MX2008007819A - Piperazine compounds with a herbicidal action - Google Patents
Piperazine compounds with a herbicidal actionInfo
- Publication number
- MX2008007819A MX2008007819A MXMX/A/2008/007819A MX2008007819A MX2008007819A MX 2008007819 A MX2008007819 A MX 2008007819A MX 2008007819 A MX2008007819 A MX 2008007819A MX 2008007819 A MX2008007819 A MX 2008007819A
- Authority
- MX
- Mexico
- Prior art keywords
- compounds
- alkyl
- formula
- phenyl
- group
- Prior art date
Links
- 150000004885 piperazines Chemical class 0.000 title claims abstract description 31
- 230000002363 herbicidal effect Effects 0.000 title claims description 29
- 239000004009 herbicide Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims description 1123
- 229910052717 sulfur Inorganic materials 0.000 claims description 873
- -1 C3-C6 cycloalkynyl Chemical group 0.000 claims description 175
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 133
- 125000000217 alkyl group Chemical group 0.000 claims description 114
- 239000001257 hydrogen Substances 0.000 claims description 106
- 229910052739 hydrogen Inorganic materials 0.000 claims description 106
- 238000000034 method Methods 0.000 claims description 102
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 71
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 61
- 239000002253 acid Substances 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 53
- 230000008569 process Effects 0.000 claims description 53
- 125000003545 alkoxy group Chemical group 0.000 claims description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 47
- 125000001424 substituent group Chemical group 0.000 claims description 44
- 239000002585 base Substances 0.000 claims description 39
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 33
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 32
- 125000003342 alkenyl group Chemical group 0.000 claims description 32
- 125000000623 heterocyclic group Chemical group 0.000 claims description 28
- 229910052702 rhenium Inorganic materials 0.000 claims description 25
- 125000000304 alkynyl group Chemical group 0.000 claims description 24
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 22
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 22
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 21
- 125000004414 alkyl thio group Chemical group 0.000 claims description 21
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- 150000002367 halogens Chemical class 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 125000001188 haloalkyl group Chemical group 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 17
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 17
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 17
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 16
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000009472 formulation Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 108010016626 Dipeptides Proteins 0.000 claims description 15
- ORTFAQDWJHRMNX-UHFFFAOYSA-N hydroxidooxidocarbon(.) Chemical group O[C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-N 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 125000004122 cyclic group Chemical group 0.000 claims description 14
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 12
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000003282 alkyl amino group Chemical group 0.000 claims description 11
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 11
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 230000010933 acylation Effects 0.000 claims description 9
- 238000005917 acylation reaction Methods 0.000 claims description 9
- 239000002671 adjuvant Substances 0.000 claims description 9
- 230000029936 alkylation Effects 0.000 claims description 9
- 238000005804 alkylation reaction Methods 0.000 claims description 9
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 9
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 7
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 125000000033 alkoxyamino group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 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 claims description 6
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 claims description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 6
- 125000001544 thienyl group Chemical group 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 5
- 125000006323 alkenyl amino group Chemical group 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000006254 cycloalkyl carbonyl group Chemical group 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000006319 alkynyl amino group Chemical group 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 4
- 125000005090 alkenylcarbonyl group Chemical group 0.000 claims description 3
- 125000005092 alkenyloxycarbonyl group Chemical group 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 125000004471 alkyl aminosulfonyl group Chemical group 0.000 claims description 3
- 125000005087 alkynylcarbonyl group Chemical group 0.000 claims description 3
- 125000005225 alkynyloxycarbonyl group Chemical group 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 125000006517 heterocyclyl carbonyl group Chemical group 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 3
- 125000004674 methylcarbonyl group Chemical group CC(=O)* 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 230000008635 plant growth Effects 0.000 claims description 3
- 125000006528 (C2-C6) alkyl group Chemical group 0.000 claims description 2
