0.6 mol) of dimethyl disulfide and 46.7 g (0.45 mol) of tert. -Butyl nitrite in 320 ml of dry methylene chloride, a solution of 50.6 g (0.3 mol) of 3-amino-5, 6 -dichloropyridine in 700 ml of methylene chloride was slowly added at 40 ° C. The mixture was then stirred at 40 ° C. for 1 hour and then at about 20 ° C. for a further 15 hours, after which 500 ml of ice water were added to the reaction mixture. The separated organic phase was washed once with 1N hydrochloric acid and once with water, dried over sodium sulfate and finally concentrated. After stirring the crude product with n-hexane, 21 g of a dark solid (94% purity according to GC) were obtained. After concentrating the hexane solution, 21.3 g of valuable product with a purity of 77% remained (according to GC). Overall yield: 62%; Mp: 66-67 ° C; 1 H-NMR (in d 6 -dimethyl sulfoxide): δ [ppm] = 2.6 (s, CH 3 ); 8.1 and 8.3 (2xd, Pyr-H).
Vorstufe ß: 2 , 3 -Dichlor-5 - ethylsulfinyl-pyridinPrecursor β: 2,3-dichloro-5-ethylsulfinyl-pyridine
Zu einer Suspension von 10 g (0,052 mol) 2, -Dichlor -5 -methyl - thio-pyridin in 60 ml Methylenchlorid wurden portionsweise 8,9 g (0,052 mol) m-Chlorperbenzoesäure gegeben. Nach 2 Std. Rühren bei ca. 20°C versetzte man die Mischung mit weiteren 0,9 g (5 mmol)
m-Chlorperbenzoesäure. Anschließend wurde noch 2 Std. auf Rück- flußtemperatur erhitzt. Nach dem Abkühlen trennte man den Fest- stoffanteil ab, wonach die organische Phase einmal mit Natriumhydrogensulfit, einmal mit Natriumhydrogencarbonat und einmal mit Wasser gewaschen wurde. Nach Trocknen über Natriumsulfat engte man ein. Das als rotes Öl erhaltene Rohprodukt wurde mittels "Flashchromatographie" an Kieselgel (Laufmittel: Cyclohexan/Es- sigester = 1:1) gereinigt. Ausbeute: 6,3 g (58 %) als braunes Öl; *H-NMR (in d6 -Dimethylsulfoxid) : δ [ppm] = 2,9 (s,CH3); 8,4 und 8,7 (2xd,Pyr-H) .8.9 g (0.052 mol) of m-chloroperbenzoic acid were added in portions to a suspension of 10 g (0.052 mol) of 2, -dichloro-5-methylthio-pyridine in 60 ml of methylene chloride. After stirring for 2 hours at about 20 ° C., the mixture was mixed with a further 0.9 g (5 mmol) m-chloroperbenzoic acid. The mixture was then heated to the reflux temperature for a further 2 hours. After cooling, the solids fraction was separated off, after which the organic phase was washed once with sodium hydrogen sulfite, once with sodium hydrogen carbonate and once with water. After drying over sodium sulfate, the mixture was concentrated. The crude product obtained as a red oil was purified by means of "flash chromatography" on silica gel (mobile phase: cyclohexane / ethyl acetate = 1: 1). Yield: 6.3 g (58%) as a brown oil; * H NMR (in d 6 -dimethylsulfoxide): δ [ppm] = 2.9 (s, CH 3 ); 8.4 and 8.7 (2xd, Pyr-H).
Vorstufe γ: 2 , 3 -Dichlor - 5 -methylsulfonyl -pyridinPrecursor γ: 2,3-dichloro-5-methylsulfonyl-pyridine
Zu einer Lösung von 73,7 g (0,38 mol) 2 , 3 -Dichlor- 5 -methylthio- pyridin in 380 ml Eisessig wurden 6,2 g (0,02 mol) Na2W04-2H20 gegeben. Nach Erhitzen auf 40-50°C versetzte man die Mischung vorsichtig mit 95 g Wasserstoffperoxid (30%ig) . Anschließend wurde noch 1 Std. bei ca. 20°C nachgerührt. Dann gab man das Gemisch in 300 ml Wasser. Von der erhaltenen Suspension wurde das Produkt abgetrennt, mit Wasser und n-Pentan gewaschen und bei reduziertem- Druck getrocknet. Ausbeute: 60 g (70 %) als braunes Pulver; Fp.: 129-130°C; *H-NMR (in d6-Dimethylsulfoxid) : δ [ppm] = 3,4 (s,CH3); 8,7 und 8,9 (2xd,Pyr-H).6.2 g (0.02 mol) of Na 2 WO 4 -2H 2 O were added to a solution of 73.7 g (0.38 mol) of 2,3-dichloro-5-methylthiopyridine in 380 ml of glacial acetic acid. After heating to 40-50 ° C, the mixture was carefully mixed with 95 g of hydrogen peroxide (30%). The mixture was then stirred at about 20 ° C for 1 hour. Then the mixture was poured into 300 ml of water. The product was separated from the suspension obtained, washed with water and n-pentane and dried under reduced pressure. Yield: 60 g (70%) as a brown powder; Mp: 129-130 ° C; * H-NMR (in d 6 -dimethyl sulfoxide): δ [ppm] = 3.4 (s, CH 3 ); 8.7 and 8.9 (2xd, Pyr-H).
Beispiel 2 (Verbindung Ia.383 in Tabelle 1):Example 2 (Compound Ia.383 in Table 1):
4,15 g der nach Beispiel 1 gewonnenen Verbindung Ia.384 und 10,2 g Pyridinhydrochlorid wurden vier Stunden unter Stickstoff - Atmosphäre auf 200°C erhitzt. Nach dem Abkühlen nahm man die Reak- tions ischung in 100 ml 10%iger Salzsäure auf. Dann extrahierte man das Produkt fünfmal mit je 90 ml Dichlormethan . Die vereinigten organischen Phasen wurden mit 100 ml Wasser gewaschen, über Natriumsulfat getrocknet und schließlich eingeengt. Die Reinigung der erhaltenen Kristalle erfolgte durch Verrühren mit MTB/Petrol- ether (1:1) . Nach Abtrennen und Trocknen erhielt man 3,6 g (90 %) weißer Kristalle; Smp. : 176-178°C.4.15 g of the compound Ia.384 obtained according to Example 1 and 10.2 g of pyridine hydrochloride were heated to 200 ° C. for four hours under a nitrogen atmosphere. After cooling, the reaction was taken up in 100 ml of 10% hydrochloric acid. The product was then extracted five times with 90 ml of dichloromethane each. The combined organic phases were washed with 100 ml of water, dried over sodium sulfate and finally concentrated. The crystals obtained were purified by stirring with MTB / petroleum ether (1: 1). After separation and drying, 3.6 g (90%) of white crystals were obtained; M.p .: 176-178 ° C.