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005089 alkenylaminocarbonyl group Chemical group 0.000 claims description 2
- 239000007819 coupling partner Substances 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 2
- 125000001786 isothiazolyl group Chemical group 0.000 claims description 2
- 125000000842 isoxazolyl group Chemical group 0.000 claims description 2
- 125000002971 oxazolyl group Chemical group 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- 229910052705 radium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 claims description 2
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 6
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims 3
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 claims 1
- 239000002168 alkylating agent Substances 0.000 claims 1
- 229940100198 alkylating agent Drugs 0.000 claims 1
- 125000005343 heterocyclic alkyl group Chemical group 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 claims 1
- 125000004193 piperazinyl group Chemical group 0.000 claims 1
- OJZNYUDKNVNEMV-UHFFFAOYSA-M trimethylstannanylium;hydroxide Chemical compound C[Sn](C)(C)O OJZNYUDKNVNEMV-UHFFFAOYSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 57
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 35
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 34
- 239000002904 solvent Substances 0.000 description 33
- 230000009466 transformation Effects 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 28
- 241000196324 Embryophyta Species 0.000 description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 25
- 239000004480 active ingredient Substances 0.000 description 25
- 238000011282 treatment Methods 0.000 description 23
- 238000009835 boiling Methods 0.000 description 21
- 239000003960 organic solvent Substances 0.000 description 19
- 150000007513 acids Chemical class 0.000 description 17
- 239000011541 reaction mixture Substances 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 239000000049 pigment Substances 0.000 description 14
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 13
- 238000007363 ring formation reaction Methods 0.000 description 13
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 229920006395 saturated elastomer Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000013543 active substance Substances 0.000 description 10
- 244000038559 crop plants Species 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 125000001072 heteroaryl group Chemical group 0.000 description 10
- 239000002270 dispersing agent Substances 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- 239000008187 granular material Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 235000011054 acetic acid Nutrition 0.000 description 8
- 125000004494 ethyl ester group Chemical group 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 8
- 235000005985 organic acids Nutrition 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 239000004359 castor oil Substances 0.000 description 7
- 235000019438 castor oil Nutrition 0.000 description 7
- 238000007865 diluting Methods 0.000 description 7
- 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 7
- 238000003306 harvesting Methods 0.000 description 7
- 239000000080 wetting agent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 125000004415 heterocyclylalkyl group Chemical group 0.000 description 6
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 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 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 5
- 229940126062 Compound A Drugs 0.000 description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 5
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- 230000012010 growth Effects 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 5
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- MSTNYGQPCMXVAQ-RYUDHWBXSA-N (6S)-5,6,7,8-tetrahydrofolic acid Chemical compound C([C@H]1CNC=2N=C(NC(=O)C=2N1)N)NC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 MSTNYGQPCMXVAQ-RYUDHWBXSA-N 0.000 description 4
- PAQZWJGSJMLPMG-UHFFFAOYSA-N 2,4,6-tripropyl-1,3,5,2$l^{5},4$l^{5},6$l^{5}-trioxatriphosphinane 2,4,6-trioxide Chemical compound CCCP1(=O)OP(=O)(CCC)OP(=O)(CCC)O1 PAQZWJGSJMLPMG-UHFFFAOYSA-N 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
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- 150000001298 alcohols Chemical class 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
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- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
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- 108090000623 proteins and genes Proteins 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000005460 tetrahydrofolate Substances 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- RWLNJFYPOAZECJ-UHFFFAOYSA-N oxane-2-thione Chemical compound S=C1CCCCO1 RWLNJFYPOAZECJ-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000004675 pentylcarbonyl group Chemical group C(CCCC)C(=O)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 125000002071 phenylalkoxy group Chemical group 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 150000008048 phenylpyrazoles Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 230000003032 phytopathogenic effect Effects 0.000 description 1
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 1
- BXRNXXXXHLBUKK-UHFFFAOYSA-N piperazine-2,5-dione Chemical compound O=C1CNC(=O)CN1 BXRNXXXXHLBUKK-UHFFFAOYSA-N 0.000 description 1