Beispiel 3 (Verbindung Ia.402 in Tabelle 1):Example 3 (Compound Ia.402 in Table 1):
Zu 1,2 g der nach Beispiel 2 hergestellten Verbindung Ia.383 und 0,99 g Kaliumcarbonat in 80 ml wasserfreiem Dimethylformamid wurden tropfenweise 0,52 g Propargylbromid gegeben. Nach zwölf - stündigem Rühren bei 23°C verdünnte man mit 200 ml Wasser. Dann extrahierte man das Produkt viermal mit je 100 ml MTB. Die ver- einigten organischen Phasen wurden mit 100 ml Wasser gewaschen, über Natriumsulfat getrocknet und schließlich eingeengt. Die Reinigung des Rohproduktes erfolgte durch Verrühren mit n-Hexan/
Diethylether (10:1). Nach Abtrennen und Trocknen erhielt man 0,9 g (67 %) weißer Kristalle; Smp. : 182-183°C.0.52 g of propargyl bromide was added dropwise to 1.2 g of the compound Ia.383 prepared according to Example 2 and 0.99 g of potassium carbonate in 80 ml of anhydrous dimethylformamide. After stirring for 12 hours at 23 ° C., the mixture was diluted with 200 ml of water. Then the product was extracted four times with 100 ml MTB each. The combined organic phases were washed with 100 ml of water, dried over sodium sulfate and finally concentrated. The crude product was purified by stirring with n-hexane / Diethyl ether (10: 1). After separation and drying, 0.9 g (67%) of white crystals were obtained; M.p .: 182-183 ° C.
Beispiel 4 (Verbindung Ia.182 in Tabelle 1; (R) -Enantiomer) :Example 4 (Compound Ia.182 in Table 1; (R) -enantiomer):
Zu 2,4 g der nach Beispiel 2 hergestellten Verbindung Ia.383 und 1,97 g Kaliu carbonat in 100 ml wasserfreiem Dimethylformamid wurden tropfenweise 1,05 g (S) -2 -Chlorpropionsauremethylester gegeben. Nach sechzigstundigem Ruhren bei 23°C verdünnte man mit 300 ml Wasser. Dann extrahierte man das Produkt viermal mit j e 80 ml MTB. Die vereinigten organischen Phasen wurden mit 100 ml Wasser gewaschen, über Natriumsulfat getrocknet und schließlich eingeengt. Die Reinigung des Rohproduktes erfolgte mittels Chromatographie an Kieselgel (Laufmittel: Cyclohexan/MTB = 5:1 → 7:1). Ausbeute: 2,6 g (86 %) eines farblosen Ols. iH-NMR (200 MHz; in CDC13): δ [ppm] = 1,70 (d,3H), 3,20 (s,3H), 3,77 (s,3H), 4,78 (q,lH), 7,00 (d, 1H) , 7,28 (d,lH), 8,33 (s.lH), 9,07 (s,lH) .To 2.4 g of the compound Ia.383 prepared according to Example 2 and 1.97 g of potassium carbonate in 100 ml of anhydrous dimethylformamide were added dropwise 1.05 g of methyl (S) -2-chloropropionate. After stirring for sixty hours at 23 ° C., the mixture was diluted with 300 ml of water. Then the product was extracted four times with 80 ml MTB each. The combined organic phases were washed with 100 ml of water, dried over sodium sulfate and finally concentrated. The crude product was purified by chromatography on silica gel (mobile phase: cyclohexane / MTB = 5: 1 → 7: 1). Yield: 2.6 g (86%) of a colorless oil. iH-NMR (200 MHz; in CDC1 3 ): δ [ppm] = 1.70 (d, 3H), 3.20 (s, 3H), 3.77 (s, 3H), 4.78 (q, lH), 7.00 (d, 1H), 7.28 (d, lH), 8.33 (s.lH), 9.07 (s, lH).
Beispiel 5 (Verbindung Ia.181 in Tabelle 1; (R) -Enantiomer) :Example 5 (Compound Ia.181 in Table 1; (R) -enantiomer):
1,2 g der nach Beispiel 4 hergestellten Verbindung Ia.182 wurden in einer Mischung aus 25 ml Eisessig und 10 ml 2m-Salzsaure1.2 g of the compound Ia.182 prepared according to Example 4 were in a mixture of 25 ml of glacial acetic acid and 10 ml of 2M hydrochloric acid
4 Stunden bei 70 bis 80 °C und anschließend 16 Stunden bei 23°C gerührt. Nach Verdünnen mit 100 ml Wasser extrahiert man fünfmal mit "je 60 ml MTB. Die vereinigten organischen Phasen wurden zweimal mit je 60 ml gesättigter wäßriger Natriumchlorid -Losung gewaschen, dann über Natriumsulfat getrocknet und schließlich eingeengt. Die Reinigung des Rohproduktes erfolgte durch Ver- rühren mit n-Hexan/Diethylether (2:1). Ausbeute: 0,75 g (65 %) weißer Kristalle; Smp.: 161-164°C.4 hours at 70 to 80 ° C and then stirred for 16 hours at 23 ° C. After dilution with 100 ml of water, the mixture is extracted five times with 60 ml of MTB each time. The combined organic phases were washed twice with 60 ml of saturated aqueous sodium chloride solution, then dried over sodium sulfate and finally concentrated. The crude product was purified by stirring with n-hexane / diethyl ether (2: 1). Yield: 0.75 g (65%) of white crystals; mp: 161-164 ° C.
Beispiel 6: 3-Chlor-2- (4 -chlor -2 -fluo - 5 -methoxyphenyl ) -5-methyl- sulfinylpyridinExample 6: 3-chloro-2- (4-chloro-2-fluo-5-methoxyphenyl) -5-methylsulfinylpyridine
4,6 g 2, 3 -Dichlor - 5 -methylsulfinylpyridin, 4,5 g 4 -Chlor-2 - fluor- 5-methoxybenzolboronsaure, 5,5 g Natriumhydrogencarbonat und 1,0 g Tetrakis- (triphenylphosphin) -palladium(O) wurden in einer Mischung aus 100 ml Wasser und 100 ml Tetrahydrofuran 180 Stunden auf Ruckflußtemperatur erhitzt. Nach Abdampfen des Tetrahydro- furans extrahierte man viermal mit je 70 ml MTB. Dann wurden die vereinigten organischen Phasen über Natriumsulfat getrocknet und schließlich eingeengt. Die Reinigung des erhaltenen Ols erfolgte mittels Chromatographie an Kieselgel (Laufmittel: Cyclohexan/MTB = 7:3 → 1:1 und Cyclohexan/Essigester = 2:1). Durch verrühren des so gereinigten Ols mit Diethylether erhielt man 2,2 g (30 %) weißer Kristalle; Smp.: 117-118°C.4.6 g of 2,3-dichloro-5-methylsulfinylpyridine, 4.5 g of 4-chloro-2-fluoro-5-methoxybenzeneboronic acid, 5.5 g of sodium hydrogen carbonate and 1.0 g of tetrakis (triphenylphosphine) palladium (O) were heated in a mixture of 100 ml of water and 100 ml of tetrahydrofuran at reflux temperature for 180 hours. After the tetrahydrofuran had been evaporated, the mixture was extracted four times with 70 ml of MTB each. Then the combined organic phases were dried over sodium sulfate and finally concentrated. The oil obtained was purified by chromatography on silica gel (mobile phase: cyclohexane / MTB = 7: 3 → 1: 1 and cyclohexane / ethyl acetate = 2: 1). By stirring the oil thus purified with diethyl ether, 2.2 g (30%) of white crystals were obtained; M.p .: 117-118 ° C.