- 244000000003 plant pathogen Species 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CAEWJEXPFKNBQL-UHFFFAOYSA-N prop-2-enyl carbonochloridate Chemical compound ClC(=O)OCC=C CAEWJEXPFKNBQL-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004673 propylcarbonyl group Chemical group 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 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
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 210000000614 rib Anatomy 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 208000005687 scabies Diseases 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000004550 soluble concentrate Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- UJMBCXLDXJUMFB-GLCFPVLVSA-K tartrazine Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-GLCFPVLVSA-K 0.000 description 1
- 235000012756 tartrazine Nutrition 0.000 description 1
- 239000004149 tartrazine Substances 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- BBNJXZZNHDFXCF-UHFFFAOYSA-N tert-butyl 2-iminoacetate Chemical compound CC(C)(OC(=O)C=N)C BBNJXZZNHDFXCF-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004562 water dispersible granule Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Abstract
The invention relates to the use of piperazine compounds of formula (I) or the agriculturally useful salts of piperazine compounds of formula (I) as herbicides, the variables in formula (I) being defined as cited in the claims and the description.
Description
COMPOUNDS OF PIPERAZINE WITH HERBICIDE ACTION
The present invention relates to the use of piperazine compounds of formula
or of the salts acceptable for agricultural use of piperazine compounds of formula I as herbicides, wherein in formula I the variables have the following meanings R1 and R2 independently denote cyano, C6 alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl. , C3-C6 cycloalkenyl, C3-C6 alkynyl, C3-C6 cycloalkynyl, phenyl, phenyl-C6alkyl, heterocyclyl, heterocyclyl-C6alkyl, phenol- [alkoxycarbon] l-C1- C6] -alqu? I (C-Oo fenilheterociclil-alkyl (C-C6), or COR21, where R21 is hydrogen, CC C3-C6 cycloalkyl, C2-C6, cycloalkenyl C3-C6 alkenyl, C2-C6, cycloalkynyl C3-C6, hydroxy, C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, amino, alkylamino d-C6, [di-alkyl (C6-6)] amine, alkenylamino C3-C6, alkynylamino C3- C6, alkylsulfonylamino C? -C6, N- (C2-C6 alkenyl) -N- (alkyl? C-C6) -am? No, N- (C2-C6 alkyl) -N- (alkyl) ? C C -? - C6) -am? no, N- (C1-C6 alkoxy) -N- (alkyl? C6) -am? no, N- (alkenyl)
C2-C6) -N- (alkox? -C? -C6) -am? No, N- (C2-C6 alkylene) -N- (C20-C6 alkoxy) -amino, phenyl , phenylamino, phenoxy, naphthyl or heterocyclyl, or NR22R23, where R22 and R23 independently of one another are hydrogen, CC C3-C6 cycloalkyl, C3-C6 alkenyl, cycloalkenyl C3-C6 alkynyl C3-C6 cycloalkynyl C3-C6 alkyl or alkylcarbonyl C-C6, or OR24, where R24 is alkyl CC C3-C6 alkyl, C3-C6 cycloalkyl, C3-C6 alkynyl C3-C6 cycloalkynyl C3-C6, phenyl or phenyl-alkyl (C Ce), or S02R25, where
R25 is C-C6 alkyl or phenyl, where the mentioned aliphatic, cyclic or aromatic portions of the substituents of R1 and R2 may be partially or fully halogenated and / or may carry one to three of the following cyano, hydroxy, alkyl groups C1-C4, C3-C6 cycloalkyl haloalkyl, CC4alkylthio alkyloxy CC4, [di-alkylene- (C? -C4)] - ammonium, alkylcarbonyl CC hydroxycarbonyl, C1-C4 alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl CC [d ? -alqu? l- (C C4)] aminocarbonyl or alkylcarbonyloxy CC and where R1 can also be hydrogen, R3 is a residue R26, OR27, SR28, NR29R30 or N (OR3) R32, where R26, R27, R28, R29 and R32 independently of one another are hydrogen, C-C6 alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, formyl, alkylcarbonyl -C cycloalkylcarbonyl C3-C6, C2-C6 alkenylcarbonyl , C2-C6 alkynylcarbonyl, CCalkyl alkoxy (CC), C -? - C6 alkoxycarbonyl, C2-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, alkylaminocarbonyl the CC CC alkenylaminocarbonyl alkynylaminocarbonyl C3-C6 alkylaminocarbonyl alquilsulfonilammocarbonilo CC CC [di-alquilammo (C C6)] Carbon? I, N- (alkene? the C3-C6) -N- (alk? l-C1-C6) -am ? nocarbon? lo, N- (alkyl? C3-C6) -N- (alkyl? C1-C6) -am? nocarbon? lo, N- (alkoxy? CC6) -N- (alkyl? CC6) -am? No-carbonyl, N- (C3-C6 alkenyl) -N- (alkox? -C1-C6) -am? Nocarbonyl, N- ( Alkyl C3-C6) - N- (alkoxy-C1-C6) -am? nocarbonyl, d? - (alkyl? C6) -am? notcarbonyl, alkylcarbonyl CCalkyl C- ? -C6, C-C6 alkoxyalkyl CC N- (alkalamy? CC6) -? M? No- CC alkyl N- (d? -alk? Lam? No CC-imino-C? Alkyl) C6 or [Tr? -alk? L- (C C4)] only, where the mentioned isocyclic or aliphatic parts of the substituents may be partially or totally halogenated and / or may carry one to three of the following groups cyano, hydroxy, CC alkyl haloalkyl CC cycloalkyl C3-C alkoxy CC alkylthio CC [d? -alkyl- (C-C4)] -amino, alkylcarbonyl CC hydroxycarbonyl, alkoxycarbonyl C1-C4, aminocarbonyl, alkylaminocarbonyl C C4, [d? -alkyl- (C? -C4)] aminocarbonyl or alkylcarbonyloxy CC or phenyl, phenyl-alkyl-phenylcarbonyl, phenylcarbonyl-C6alkyl,
CC Phenoxicarbonilo, phenylaminocarbonyl, phenylsulfonylaminocarbonyl, N- (alk? The Cr C6) -N- (phen? L) -am? Nocarbon? I, phenyl-alkylcarbonyl CC heterocyclyl, heterocyclylcarbonyl heterocichl- CC alkyl, heterocyclylcarbonyl-alkyl