^
Be i spiel 7^ Example 7
Herstellung des Vorproduktes 2, 3-Dichlor-5-ethylsulfonyl-pyridin:Preparation of the intermediate 2, 3-dichloro-5-ethylsulfonyl-pyridine:
Analog Beispiel 1, Vorstufe γ wurden 5 g (0,024 mol) 2,3-Dichlor- 5 5-ethylthio-pyridin mit 0,4 g (1,2 mol) Na2W0 -2H20 und 6 gAnalogously to Example 1, precursor γ, 5 g (0.024 mol) of 2,3-dichloro-5 5-ethylthio-pyridine with 0.4 g (1.2 mol) of Na 2 WO-2H 2 0 and 6 g
Wasserstoffperoxid (30%ig) in 25 ml Eisessig umgesetzt. Nach der Aufarbeitung erhielt man 5,1 g Wertprodukt als weißen Feststoff. Ausbeute: 88,5 %; Fp . : 141-142°C; i-H-NMR (in d6-Dimethylsulfoxid) : δ [ppm] = 1,2 (t,CH3); 3,5 (q,CH2); 8,6 und 8,8 (2xd,Pyr-H). 10Hydrogen peroxide (30%) implemented in 25 ml glacial acetic acid. After working up, 5.1 g of valuable product were obtained as a white solid. Yield: 88.5%; Mp : 141-142 ° C; i -H NMR (in d 6 -dimethyl sulfoxide): δ [ppm] = 1.2 (t, CH 3 ); 3.5 (q, CH 2); 8.6 and 8.8 (2xd, Pyr-H). 10
Vorstufe α: 2 , 3-Dichlor-5-ethylthio-pyridinPrecursor α: 2, 3-dichloro-5-ethylthio-pyridine
Analog Beispiel 1, Vorstufe α wurden 24,45 g (0,15 mol) 3-Amino- 5, 6-dichlorpyridin in 280 ml Methylenchlorid mit 36,6 g (0,3 mol) 15 Diethyldisulf id und 23,2 g (0,225 mol) tert . -Butylnitri in 130 ml Methylenchlorid umgesetzt. Nach Aufarbeitung und anschließendem Auswaschen des Rohprodukts mit Ethanol erhielt man 13,3 g Wertprodukt. Ausbeute: 42 %; 1H-NMR (in d6-Dimethylsulfoxid) : δ [ppm] = 1,25 (t,CH3); 3,10 (d,CH2); 8,15 und 8,3 (2xd,Pyr-H).Analogously to Example 1, precursor α, 24.45 g (0.15 mol) of 3-amino-5, 6-dichloropyridine in 280 ml of methylene chloride with 36.6 g (0.3 mol) of 15 diethyl disulfide and 23.2 g ( 0.225 mol) tert. -Butylnitri implemented in 130 ml methylene chloride. After working up and then washing out the crude product with ethanol, 13.3 g of valuable product were obtained. Yield: 42%; 1 H NMR (in d 6 -dimethyl sulfoxide): δ [ppm] = 1.25 (t, CH 3 ); 3.10 (d, CH 2 ); 8.15 and 8.3 (2xd, Pyr-H).
2020th
Vorstufe ß: 2 , 3-Dichlor-5-ethylsulfinyl-pyridinPrecursor β: 2, 3-dichloro-5-ethylsulfinyl-pyridine
Analog Beispiel 1, Vorstufe ß wurden 4 g (0,02 mol) 2,3-Dichlor- 5-ethylthio-pyridin mit 3,47 g (0,02 mol) m-Chlorperbenzoesäure inAnalogously to Example 1, precursor β, 4 g (0.02 mol) of 2,3-dichloro-5-ethylthio-pyridine were mixed with 3.47 g (0.02 mol) of m-chloroperbenzoic acid
25 30 ml Methylenchlorid umgesetzt. Nach Reinigung des Rohproduktes mittels Flashchromatographie an Kieselgel (Laufmittel: Cyclo- hexan/Essigester = 2:1) erhielt man 1,9 g Wertprodukt in Form von weißen Kristallen. Ausbeute: 42 %. Fp. : 78-79°C; iH-NMR (d6-Dimethylsulfoxid) : δ [ppm] = 1,1 (t;CH3); 3,0 und 3,225 30 ml of methylene chloride reacted. After purification of the crude product by means of flash chromatography on silica gel (mobile phase: cyclohexane / ethyl acetate = 2: 1), 1.9 g of valuable product were obtained in the form of white crystals. Yield: 42%. Mp: 78-79 ° C; iH-NMR (d 6 -dimethyl sulfoxide): δ [ppm] = 1.1 (t; CH 3 ); 3.0 and 3.2
30 (2xm,CH2); 8,35 und 8,6 (2xs,Pyr-H).30 (2xm, CH 2 ); 8.35 and 8.6 (2xs, Pyr-H).
Beispiel 8Example 8
Herstellung des Vorproduktes 2 , 3-Dichlor-5-isopropylsulfonyl- pyridin:Preparation of the intermediate 2, 3-dichloro-5-isopropylsulfonylpyridine:
3535
Analog zu Beispiel 1, Vorstufe γ wurden 15 g (0,068 mol) 2, 3-Dichlor-5-isopropylthio-pyridin (Rohprodukt) mit 1,11 g (3,6 mmol) NaW0 *2H20 und 17 g Wasserstoffperoxid (30%ig) in 80 ml Essigsäure umgesetzt. Nach Aufarbeitung und zusätzlichem Aus-Analogously to Example 1, precursor γ, 15 g (0.068 mol) of 2,3-dichloro-5-isopropylthio-pyridine (crude product) with 1.11 g (3.6 mmol) of NaW0 * 2H 2 0 and 17 g of hydrogen peroxide (30 %) implemented in 80 ml of acetic acid. After processing and additional training
40 rühren des Rohprodukts mit Ethanol erhielt man 3,5 g Wertprodukt als helles Pulver. Ausbeute: 20%; Fp. : 146°C; iH-NMR (in d6-Di- methylsulfoxid) : δ [ppm] = 1,2 (d,2xCH3); 3,65 (m,CH); 8,6 und 8, 8 (2xd, Pyr-H) .40 stirring of the crude product with ethanol gave 3.5 g of valuable product as a light powder. Yield: 20%; Mp: 146 ° C; i H-NMR (in d 6 -dimethylsulfoxide): δ [ppm] = 1.2 (d, 2xCH 3 ); 3.65 (m, CH); 8,6 and 8, 8 (2xd, Pyr-H).
45
Vorstufe α: 2 , 3-Dichlor-5-isopropylthio-pyridin45 Precursor α: 2,3-dichloro-5-isopropylthio-pyridine
Analog zu Beispiel 1, Vorstufe α wurden 13,1 g (0,08 mol) 3-Amino- 5, 6-dichlorpyridin in 120 ml Methylenchlorid mit 25 g (0,16 mol) Diisopropyldisulfid und 12,4 g (0,12 mol) tert . -Butylnitrit in 70 ml Methylenchlorid umgesetzt. Man erhielt 30 g eines dunklen Ols (ca. 40 % Wertprodukt), das ohne weitere Reinigung weiter umgesetzt wurde. 1H-NMR (in d6-Dimethylsulfoxid) : δ [ppm] = 1,25 (d,2xCH3); 3,7 (m,CH); 8,2 und 8,3 (2xd,Pyr-H).Analogously to Example 1, precursor α, 13.1 g (0.08 mol) of 3-amino-5, 6-dichloropyridine in 120 ml of methylene chloride with 25 g (0.16 mol) of diisopropyl disulfide and 12.4 g (0.12 mol) tert. -Butyl nitrite implemented in 70 ml methylene chloride. 30 g of a dark oil (approx. 40% product of value) were obtained, which was reacted further without further purification. 1 H-NMR (in d 6 -dimethylsulfoxide): δ [ppm] = 1.25 (d, 2xCH 3 ); 3.7 (m, CH); 8.2 and 8.3 (2xd, Pyr-H).
Vorstufe ß: 2 , 3-Dichlor-5-isopropylsulf inyl-pyridinPrecursor β: 2, 3-dichloro-5-isopropylsulfinyl-pyridine
Analog zu Beispiel 1, Vorstufe ß wurden 10 g (0,045 mol)Analogously to Example 1, precursor β, 10 g (0.045 mol)
2, 3-Dichlor-5-isopropylthio-pyridin (als Rohprodukt) mit 7,8 g (0,045 mol) m-Chlorperbenzoesäure in 60 ml Methylenchlorid umgesetzt. Nach Reinigung des Rohprodukts mittels Flashchromatographie an Kieselgel (Laufmittel: Cyclohexan/Essigester = 1:1) erhielt man 1,7 g Wertprodukt. Ausbeute: 16 %; Fp.: 62-64°C; XH-NMR (in d6-Dimethylsulfoxid) : δ [ppm] = 1,0 und 1,25 (2xd,2xCH3); 3,2 (m,CH); 8,3 und 8,5 (2xd,Pyr-H).2, 3-dichloro-5-isopropylthio-pyridine (as crude product) with 7.8 g (0.045 mol) of m-chloroperbenzoic acid in 60 ml of methylene chloride. After purification of the crude product by means of flash chromatography on silica gel (mobile phase: cyclohexane / ethyl acetate = 1: 1), 1.7 g of valuable product were obtained. Yield: 16%; M.p .: 62-64 ° C; X H NMR (in d 6 -dimethyl sulfoxide): δ [ppm] = 1.0 and 1.25 (2xd, 2xCH 3 ); 3.2 (m, CH); 8.3 and 8.5 (2xd, Pyr-H).
In der folgenden Tabelle 2 sind weitere substituierte 2 - Phenyl • pyridine I aufgeführt:The following Table 2 lists further substituted 2-phenyl • pyridines I:
Tabelle 2Table 2
57
57
Anwendungsbeispiele (herbizide Wirksamkeit)Examples of use (herbicidal activity)
Die herbizide Wirkung der substituierten 2 -Phenylpyridine I ließ sich durch die folgenden Gewächshausversuche zeigen:The herbicidal activity of the substituted 2-phenylpyridines I was demonstrated by the following greenhouse tests:
Als Kulturgefäße dienten Plastikblumentöpfe mit lehmigem Sand mit etwa 3,0 % Humus als Substrat. Die Samen der Testpflanzen wurden nach Arten getrennt eingesät.Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels. The seeds of the test plants were sown separately according to species.
Bei Vorauf laufbehandlung wurden die in Wasser suspendierten oder emulgierten Wirkstoffe direkt nach Einsaat mittels fein verteilender Düsen aufgebracht. Die Gefäße wurden leicht beregnet, um Keimung und Wachstum zu fördern, und anschließend mit durchsichtigen Plastikhauben abgedeckt, bis die Pflanzen angewachsen waren. Diese Abdeckung bewirkt ein gleichmäßiges Keimen der Test- pflanzen, sofern dies nicht durch die Wirkstoffe beeinträchtigt wurde .In pre-run treatment, the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles. The tubes were lightly sprinkled to promote germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
Zum Zweck der Nachauflaufbehandlung wurden die Testpflanzen je nach Wuchsform erst bis zu einer Wuchshöhe von 3 bis 15 cm angezogen und erst dann mit den in Wasser suspendierten oder emulgierten Wirkstoffen behandelt. Die Testpflanzen wurden dafür entweder direkt gesät und in den gleichen Gefäßen aufgezogen oder sie wurden erst als Keimpflanzen getrennt angezogen und einige Tage vor der Behandlung in die Versuchsgefäße verpflanzt. Die Aufwandmenge für die Nachauflaufbehandlung betrug 0,0313 oder 0,0156 kg/ha a.S. (aktive Substanz).For the purpose of post-emergence treatment, the test plants, depending on the growth habit, were first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment. The application rate for post-emergence treatment was 0.0313 or 0.0156 kg / ha a.S. (active substance).
Die Pflanzen wurden artenspezifisch bei Temperaturen von 10 bis 25°C bzw. 20 bis 35°C gehalten. Die Versuchsperiode erstreckte sich über 2 bis 4 Wochen. Während dieser Zeit wurden die Pflanzen gepflegt, und ihre Reaktion auf die einzelnen Behandlungen wurde ausgewertet.The plants were kept in a species-specific manner at temperatures of 10 to 25 ° C and 20 to 35 ° C. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.