heterocyclyloxycarbonyl, heterocyclylaminocarbonyl, heterocyclylsulfonyl-ammocarbonyl, N- (C1-C6alkyl) -N- (heterocyclo?) -am? nocarbonyl, or heterocyclic alkylcarbonyl C Ce, where the phenyl or heterocyclyl portions of the substituents may be partially or totally halogenated and / or may carry one to three of the following nitro, cyano, CC haloalkyl, CCalkoxy CC or haloalkoxy CC or S (O) nR33 groups, where n means 1 or 2, and R33 means alkyl CC haloalkyl CRC6 or phenyl, and wherein the phenyl substituent may be halogenated, partially or wholly and / or you can carry one to three of the following nitro, cyano, alkyl CC haloalkyl CC alkoxy CC or haloalkoxy and R30 and R31 independently each are hydrogen, CC C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 where aliphatic or parts isociclicas of the substituents may be halogenated, partially or wholly and / or can carry one to three of the following cyano groups , hi droxy, CC alkyl haloalkyl CC cycloalkyl CC alkoxy CC alkylthio CrC4, [d? -alkyl- (CC)] - amino, alkylcarbonyl CrC4, hydroxycarbonyl, alkoxycarbonyl CrC4, aminocarbonyl, alkylaminocarbonyl CC [d? -alkyl- (CC4 )] am? nocarbon? I or alkylcarbonyloxy C C4 are phenyl, CRC6 phenyl-alkyl, heterocic at or heterocyclyl-alkyl CRC6 where the phenyl parts or heterocichlo of the substituents may be halogenated, partially or wholly and / or may carry one to three of the following nitro, cyano, alkyl CC haloalkyl CC alkoxy CC or haloalkoxy CC R4, R5, R6 independently of one another are hydrogen, CC alkyl alkoxy CC where ahfaticas mentioned parts of the substituents R4, R5 or R6 may you be halogenated, partially or wholly and / or may carry one to three of the following cyano, hydroxy, alkyl CC haloalkyl CC C3-C6 alkyl, CC alkylthio CRC4 [d -alqu l- (CRC4)?] - am? no, alkylcarbonyl CC hydroxycarbonyl, alkoxycarbonyl CrC4, ammocarbonyl, alkylammocarbonyl Cr
C4, [d? -alkyl- (C? -C4)] ammoncarbonyl or C4 alkylcarbonyloxy, R3 and R4 can also together mean a keto group, R7, R8 independently of one another mean hydrogen, hydroxy, CrC6 alkyl, which can
is partially or totally halogenated and / or can carry one to three of the following groups cyano, hydroxy, CC alkyl haloalkyl CC cycloalkyl C3-C alkoxy CC alkylthio CC [d? -alkyl- (CC4)] - am? no, C4 alkylcarbonyl, hydroxycarbonyl, CrC4 alkoxycarbonyl, aminocarbonyl, CC alkylammocarbonyl [d? -alkyl- (CrC4)] ammoncarbonyl or alkylcarbonyloxy CC A1, A2 independently of each other means aryl or heteroaryl, with the exception of indolyl, where Ra is attached ortho to the binding site of A1 to a C atom or an N atom of A1 and where Ra has one of the meanings indicated below Ra halogen, cyano, nitro, CC cycloalkyl, CC alkenyl C2 -C6, cycloalkenyl CC alkanedienyl CC alkynyl CC [Tr? -alkyl- (C? -C6) -s? I?] -alkynyl (C2-C6), cycloalkynyl C3-C6, alkylthio CrC6, alkylsulfinyl CC aplo, phenyl-alkyl (C6), phenol-alkenyl- (C2-C6), phenylsulfonyl-alkyl (Cr6), heterocyclyl, heterocyclyl-alkyl (Cr6) or phenol- [ x? carbon? l-C1-C6] -alkyl (CrC6), Z1P (0) (OR9) 2, Z2B (OR10) 2, where R9 and R10 in their case mean hydrogen or alkyl CC and R 0 in Z2B (OR10) 2 can together form an alkylene chain CC or Z3COR11, wherein R11 hydrogen, C3-C6 cycloalkyl C3 alkyl, C3-C6 CC cycloalkenyl, C3-C6 CC cycloalkynyl alkynyl, hydroxy, C6 alkoxy, C3-C6 alkenyloxy, alkynyloxy CC amino, alkylamino CrC6, [di-alkyl
(CC)] ammonium, alkoxyamino C? -C6, [d? - (CrC6) -alcox?] Amine, alkylsulfonylamino CC alkylamino CrC6sulfon? Lam? No, [di-alkylamino
(CrC6)] sulfonamide, C3-C6 alkenylamino, C3-C6 alkynylamino, N- (C2-C6 alkenyl) -N- (alkyl? CrC6) -am? No, N- (alk? the CC6) -N- (alkyl? O-amino, N- (alkoxy? CrC6) -N- (alkyl? CrC6) -am? no, N- (alken? lo C2-C6) -N- ( Alcox? -CrC6) -am? no, N- (alk? n? I C2-C6) -N- (Alcox? -CrC6) -am? no, phenyl, phenoxy, phenylamino, naphthyl or heterocic it, or Z4NR12R13, where R12 and R13 independently means hydrogen, C3-C6 cycloalkyl, C3-C6 alkenyl, C3-C6 cycloalkenyl, C3-C6 cycloalkynyl alkynyl, C6 alkylcarbonyl, C3-C6 cycloalkylcarbonyl, [di-alkylamino (CrC6) ] carbonyl, alkoxycarbonyl CrC6, alkoxyl carbon? lC C6-
alkyl (CC alkylsulfonyl CrC6, alkylaminosulfonyl CrC6, [di-alkylamino (CrC6)] sulfonyl, phenylcarbonyl, phenylaminocarbonyl, phenylsulfonyl, phenylsulfonylaminocarbonyl or heterocyccarbonyl, or Z5CH = NO-R14, where R14 means hydrogen or CC alkyl or Z6OR15, where R15 is hydrogen, C3-C6 alkenyl CC, C3-C6 cycloalkenyl, C3-C6 alkynyl, C3-C6 cycloalkynyl, C6 alkylcarbonyl, C6-alkyl alkoxycarbonyl, (C-C6), [d ? -alcox? carbon? l- (CrC6)] - alkyl (CrC6), phenyl or phenyl-alkyl (C-C6), or Z7SO2R16, where R16 signifies CC alkyl or phenyl, and where Z1, Z2, Z3, Z4, Z5, Z6, Z7 independently of each other means a bond, -CH2-, - CH2-CH2-, -O-CH (R17) -, -S-CH (R18) -, -S (0) -CH ( R19) - or -S02CH (R20) -, and where R17, R18, R19 and R20 independently of each other mean hydrogen or CC alkyl and where the mentioned aliphatic, cyclic or aromatic portions of the Ra substituent may be partially or totally halogenated and / or they can carry a or to three of the following groups cyano, hydroxy, CC alkyl haloalkyl CC cycloalkyl CC alkoxy CC alkylthio CC [d? -alkyl- (CC4)] - amine, C-C4 alkylcarbonyl, hydroxycarbonyl, alkoxycarbonyl CC aminocarbonyl, alkylammocarbonyl C C4, [d? -alkyl- (CC4)] ammoncarbonyl or alkylcarbonyloxy CrC4, and Rb, Rc, Rd, Re and Rf in each case independently of each other are equivalent to hydrogen or have a meaning indicated for Ra and where two residues Ra, R or Rc linked to adjacent cyclic atoms A1 or two residues Rd, Re or Rf linked to adjacent cyclic atoms A2 also represent linear C3-C6 alkylene, which may be fully or partially halogenated and may carry one to three of the following groups: cyano, hydroxy, CC alkyl haloalkyl, C3-C6 cycloalkyl, CrC4 alkoxy, CC alkylthio [d? -alkyl- (CrC4)] - ammonium, CrC4 alkylcarbonyl, hydroxycarbonyl, CrC4 alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl CrC4, [d? -alkyl- (C C4)] ammoncarbonyl or alkylcarbonyloxy CrC4, where a CH2 group in C3-C6 alkylene can be substituted with a carbonyl group, thiocarbonyl group or sulfonyl group and where one or two non-adjacent CH2 groups in C3-C6 alkylene can be substituted in each case with oxygen, sulfur or a group NR34, where R34 has a meaning indicated for R12 Taxtomins A and B (King RR et al, J Agrie Food Chem (1992) 40, 834-837)