S~2
Bewertet wurde nach einer Skala von 0 bis 100. Dabei bedeutet 100 kein Aufgang der Pflanzen bzw. völlige Zerstörung zumindest der oberirdischen Teile und 0 keine Schädigung oder normaler Wachstumsverlauf .S ~ 2 Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
Die in den Gewächshausversuchen verwendeten Pflanzen setzten sich aus folgenden Arten zusammen:The plants used in the greenhouse experiments are composed of the following types:
Bei Aufwandmengen von 0,0313 und 0,0156 kg/ha a.S. zeigte die Verbindung Nr. Ia.384 im Nachauflaufverfahren eine sehr gute herbizide Wirkung gegen die obengenannten breitblättrigen Pflanzen.At application rates of 0.0313 and 0.0156 kg / ha a.S. Compound No. Ia.384 showed a very good herbicidal activity against the above-mentioned broad-leaved plants in the post-emergence process.
Anwendungsbeispiele (desikkative/defoliante Wirksamkeit)Examples of use (desiccative / defolian effectiveness)
Als Testpflanzen dienten junge, 4blättrige (ohne Keimblätter) Baumwollpflanzen, die unter Gewächshausbedingungen angezogen wurden (rel. Luftfeuchtigkeit 50 bis 70 %; Tag-/Nachttemperatur 27/20°C) .Young, 4-leaf (without cotyledons) cotton plants served as test plants, which were grown under greenhouse conditions (relative humidity 50 to 70%; day / night temperature 27/20 ° C.).
Die jungen Baumwollpflanzen wurden tropfnaß mit wäßrigen Aufbereitungen der Wirkstoffe (unter Zusatz von 0,15 Gew. -% des Fettalkoholalkoxylats Plurafac® LF 700 2) , bezogen auf dieThe young cotton plants were dripping wet with aqueous preparations of the active ingredients (with an addition of 0.15 wt -.% Of the fatty alcohol alkoxylate Plurafac LF 700 ® 2), based on the
Spritzbrühe) blattbehandelt. Die ausgebrachte Wassermenge betrug umgerechnet 1000 1/ha. Nach 13 Tagen wurde die Anzahl der abgeworfenen Blätter und der Grad der Entblätterung in % bestimmt.Spray broth) treated with leaves. The amount of water applied was the equivalent of 1000 l / ha. After 13 days, the number of leaves dropped and the degree of defoliation in% were determined.
Bei den unbehandelten Kontrollpflanzen trat kein Blattfall auf .No leaf fall occurred in the untreated control plants.
2) ein schaumarmes, nichtionisches Tensid der BASF AG 2) a low-foaming, nonionic surfactant from BASF AG
$3
$ 3
Claims
Substituierte 2 - Phenylpyridine der allgemeinen Formel ISubstituted 2 - phenylpyridines of the general formula I
in der die Variablen folgende Bedeutungen haben: in which the variables have the following meanings:
n Null oder 1;n zero or 1;
R1 Mercapto, Hydroxysulfonyl, Chlorsulfonyl , Amino- sulfonyl, Ci -C6 -Alkylthio, Cx -C6 -Alkylsulfinyl , Cι-C6 -Alkylsulfonyl , Ci - C$ -Alkylaminosulfonyl oder Di- (Ci -C6 -alkyl) aminosulfonyl ;R 1 mercapto, hydroxysulfonyl, chlorosulfonyl, aminosulfonyl, Ci -C 6 alkylthio, C x -C 6 alkylsulfinyl, Cι -C 6 alkylsulfonyl, Ci - C $ alkylaminosulfonyl or di- (Ci -C 6 alkyl) ) aminosulfonyl;
R2 , R3 unabhängig voneinander Wasserstoff oder Halogen;R 2 , R 3 independently of one another are hydrogen or halogen;
R4 Cyano, Hydroxy, Halogen, Cι-C6 -Alkoxy oder Phenyl - methoxy, wobei der Phenylring unsubstituiert sein oder ein bis drei Substituenten tragen kann, jeweils ausgewählt aus der Gruppe bestehend aus Hydroxy, Halogen, Ci-Cβ-Alkyl, Ci -C6- Halogenalkyl , Ci -CÖ -Alkoxy, Ci-Cδ-Halogenalkoxy, Hydroxycarbonyl, (Cι-C6-Alkoxy) - carbonyl und (CI-CÖ -Alkoxy) carbonyl -Ci -C6 - alkoxy ;R 4 cyano, hydroxy, halogen, -CC 6 alkoxy or phenyl - methoxy, where the phenyl ring can be unsubstituted or can carry one to three substituents, each selected from the group consisting of hydroxy, halogen, Ci-Cβ-alkyl, Ci -C 6 - haloalkyl, Ci -C Ö alkoxy, Ci-C δ -haloalkoxy, hydroxycarbonyl, (-C-C 6 alkoxy) - carbonyl and (CI-C Ö alkoxy) carbonyl -Ci -C 6 - alkoxy;
R5 Wasserstoff, Nitro, Cyano, Hydroxylamino, Halogen, Cι-C6-Alkyl, Cι-C6 -Halogenalkyl, -COCl, -CO-OR6, -CO-N(R )Ra, -CO-O- (Cι-C -Alkylen) -CO-OR6, -CO-O- (Cι-C4 -Alkylen) -C0-N(R7)Re, -X1- (Ci -C4 -Alkylen) - CO-R6, -X1- (Cι-C4-Alkylen) -CO-OR6, -X1 - (Cι-C4 -Alkylen) - CO-O- (C!-C -Alkylen) -CO-OR6, -X1- (Cι-C -Alkylen) - CO-N(R7)Rθ, -X^R9, -CH=C(R10) -CO-OR6, -CH=C (R10) -CO-O- (Cι-C -Alkylen) -CO-OR6, -CH=C(R10) -CO-N(R7)R8, Formyl, -CO-R6,R 5 is hydrogen, nitro, cyano, hydroxylamino, halogen, Cι-C 6 -alkyl, C 6 haloalkyl, -COCl, -CO-OR 6, -CO-N (R) R a, -CO-O- (-C-C alkylene) -CO-OR 6 , -CO-O- (-C-C 4 alkylene) -C0-N (R 7 ) R e , -X 1 - (Ci -C 4 alkylene) - CO-R 6 , -X 1 - (-C-C 4 alkylene) -CO-OR 6 , -X 1 - (Cι-C 4 alkylene) - CO-O- (C ! -C alkylene) -CO -OR 6 , -X 1 - (-C-alkylene) - CO-N (R 7 ) R θ , -X ^ R 9 , -CH = C (R 10 ) -CO-OR 6 , -CH = C (R 10 ) -CO-O- (-C-alkylene) -CO-OR 6 , -CH = C (R 10 ) -CO-N (R 7 ) R 8 , formyl, -CO-R 6 ,