produced by the plant pathogen S Scabies are natural substances with a central ring of p? peraz? n-2,5-d? ona, which in position 3 carries a rest 4-N? tro-? ndol- 3-? Lmet? Lo and in position 2 a benzyl residue that may be eventually substituted with OH Due to its harmful effect for plants, the possibility of using this class of compounds as herbicides was also studied (King RR et al, J Agrie Food Chem (2001) 49, 2298-2301) EP-A 181 152 and EP-A 243122 disclose piperazm compounds of similar structure and their use as antagonists of Platelet Activating Factor In US 2003/0171379 A1 the use of mactanamide, a fungistatic diketopiperazine of formula A,
where R represents H or methyl, as an active principle inhibitors of infections in medicine In WO 99/48889, WO 01/53290 and WO 2005/01 1699 there are disclosed compounds of 2,5-d? cetop? peraz? na, which they have in the 3-position or in the 6-position an imidazolyl radical bound through a methylene or methyl group and in the other 3-position or 6-a benzyl radical These compounds are antitumor active substances Compound 1, 4- is known d? acet? l-3,6-d? - (2-chlorophen? l) p? peraz? n-2,5-d? ona (LX Wang, YZ Shi, ZM Du, HW Hu, take Chem Lett ( 1993) 4, 687-688) An object of the present invention is the arrangement of compounds with herbicidal action. In particular, it is desired to provide those having a high herbicidal action, especially already with low application amount and whose tolerance to plants of cultivation is sufficient for a commercial use These and other objectives are met by the compounds of formula I that were mentioned previously and by its salts acceptable for agricultural use Correspondingly, the present invention relates to the use of piperazine compounds of general formula I or of the acceptable salts for agricultural use of piperazine compounds of formula I as herbicides, that is, to combat harmful plants The invention also relates to media, which contain an effective amount
as a herbicide of at least one piperazine compound of formula I or of a salt acceptable for agricultural use of I and the usual adjuvants for the formulation of herbicides. The invention also relates to a method for combating unwanted plant growth, wherein an herbicidally effective amount of at least one piperazine compound of formula I or of an acceptable salt for agricultural use of I on plants, their seeds and / or their habitat is allowed to act. The piperazine compounds of formula I are new and are also object of the present invention, - excluding the compounds of formula I, wherein A1 and A2 signify phenyl, R1 is methyl, R2 is hydrogen or methyl, R3, R4, R5, R6, R7, R8 signify hydrogen, substituents Ra and Rb in each case equals hydroxy, which are arranged in the two ortho positions of the phenyl ring A1 and Rc, Rd, Re and Rf signify hydrogen, further excluding the compound of formula I, wherein A1 represents phenyl and A2 means 4-? M? Dazol? Or A1 represents 4-? M? Dazol? And A2 means phenyl, further excluding the compound of formula I, where A1 represents phenyl, Ra means chlorine, Rb and Rc are hydrogen, the group A2 (RdReRf) represents o-chlorophenyl, R1 and R2 signify methylcarbonyl and R3 to R8 where appropriate mean hydrogen The invention further relates to processes and intermediates for the preparation of compounds of formula I Other embodiments of the present invention may to be extracted from the claims, the description and the examples It is understood that the features that were previously indicated and will still be explained below the object according to the invention, can be used not only in the combination indicated in each case, but also in other combinations, without being excluded from the scope of the invention The compounds of formula I can contain, according to the substitution pattern, one or several chiral centers and are presented Then, mixtures of enantiomers or diaesteromers The object of the invention are presented both in the pure enantiomers or diaesteromers as well as in their mixtures. The compounds of formula I can also be presented in the form of their salts of agricultural utility, where in general it is not significant. what kind of salt it is In general, these are the salts of those cations or the acid addition salts of
those acids whose cations or anions do not adversely affect the herbicidal action of the compounds I The cations include, in particular, ions of the alkali metals, preferably lithium, sodium or potassium, of the alkaline earth metals, preferably calcium or magnesium and of the transition metals, preferably manganese, copper, zinc or iron In the same way, ammonium can also be used as a cation, where here, if desired, one to four hydrogen atoms can be substituted with CC-alkyl-hydroxy-alkyl-CC-alkoxy-CC-alkyl CC hydroxy-alkoxy CCalkyl CC phenyl or benzyl, preferably ammonium, dimethylammonium, dnsopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydrox? et-1-ox?) et-1-?? lamon? o, D? (2 -h? drox? et-1 -? l) ammonium, tpmethylbenzylammonium Also included are phosphonium, sulfonium ions, preferably tr? (alk? CC) sulfon? o or sulfoxonium ions, preferably tr? alkyl-CC4) sulfoxon? or Anions of acid addition salts useful es are in the first instance chloride, bromide, fluoride, acid