fι -C(R8)=N-OR15, -X1- (Cι-C4-Alkylen) -C (R8) =N-0R15 , -CH=C(R10) -C(R8)=N-OR15, -CH (Cλ -C6 -Alkoxy) 2 , -N(R16)R17, -N(R16) -S02- (Cx-Ce-Alkyl) , -N(R*6) -CO- (Cα'-Cβ -Alkyl) , Chlorsulfonyl, Hydroxysulfonyl oder - S02 -N (R18) R19 ; f ι -C (R 8 ) = N-OR 15 , -X 1 - (-Cι-C 4 -alkylene) -C (R 8 ) = N-0R 15 , -CH = C (R 10 ) -C (R 8 ) = N-OR 15 , -CH (C λ -C 6 alkoxy) 2 , -N (R 16 ) R 17 , -N (R 16 ) -S0 2 - (Cx-Ce-alkyl), -N (R * 6 ) -CO- (Cα ' -Cβ-alkyl), chlorosulfonyl, hydroxysulfonyl or - S0 2 -N (R 18 ) R 19 ;
R6 Wasserstoff, Cι-C6-Alkyl, Ci -C6 -Halogenalkyl, C3-C6-Alkenyl, C3 -C6 -Alkinyl , C3 -C6 -Cycloalkyl, Cι-C6-Alkoxy-Cι-C6-alkyl oder 3-Oxetanyl;R 6 are hydrogen, C 6 alkyl, Ci-C6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, Cι-C alkoxy-Cι 6 -C 6 alkyl or 3-oxetanyl;
R7 Wasserstoff oder Cι-C6 -Alkyl;R 7 is hydrogen or -CC 6 alkyl;
R8 Wasserstoff, Hydroxy, Cι-C6 -Alkyl, Hydroxycarbonyl -Cι-C6 -alkyl, (Cι-C6 -Alkoxy) carbonyl -Ci -C6 -alkyl , Ci -Cß -Alkoxy, Ci -C6 -Halogenalkoxy, Phenyl -Ci -C6 -alkoxy, C3 -C6 -Alkenyloxy oder C3 -C6 -Alkinyloxy oderR 8 is hydrogen, hydroxy, Cι-C6 alkyl, hydroxycarbonyl -Cι-C 6 alkyl, (Cι-C 6 -alkoxy) carbonyl -C -C 6 alkyl, C -C ß alkoxy, Ci-C6 -Halogenalkoxy, phenyl -Ci -C 6 alkoxy, C 3 -C 6 alkenyloxy or C 3 -C 6 alkynyloxy or
R7 und Rθ zusammen eine Tetra- oder Pentamethylenkette, die einen (Ci -Cδ-Alkoxy) carbonylrest tragen kann;R 7 and R θ together form a tetra or pentamethylene chain which can carry a (Ci -C δ alkoxy) carbonyl radical;
R9 Wasserstoff, Cι-C6-Alkyl, Ci -C6- Halogenalkyl , C3-C6-Alkenyl, C3 -C6 -Alkinyl , C3 -C6 -Cycloalkyl oder Ci-Cö-Alkoxy-Ci-Cδ-alkyl;R 9 is hydrogen, -CC 6 alkyl, Ci -C 6 - haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl or Ci-C ö alkoxy-Ci -C δ alkyl;
R10 Wasserstoff, Halogen oder Ci-Cö-Alkyl;R 10 is hydrogen, halogen or Ci-C ö alkyl;
Riι.^14 unabhängig voneinander Wasserstoff, Cι-C6 -Alkyl oder (Ci -C6-Alkoxy) carbonyl;Riι. ^ 14 independently of one another hydrogen, -CC 6 alkyl or (Ci -C 6 alkoxy) carbonyl;
R15 Wasserstoff, Cι-C6 -Alkyl, Phenyl -C!-C6 -alkyl , (Cι-C6 -Alkoxy) carbonyl -Cι-C6 -alkyl, C3-C6 -Alkenyl oder C3 -C6-Alkinyl;R 15 is hydrogen, -CC 6 alkyl, phenyl -C ! -C 6 alkyl, (Cι-C 6 alkoxy) carbonyl -Cι-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
R16 Wasserstoff oder Ci -C6-Alkyl;R 16 is hydrogen or Ci -C 6 alkyl;
R17 Wasserstoff, Cι-C6-Alkyl, Hydroxycarbonyl -Cι-C6 -alkyl , (Ci-Cß -Alkoxy) carbonyl -Cι-C6-alkyl oder Ci -Cδ-Alkoxy;R 17 is hydrogen, -CC 6 alkyl, hydroxycarbonyl -C 6 alkyl, (Ci-C ß alkoxy) carbonyl -C 6 alkyl or Ci -C δ alkoxy;
R18 Wasserstoff oder Ci -C6-Alkyl;R 18 is hydrogen or Ci -C 6 alkyl;
R19 Wasserstoff, Cι-C6-Alkyl, Hydroxycarbonyl -Ci -C6-alkyl , (Ci - C6 -Alkoxy) carbonyl -Cι-C6-alkyl oder CI-CÖ-Alkoxy oderR 19 is hydrogen, -CC 6 alkyl, hydroxycarbonyl -C 6 -C 6 alkyl, (Ci - C 6 alkoxy) carbonyl -C -C 6 alkyl or CI-C Ö alkoxy or
R18 und R19 zusammen eine Tetra- oder Pentamethylenkette, die einen (Cι-C6 -Alkoxy) carbonylrest tragen kann;R 18 and R 19 together form a tetra or pentamethylene chain, which can carry a (-C 6 alkoxy) carbonyl radical;
Xx-X3 unabhängig voneinander Sauerstoff oder Schwefel,X x -X 3 independently of one another oxygen or sulfur,
5T sowie die landwirtschaftlich brauchbaren Salze der Verbindungen I mit R6 = Wasserstoff.5T and the agriculturally useful salts of the compounds I with R 6 = hydrogen.
2. Substituierte 2-Phenylpyridine der Formel I und deren Salze, nach Anspruch 1, wobei2. Substituted 2-phenylpyridines of formula I and their salts, according to claim 1, wherein
R5 für Wasserstoff, Nitro, Cyano, Hydroxylamino, Ci-Cβ-Alkyl, Cι-C6-Halogenalkyl, -C0C1, -CO-OR6, -CO-O- (Cι-C-Alkylen) -CO-OR6, -O- (Cχ-C -Alkylen) -CO-OR6 , -0- (C!-C4-Alkylen) -CO-O- (C!-C4-Alkylen) -CO-OR6, -OR9 ,R 5 for hydrogen, nitro, cyano, hydroxylamino, Ci-Cβ-alkyl, -C-C 6 -haloalkyl, -C0C1, -CO-OR 6 , -CO-O- (-C-C-alkylene) -CO-OR 6 , -O- (Cχ-C -alkylene) -CO-OR 6 , -0- (C! -C 4 -alkylene) -CO-O- (C! -C 4 -alkylene) -CO-OR 6 , - OR 9 ,
Formyl, -CH=N-OR15 oder -NH ;Formyl, -CH = N-OR 15 or -NH;
R6 für Wasserstoff, Cι-C6-Alkyl, C3-C6-Alkenyl , C3-C6-Alkmyl oder Cι-C6-Alkoxy-Cι-Cδ-alkyl ;R 6 are hydrogen, C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 -Alkmyl or Cι-C6-alkoxy-Cι-C alkyl δ;
R9 für Wasserstoff, Cι-C6-Alkyl, C3-Cfa-Alkenyl oder C3-C6-Alkinyl undR 9 for hydrogen, -CC 6 alkyl, C 3 -C fa alkenyl or C 3 -C 6 alkynyl and
R15 für Cι-C6-Alkyl stehen.R 15 represent -C 6 alkyl.