sulfate, sulfate, acid diphosphate, acid phosphate, nitrate, hydrophophate, nitrate, hydrocarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, as well as the CC alkane acids anions preferably formate , acetate, propionate butyrate The organic molecular parts indicated for the compounds of the invention constitute collective concepts for individual statements of the various members of the group All carbon chains, such as alkyl, haloalkyl, as well as the alkyl parts in cyanoalkyl, alkoxy, halo-alkoxyalkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, N-alkylaminosulfonyl, N, Nd-alkallammonosulfonyl, dialkylamino-, N-alkylsulfonylamino, N-haloalkylsulfonylamino, N-alkylN-alkylsulfonylamino, N-alkylN -halogenalquilsulfonilamino, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylcarbonyloxy-, alkylaminocarbonyl, dialquilammocarbonilo, dialkylaminothiocarbonyl, alkoxyalkyl, dialkoxyalkyl, alkylthioalkyl, dialkylaminoalkyl, dialquilhidrazinoalquilo, alquiliminooxialquilo, alkylcarbonylalkyl, alcoxnminoalquilo, N- (alk lam not?) -? m noalqu It, N- (d? alkylamine) -? myalnoalkyl, alkoxycarbonylalkyl, dialkylaminocarbonylalkyl, phenylalkenylcarbonyl, heterocyclylalkenylcarbonyl, N-alkoxy-N-alkylaminocarbonyl, N-alkylN-phenylaminocarbonyl, N-alkylN-heterocyclylammocarbonyl, phenylalkyl, heterocyclylalkyl, phenylcarbonylalkyl, heterocyclylcarbonylalkyl,
dialkylaminoalkoxycarbonyl, alkoxyalkoxycarbonyl, alkenylcarbonyl, alkenyloxycarbonyl, alkenylaminocarbonyl, N-alkenyl-N-alkylaminocarbonyl, N-alkenyl-N-alkoxycarbonyl, alkynylcarbonyl, alkynyloxycarbonyl, alkynylaminocarbonyl, N-alkynyl-N-alkylaminocarbonyl, N-alkynyl-N-alkoxyaminocarbonyl, alkenyl, alkynyl, haloalkenyl, haloalkynyl- and alkoxyalkoxy, can be straight or branched chain prefix CC- indicates the respective carbon number of the hydrocarbon unit Unless otherwise indicated, the halogenated substituents preferably have one to five same or different halogen atoms, especially fluorine atoms or chlorine atoms The halogen meaning in each case represents fluorine, chlorine, bromine or iodine. For example, alkyl, as well as alkyl groups, for example, alkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl, alkylcarbonyl, alkylamino, alkylsilyl, phenylalkyl, phenylsulfonylalkyl, tertiarycylalkyl saturated, branched or straight chain hydrocarbon radicals with one or more C atoms, eg 1 to 2, 1 to 4, or 1 to 6 carbon atoms, eg CC alkyl such as methyl, ethyl, propyl, 1-met? let's do it, butyl, 1 -met? lprop ?, 2-met? lprop? lo, 1, 1-d? met? let ?, it, pentyl, 1-methyl?, 2-methyl? what, 3-methyl butyl, 2,2-d? -methylpropyl, 1 -ethylpropyl, hexyl, 1, 1-d? metapropyl, 1, 2-d ? met? lprop ?, 1-metpentpentlo, 2-metpentpentlo, 3-metpentpentlo, 4- methylpentyl, 1, 1-d? met? l? l? l, 1, 2 -d? metabutyl, 1, 3-d? methyl butyl, 2,2-d? methyl butyl, 2,3-dimethylbutyl, 3,3-d? methyl? , 1-butyl, 2-butyl, 1, 1, 2-methylmethopropyl, 1, 2,2-t-methylpropyl, 1-ethyl-1-methylpropyl, 1 -et In an embodiment according to the invention, alkyl replaces small alkyl groups such as CC alkyl. In another embodiment according to the invention alkyl substitutes larger alkyl groups such as alkyl-Haloalkyl, an alkyl moiety as previously indicated, whose atoms from hi drogeno are partially or totally substituted with halogen atoms such as fluorine, chlorine, bromine and / or iodine, eg chloromethyl, dichloromethyl, t-chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroet It, 2-bromomethol, 2-iododetyl, 2,2-d? fluoroetheyl, 2,2,2-tr? fluoroetheyl, 2-chloro-2-fluoroetheyl, 2-chloro -2,2-d? Fluoroetheyl, 2,2-d? Chloro-2-fluoroquinol, 2,2,2-tr? Chloroetheyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl , 2,2-d? Fluoropropyl, 2,3-d? Fluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-d? Chloropropyl, 2-bromopropyl, 3-bromoprop It, 3,3,3-tpfluoropropyl, 3,3,3-tr? chloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-
(fluoromet? l) -2-fluoroether, 1 - (chlorometyl) -2-chloroether, 1 - (bromomet? l) -2-bromoetyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl Cycloalkyl as well as cycloalkyl parts for example in cycloalkoxy or cycloalkylcarbonyl saturated monocyclic hydrocarbon groups with three or more C atoms, eg 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl Alkenyl as well as the alkenyl portions, for example in phenol-alkenyl- (C2-C6) or alkenylamino unsaturated, branched or straight-chain hydrocarbon radicals with two or more C atoms, eg, 2 to 4, 2 to 6 or 3 to 6 carbon atoms and a double bond at any position, eg CC alkenyl such as ethenyl, 1 -propene, 2-propene, 1-methylethinyl, 1 -Buthene, 2-Butene, 3-Buten It, 1-methyl-1-propenoyl, 2-methyl-1-propenoyl, 1-methyl-2-propene, 2-methyl-2-propene , 1-penten? Lo, 2-penten? Lo, 3-penten? Lo, 4-penten? Lo, 1-met? L-1-buten? Lo, 2-met? L-1-buten? Lo, 3 -met? l-1 -b use, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-d? Met? L-2-propene, 1, 2-d? Met? L- 1-propenoyl, 1, 2-d? Met? L-2-propen? Lo, 1 -et? L-propenyl, 1-et? L-2-propen? Lo, 1-hexene, 2- Hexenon, 3-Hexenon, 4-Hexenon, 5-Hexenol, 1-methyl-1-peptide, 2-methyl-1-peptide, 3-methyl-1-pentenyl, 4-methyl-1 -penten? lo, 1 -met? l-2-penten? lo, 2-met? l-2-pentenilo, 3-met? l-2-penten? lo, 4-met? l-2-penten? lo , 1-methyl-3-pentenyl, 2-methyl-3-pentyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1 -met 4-pentene, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1-d-met. L-2-butenyl, 1,1-d? met? l-3-buten? lo, 1, 2-d? met? l-1-butenyl, 1, 2-d? met? l-2 -bute? 1, 2-d? met? l-3-buten? lo, 1, 3-d? met? l-1-butenilo, 1, 3-d? met? l-2-butenilo, 