3. Verwendung der substituierten 2-Phenylpyridine der Formel I und der landwirtschaftlich brauchbaren Salze von I, gemäß Anspruch 1, als Herbizide oder zur Desikkation und/oder Defoliation von Pflanzen.3. Use of the substituted 2-phenylpyridines of the formula I and the agriculturally useful salts of I, according to claim 1, as herbicides or for desiccation and / or defoliation of plants.
4. Herbizides Mittel, enthaltend eine herbizid wirksame Menge mindestens eines substituierten 2-Phenylpyridins der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I, gemäß Anspruch 1, und mindestens einen inerten flüssigen und/oder festen Trägerstoff sowie gewunschtenf lls mindestens einen oberflächenaktiven Stoff.4. Herbicidal composition containing a herbicidally effective amount of at least one substituted 2-phenylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, and at least one inert liquid and / or solid carrier and, if desired, at least one surfactant.
5. Mittel zur Desikkation und/oder Defoliation von Pflanzen, enthaltend eine desikkant und/oder defoliant wirksame Menge mindestens eines substituierten 2-Phenylpyridins der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I, gemäß Anspruch 1, und mindestens einen inerten flüssigen und/oder festen Trägerstoff sowie gewunschtenfalls mindestens einen oberflächenaktiven Stoff.5. Agent for the desiccation and / or defoliation of plants, containing a desiccant and / or defoliantly effective amount of at least one substituted 2-phenylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, and at least one inert liquid and / or solid carrier and, if desired, at least one surface-active substance.
6. Verfahren zur Herstellung von herbizid wirksamen Mitteln, dadurch gekennzeichnet, daß man eine herbizid wirksame Menge mindestens eines substituierten 2-Phenylpyridins der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I, gemäß Anspruch 1, und mindestens einen inerten flussigen und/oder festen Trägerstoff sowie gewunschtenfalls mindestens einen oberflächenaktiven Stoff mischt. s-t 6. A process for the preparation of herbicidally active agents, characterized in that a herbicidally effective amount of at least one substituted 2-phenylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, and at least one inert liquid and / or solid carrier and, if desired, mixes at least one surfactant. st
7. Verfahren zur Herstellung von desikkant und/oder defoliant wirksamen Mitteln, dadurch gekennzeichnet, daß man eine desikkant und/oder defoliant wirksame Menge mindestens eines substituierten 2-Phenylpyridιns der Formel I oder eines land- wirtschaftlich brauchbaren Salzes von I, gemäß Anspruch 1, und mindestens einen inerten flussigen und/oder festen Tragerstoff sowie gewunschtenfalls mindestens einen oberflächenaktiven Stoff mischt.7. A process for the preparation of desiccant and / or defoliant agents, characterized in that a desiccant and / or defoliant amount of at least one substituted 2-phenylpyridine of formula I or an agriculturally useful salt of I, according to claim 1, and mixes at least one inert liquid and / or solid carrier material and, if desired, at least one surface-active substance.
8. Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs, dadurch gekennzeichnet, daß man eine herbizid wirksame Menge mindestens eines substituierten 2-Phenylpyridins der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I, gemäß Anspruch 1, auf Pflanzen, deren Lebensraum oder auf Saatgut einwirken läßt.8. A method for controlling undesirable plant growth, characterized in that a herbicidally effective amount of at least one substituted 2-phenylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, is allowed to act on plants, their habitat or on seeds.
9. Verfahren zur Desikkation und/oder Defoliation von Pflanzen, dadurch gekennzeichnet, daß man eine desikkant und/oder defoliant wirksame Menge mindestens eines substituierten 2-Phenylpyridins der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I, gemäß Anspruch 1, auf Pflanzen einwirken laßt.9. A process for the desiccation and / or defoliation of plants, characterized in that a desiccant and / or defoliantly effective amount of at least one substituted 2-phenylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, is allowed to act on plants .
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß man Baumwolle behandelt.10. The method according to claim 9, characterized in that cotton is treated.
11. Verfahren zur Herstellung von substituierten 2-Phenyl- pyridinen der Formel I gemäß Anspruch 1, bei denen n für 1 steht und R1 und R5 keinen oxidierbaren Schwefel enthalten, dadurch gekennzeichnet, daß man die entsprechenden substituierten 2-Phenylpyridine, bei denen aber n Null bedeutet, in einem inerten Lösungs-/Verdunnungsmittel oxidiert.11. A process for the preparation of substituted 2-phenylpyridines of the formula I according to claim 1, in which n is 1 and R 1 and R 5 do not contain any oxidizable sulfur, characterized in that the corresponding substituted 2-phenylpyridines in which but n means zero, oxidized in an inert solvent / diluent.
12. Verfahren zur Herstellung von substituierten 2-Phenyl- pyridinen der Formel I gemäß Anspruch 1, bei denen R1 für Cι-C6-Alkylsulfinyl oder Ci-Cβ-Alkylsulfonyl steht und der Substituent R5 keinen oxidierbaren Schwefel enthält, dadurch gekennzeichnet, daß man die entsprechenden substituierten 2-Phenylpyridine, bei denen aber R1 Ci-Cβ-Alkylthio oder Ci-Cβ-Alkylsulfinyl bedeutet, in einem inerten Losungs-/Ver- dünnungsmittel oxidiert. 12. A process for the preparation of substituted 2-phenylpyridines of the formula I according to claim 1, in which R 1 is C 1 -C 6 -alkylsulfinyl or Ci-Cβ-alkylsulfonyl and the substituent R 5 contains no oxidizable sulfur, characterized in that that the corresponding substituted 2-phenylpyridines, but in which R 1 is Ci-Cβ-alkylthio or Ci-Cβ-alkylsulfinyl, is oxidized in an inert solvent / diluent.