1 , 3-d? Met? L-3-buten? Lo, 2,2-d? Met? L-3-buten? Lo, 2,3-d? Met? L-1-buten? Lo, 2,3 -d? methyl-2-butenyl, 2,3-d? met? l-3-buten? lo, 3,3-d? met? l-1-buten? lo, 3,3-d? met l-2-butenyl, 1-et? l-1-butenyl, 1-et? l-2-buten? lo, 1 -et? l-3-buten? lo, 2-et? l-1 -buten? lo, 2-et? l-2-buten? lo, 2-et? l-3-butenilo, 1, 1, 2-tr? met? l-2-propen? lo, 1 -et? l -1-methyl-2-propenoyl, 1-et? L-2-met? L-1-propen? Lo, 1- et? L-2-met? L-2-propen? Lo In a according to the invention groups are used to Lkenyl as C2-C6 alkenyl In another embodiment according to the invention alkenyl groups are used as C3-C alkenyl cycloalkenyl, as well as cycloalkenyl parts monocyclic unsaturated hydrocarbon groups with three or more C atoms, eg, 3 to 6, preferably 5 to 6 members of the carbon ring, such as c? Clopenten-1-? Lo, c? Clopenten-3? Lo, c? Clohexen-1? -lo, cyclohexen-3? Lo, c? Clohexen-4?
Alkynyl as well as alkyl groups for example in [Tp-alkyl (C C6) s? I-alk? N?
(C2-C6) or alkynylamino branched or straight chain hydrocarbon groups with two or more C atoms, eg, 2 to 4, 2 to 6, or 3 to 6 carbon atoms and one or two triple bonds in any position that does not is adjacent, eg, C2-C6 alkynyl as ethinyl, 1 -propylene, 2-propinyl, 1-butyl, 2-butyl, 3-butyl, 1 -met? l-2-prop? n? lo, 1-pent? n? lo, 2-pent? n? lo, 3-pentinilo, 4-pent? n? lo, 1 -met? l-2-but Only 1-methyl-3-butyl, 2-methyl-3-butyl, 3-methyl-1-butynyl, 1, 1 -d? met. I-2-propylene, 1 -et-2-propylene, 1-hex, 2-hex, 3-hex, 4 -hexinyl, 5-hexylene, 1-methyl-2-pentene, 1-methyl-3-pentene, 1-methyl-4-pentene It, 2-met? l-3-pentinil, 2-met? l-4-pent? n? lo, 3-met? l-1 -pentinil, 3-met? l-4-pent? n? lo , 4-met? L-1-pent? N? Lo, 4-met? L-2-pent? N? Lo, 1, 1-d? Met? L-2-but? N? Lo, 1, 1 -d? met? l-3-but? n? lo, 1, 2-d? met? l-3-but? n? it, 2,2-d? met? l-3-but? n? it , 3,3-d? Met? L-1-but? Nol, 1 -et? L-2-but? N? Lo, 1 -et? L-3-but? N? Lo, 2-et ? l-3-but? n? lo, 1-et? l-1 -met? l-2-prop? n? lo Cycle alkynyl as well as cycloalkynyl cycloalkynyl groups with monocyclic hydrocarbon groups having three or more C atoms, eg, 3 to 6, preferably 5 to 6 carbon ring members and a triple bond, such as c? clohex? n-1-? lo, c? clohex? n-3-? lo, c? clohex? n-4?? Alcadienil CC hydrocarbon radicals doubly unsaturated, branched or straight chain with four or more C atoms and two double bonds in any position that is not adjacent, p eg, 4 to 10 carbon atoms and two double bonds in any position that is not adjacent, eg, 1, 3-Butad? en? lo, 1-met? l-1, 3-butad? en? lo, 2 -met? -1,3-butadienyl, penta-1,3-d? en-1-yl, hexa-1, 4-d? en-1-? lo, hexa-1, 4-d? -3-? Lo, hexa-1, 4-d? En-6-yl, hexa-1, 5-d? En-1-? Lo, hexa-1, 5-d? En-3-? Lo, hexa-1, 5-d? en-4-? lo, hepta-1, 4-d? en-1-? lo, hepta-1, 4-d? en-3-? lo, hepta-1, 4 -d? en-6-? lo, hepta-1, 4-d? en-7-? lo, hepta-1, 5-d? en-1-? lo, hepta-1, 5-d? en- 3-? Lo, hepta-1, 5-d? En-4-? Lo, hepta-1, 5-d? En-7-? Lo, hepta-1, 6-d? En-1-? Lo, hepta-1, 6- d? en-3-? lo, hepta -1, 6-d? En-4-? Lo, hepta-1, 6-d? En-5-? Lo, hepta-1, 6-d? En-2-? Lo, octa-1, 4- d-en-1- ilo, octa-1, 4-d? en-2-? lo, octa-1, 4-d? en-3-? lo, octa-1, 4-d? en-6- It is octa-1, 4-d? en-7-? lo, octa-1, 5- d? en-1?? lo, octa-1, 5-d? en-3-? lo, octa- 1, 5-d? En-4-? Lo, octa-1, 5-d? En-7-? Lo, octa-1, 6-d? En-1-? Lo, octa-1, 6-d ? in-3-? lo, octa-1, 6-d? en-4-? lo, octa-1, 6-d? en-5-? lo, octa-1, 6-d? en-2- It, deca-1, 4-dienyl, deca-1, 5-d? en? lo, deca-1, 6-d? en? lo, deca-1, 7-d? en? lo, deca-1 , 8-d? En? Lo, deca-2,5-dienyl, deca-2,6-d? En? Lo, deca-2,7-d? En? Lo, deca-2,8-d? Alkoxy or alkoxy moieties for example in phenylalkoxy, alkoxyamino, alkoxycarbonyl alkyl, as defined above, which is attached through an oxygen atom. eg, methoxy, ethoxy, n-propoxy, 1-met? lethox ?, butoxy, 1-met? lpropox ?, 2-met? lpropox? or 1, 1-dimethylethyloxy, pentoxy, 1-methoxybutox ?, 2-methoxytox, 3-methoxybutox ?, 1, 1 -d? met? lpropox ?, 1, 2-
dimethylpropoxy, 2,2-d? met? lpropox ?, 1-et? lpropox ?, hexoxy, 1 -met? lpentox ?, 2-met? lpentox ?, 3-methylpentoxy, 4-met? lpentox ?, 1, 1 -d? met? lbutox ?, 1, 2-d? met? lbutox ?, 1, 3-d? met? lbutox ?, 2,2-dimethylbutoxy, 2,3-d? met? lbutox ?, 3.3 -d? met? lbutox ?, 1 -et? lbutox ?, 2-et? lbutox ?, 1, 1, 2-tpmetilpropoxi, 1, 2,2-tr? met? lpropox ?, 1 -et? l-1 -methylpropoxy or 1 -et? l-2-met? lpropox? In one embodiment according to the invention, small alkoxy groups such as CC4 alkoxy are used. In another embodiment according to the invention, larger alkoxy groups such as C5-C6 alkoxy Alkenyloxy alkenyl are used as indicated previously, which is attached through an oxygen atom, eg, C3-C6 alkenyloxy such as 1-propen? lox ?, 2-propen? lox ?, 1-methylethenyloxy, 1 -Buten? lox ?, 2-Buten? lox ?, 3-Buten? lox ?, 1 -met? l-1-propen? lox ?, 2-met? l-1-propenyloxy, 1-met? l-2-propen? lox ?, 2-met? l-2-propen? lox ?, 1 -penten? lox ?, 2-penten? Lox ?, 3-penteniloxy, 4-penten? Lox ?, 1-met? L-1-buten? Lox ?, 2-met? L-1-butene? Lox ?, 3-met? l-1-buten? lox ?, 1-met? l-2-buten? lox?, 2-met? L-2-buten? Lox ?, 3-met? L-2-buten? Lox ?, 1 -met? L-3-buten? Lox ?, 2-met? L-3-buteniloxi, 3-met? L-3-buten? Lox ?, 1, 1-d? Met? L-2-propen? Lox ?, 1, 2-d? Met? L-1-propen? Lox ?, 1, 2 -d? met? l-2-propen? lox ?, 1 -et? l-1-propenyloxy, 1-et? l-2-propen? lox ?, 1-hexen? lox ?, 2-hexen? lox? , 3-hexenyloxy, 4-hexen? Lox ?, 5-hexen? Lox ?, 1-met? L-1-penten? Lox ?, 2-met? L-1-penten? Lox ?, 3-met? L -1- pentenyloxy, 4-met? L-1-penten? Lox ?, 1-met? L-2-penten? Lox ?, 2-met? L-2-penten? Lox ?, 3-met? L- 2- Pentenyloxy, 4-met? L-2-penten? Lox ?, 1-met? L-3-penten? Lox ?, 