13. Verfahren zur Herstellung von substituierten 2-Phenyl- pyridinen der Formel I gemäß Anspruch 1, dadurch gekennzeichnet, daß man ein 2-Halogenpyrid der Formel II13. A process for the preparation of substituted 2-phenylpyridines of the formula I according to claim 1, characterized in that a 2-halopyride of the formula II
wobei Hai für Chlor oder Brom steht, in Gegenwart eines ϋbergangsmetallkatalysators mit einer metallorganischen Verbindung der Formel III where shark represents chlorine or bromine, in the presence of a transition metal catalyst with an organometallic compound of the formula III
wobei M1 für B(0H)2, Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br, Zn-J, Lithium, Kupfer oder Zinntri (Cι-C4-alkyl) steht, oder mit einem Boroxin der Formel IV where M 1 is B (0H) 2 , Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br, Zn-J, lithium, copper or tin tri (-C-C 4 alkyl), or with a boroxin of formula IV
umsetzt. implements.
14. Verfahren nach Anspruch 13, dadurch gekennzeichnet, daß man II mit einer metallorganischen Verbindung der Formel III umsetzt, wobei M1 für B(0H) , Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br oder Zn-J steht.14. The method according to claim 13, characterized in that II is reacted with an organometallic compound of the formula III, where M 1 for B (0H), Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br or Zn-J stands.
15. Verfahren zur Herstellung von substituierten 2-Phenyl- pyridinen der Formel I gemäß Anspruch 1, bei denen R1 für Ci-Cβ-Alkylthio steht, dadurch gekennzeichnet, daß man 5-Nitro-2-phenylpyridine der Formel V15. A process for the preparation of substituted 2-phenylpyridines of the formula I according to claim 1, in which R 1 is Ci-Cβ-alkylthio, characterized in that 5-nitro-2-phenylpyridines of the formula V
V,V,
wobei n und R2 bis R5 die in Anspruch 1 angegebenen Bedeutungen haben, reduziert, die hierbei erhaltenen 5-Amino-2-phenylpyridine der Formel VI where n and R 2 to R 5 have the meanings given in claim 1, the resulting 5-amino-2-phenylpyridines of the formula VI are reduced
diazotiert und die Diazoniumsalze schließlich mit symmetrischen aliphatischen Disulfiden der Formel VII diazotized and finally the diazonium salts with symmetrical aliphatic disulfides of the formula VII
(Cι-C6-Alkyl) -S-S- (Ci-Ce-Alkyll VII(-C-C 6 alkyl) -SS- (Ci-Ce alkyl VII
15 umsetzt ,15 implements
16. 15-Nitro-2-phenylpyridine der Formel V16. 15-nitro-2-phenylpyridines of the formula V
25 wobei n für 0 oder 1 steht und die Substituenten R2 bis R5 die in Anspruch 1 angegebenen Bedeutungen haben, ausgenommen 2 - (4 -Chlor- 3 -methoxyphenyl) -5 -nitropyridin und 2 - (4 -Chlor -3 -methoxyphenyl) -3 -chlor- 5 -nitropyridin.25 where n is 0 or 1 and the substituents R 2 to R 5 have the meanings given in claim 1, except 2 - (4-chloro-3-methoxyphenyl) -5-nitropyridine and 2 - (4-chlorine -3 - methoxyphenyl) -3-chloro-5 -nitropyridine.
30 17. 5-Amino-2-phenylpyridine der Formel VI30 17. 5-Amino-2-phenylpyridines of the formula VI
wobei n für 0 oder 1 steht und die Substituenten R2 bis R5 die in Anspruch 1 angegebenen Bedeutungen haben, 0 ausgenommen 5-Amino-2 - (4 -chlor-3 -methoxyphenyl) -pyridin und 5 -Amino-2 - (4 -chlor -3 -methoxyphenyl) -3 -chlorpyridin. where n is 0 or 1 and the substituents R 2 to R 5 have the meanings given in claim 1, 0 except 5-amino-2 - (4-chloro-3-methoxyphenyl) pyridine and 5 -amino-2 - ( 4-chlorine -3-methoxyphenyl) -3-chloropyridine.
55
η η
18. 2 -Halogenpyridine der Formel Ila18. 2 halopyridines of the formula Ila
wobei Hai für Chlor oder Brom steht und R1 die in Anspruch 1 angegebene Bedeutung hat. wherein shark is chlorine or bromine and R 1 has the meaning given in claim 1.
i i
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PCT/EP1997/004420 WO1998007700A1 (en) | 1996-08-22 | 1997-08-13 | Substituted 2-phenylpyridine as herbicide |
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US20040043903A1 (en) * | 2000-11-22 | 2004-03-04 | Michael Puhl | 2-Aryl-5-trifluoromethylpyridines |
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JPH08501100A (en) | 1992-09-09 | 1996-02-06 | イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー | Herbicidal benzene compound |
GB9222253D0 (en) | 1992-10-23 | 1992-12-09 | Celltech Ltd | Chemical compounds |
DE4323916A1 (en) * | 1993-07-16 | 1995-01-19 | Basf Ag | Substituted 2-phenylpyridines |
DE19500760A1 (en) * | 1995-01-13 | 1996-07-18 | Basf Ag | Substituted 2-phenylpyridines |
DE19500911A1 (en) | 1995-01-13 | 1996-07-18 | Basf Ag | Substituted 2-phenylpyridines |
DE19500758A1 (en) | 1995-01-13 | 1996-07-18 | Basf Ag | Substituted 2-phenylpyridines |
DE19528943A1 (en) | 1995-08-07 | 1997-02-13 | Basf Ag | Substituted 2-phenylpyridines |
DE19534466A1 (en) | 1995-09-18 | 1997-03-20 | Basf Ag | Substituted 2-phenylpyridines |
DE19605766A1 (en) | 1996-02-16 | 1997-08-21 | Basf Ag | Substituted 2-phenylpyridines |
DE19610571A1 (en) | 1996-03-18 | 1997-09-25 | Basf Ag | Process and intermediates for the preparation of pyridyl-4-fluoroanilines |
-
1996
- 1996-08-22 DE DE19633746A patent/DE19633746A1/en not_active Withdrawn
-
1997
- 1997-08-13 WO PCT/EP1997/004420 patent/WO1998007700A1/en not_active Application Discontinuation
- 1997-08-13 US US09/242,463 patent/US6448205B1/en not_active Expired - Fee Related
- 1997-08-13 CA CA002263093A patent/CA2263093A1/en not_active Abandoned
- 1997-08-13 JP JP10510363A patent/JP2000517303A/en active Pending
- 1997-08-13 AU AU41183/97A patent/AU4118397A/en not_active Abandoned
- 1997-08-13 EP EP97938899A patent/EP0920415A1/en not_active Withdrawn
- 1997-08-22 AR ARP970103827A patent/AR009305A1/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9807700A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2263093A1 (en) | 1998-02-26 |
US6448205B1 (en) | 2002-09-10 |
AU4118397A (en) | 1998-03-06 |
AR009305A1 (en) | 2000-04-12 |
JP2000517303A (en) | 2000-12-26 |
DE19633746A1 (en) | 1998-02-26 |
WO1998007700A1 (en) | 1998-02-26 |
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