2-met? L-3-penten? Lox ?, 3-met? L-3 - pentenyloxy, 4-met? l-3-penten? lox ?, 1 -met? l-4-penten? lox ?, 2-met? l-4-penten? lox ?, 3-met? l-4- pentenyloxy, 4-met? l-4-penten? lox ?, 1, 1 -d? met? l-2-buten? lox ?, 1, 1 -d? met? l-3-buten? lox ?, 1 , 2-d? Met? L-1-buteniloxi, 1, 2-d? Met? L-2-buten? Lox ?, 1, 2-d? Met? L-3-buten? Lox ?, 1, 3 -d? met? l-1-buteniloxi, 1,3-d? met? l-2-buten? lox ?, 1, 3-d? met? l-3-buten? lox ?, 2,2-d ? met? l-3-buten? lox ?, 2,3-d? met? l-1-buten? lox ?, 2,3-d? met? l-2-buten? lox ?, 2,3- d? met? L-3-buten? lox ?, 3,3-d? met? l-1-butenyloxy, 3,3-d? met? l-2-buten? lox ?, 1 -et? l-1-butenyloxy, 1 -et? L-2-buten? Lox ?, 1 -et? L-3-buten? Lox ?, 2-et? L-1-butenyloxy, 2-et? L-2-buten? Lox ?, 2 -et? l-3-buten? lox ?, 1, 1, 2-tmetmet? l-2-propen? lox ?, 1 -et? l-1- met? l-2-propen? lox ?, 1 - et? l-2-met? l-1 propepiloxi and 1 -et? l-2-met? l-2-propen? lox? In one embodiment according to the invention, small alkenyloxy groups are used as C3-C4 alkenyloxy. In another embodiment according to the invention, larger alkenyloxy groups are used as alkenyloxy CC Alkynyloxy alkynyl as indicated previously, which is attached through an oxygen atom, eg, C3-C6 alkynyloxy such as 2-prop? n? lox ?, 2-but? n? lox ?, 3-but? n? lox ?, 1- met? l-2-prop? n? lox ?, 2 -pent? n? lox ?, 3-penty? lox ?, 4-penty? lox ?, 1 -met? l-2-but? n? lox ?, 1-met? l -3-butynyloxy , 2-met? L-3-but? N? Lox ?, 1 -et? L-2-prop? N? Lox ?, 2-hex? N? Lox ?, 3-hex? N? Lox ?, 4 -hex? n? lox ?, 5-
Hexynyloxy, 1 -met? l-2-pent? n? lox ?, 1 -met? l-3-pent? n? lox? In an embodiment according to the invention, small alkynyloxy groups such as C3-C4 alkynyloxy are used. In another embodiment according to the invention, larger alkyloxy groups are used, such as alkyloxy CC alkyl alkylthio, as defined above, which is attached through an S-alkyl arylsulfinyl atom. , as defined above which is attached through an SO alkyl alkyl sulfonyl group, as defined above, which is attached through a S (O) 2 alkyl alkylcarbonyl group, as defined above, which is attached through a group (C = O) -, p. eg, Methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methyl-ethylcarbonyl, butylcarbonyl, 1-methyl-ethylcarbonyl, 2-methylpropylcarbonyl or 1,1-dyl-methyl? lcarbonyl, pentylcarbonyl, 1-methylbutylcarbon, 2-methylbutylcarbon, 3-methylbutylcarbon, 2,2-dimethylpropylcarbonyl, 1-ethylpropylcarbon. What is hexylcarbonyl, 1,1-d? -methylcarbonyl, 1, 2-dimethylpropylcarbonyl, 1-methyl? -carbonyl, 2-methyl? carbonyl, 3-methyl? Carbon, 4-methylpentyl, 1, 1-methyl, butylcarbon, 1, 2-methyl, butylcarbon, 1,3-dimethylbutylcarbonyl, 2, 2, -d? Methyl butylcarbon, 2,3-d? Methyl butylcarbon, 3,3-dimethylbutylcarbonyl, 1-ethylbutylcarbon, 2-ethylbutylcarbon 1, 1, 2-tr? methylpropylcarbon, 1, 2,2-tr? methypropylcarbon, 1-ethyl-1-methylpropylcarbon or 1-ethyl-carbonyl alkenyl, as defined above, which is attached through a group (C = O), eg 1-ethenecarbonyl or alkynylcarbonyl alkynyl, as defined above It is linked through a group (C = 0), eg 1-propylenecarbon or heterocyclyl, a monocyclic or bicyclic, saturated, partially unsaturated or aromatic heterocyclic ring with three or more, eg 3 a 10 Cyclic atoms, eg a monocyclic 3-, 4-, 5-, 6-, 7- or 7-membered heterocyclic ring containing one to four identical or different heteroatoms, selected from the oxygen, sulfur or nitrogen group, and may be bonded through C or N, eg, saturated or unsaturated rings of 3-4 members joined by C such as 2-oxanthione, 2-oxetane, 3-oxetane, 2-azine ? d? n? lo, 3-t? eta? lo, 1-a d? n? lo, 2-a d? n? the Rings saturated of 5 members joined by C, as tetrah? drofuran-2- It, tetrah? drofuran-3-? lo, tetrah? drot? en-2-? lo, tetrah? drot? en-3-? lo, tetrah? drop? rrol-2-? lo, tetrah? drop? rrol -3-? Lo, tetrah? Drop? Razol-3-? Lo, tetrah? Dro-p? Razol-4-? Lo, tetrahedron? Soxazol-3-? Lo,
tetrahydro? soxazol-4-? lo, tetrahydro? soxazol-5-? lo, 1, 2-oxat? olan-3-? lo, 1, 2-oxat? olan-4-? lo, 1, 2-oxat? Olan-5-? Lo, tetrahydro? Sot? Aol-3-? Lo, tetrahydro? Sot? Aol-4-? Lo, tetrahydro? Sot? Azol-5-? Lo, 1, 2-d? T? Olan-3-? Lo, 1, 2-d? T? Olan-4-? Lo, tetrah? Dro? M? Dazol-2-? Lo, tetrah? Dro? M? Dazol The tetrahydrooxazole, tetrahydrooxazole, tetrahydrooxazole, tetrahydrofolate, tetrahydrofolate, tetrahydrofolate, tetrahydrofolate, 4-? Lo, tetrahydrate, azol-5-? Lo, 1,3-d? Oxolan-2-? Lo, 1,3-d? Oxolan-4-? Lo, 1, 3-oxat? Olan- 2-? Lo, 1, 3-oxat? Olan-4-? Lo, 1, 3-oxat? Olan-5-? Lo, 1, 3-d? T? Olan-2-? Lo, 1, 3- d? t? olan-4-? lo, 1, 3,2-d? oxat? olan-4-? lo Rings saturated with 6 members joined by C as tetrah? drop? ran? 2-? lo, tetrah? drop ? -3???, tetrah? drop? 4-? lo ?, p? pep? n? 2-? it ?, p? pep? n? 3-? it, p? per? d? n-4 -? lo, tetrah? drot? op? ran-2-? lo, tetrah? drot? op? ran-3-? lo, tetrah? drot? op? ran-4-? lo, 1, 3-d? oxan -2-? Lo, 1, 3-d? Oxan-4-? Lo, 1, 3-d? Oxan-5-? Lo, 1, 4-d? Oxan-2-? Lo, 1, 3-d ? t? an? 2-? lo, 1, 3-d? t? an-4-? lo, 1, 3-d? t? an-5-yl, 1, 4-d? t an-2-, 1, 3-oxat? an-2-? lo, 1, 3-oxat? an-4-? lo, 1, 3-oxat? an-5-? lo, 1, 3 -oxat? an-6-? lo, 1, 4-oxat? an-2-? lo, 1, 4-oxat? an-3-? lo, 1, 2-d? t? an-3-? lo , 1, 2-d? T? An-4-? Lo, hexah? Drop? R? M? D? N-2-? Lo, hexah? Drop? R? M? D? N? 4-? Lo, hexah? drop? r? m? d? n? 5-?, hexah? drop? raz? n? 2-? it, hexah? drop? r? daz? n? 3-? it, hexah? drop? r ? daz? n-4-? lo, tetrah? dro-1, 3-oxaz? n-2-? lo, tetrah? dro-1, 3-oxaz? n-4-? lo, tetrah? dro-1, 3-oxaz? N-5-? Lo, tetrahydro-1, 3-oxaz? N-6? Lo, tetrah? Dro-1, 3-t? Az? N-2-yl, tetrahydro-1, 3-t? az? n-4-? lo, tetrahydro-1, 3-t? az? n-5-? lo, tetrah? dro-1, 3-t? az ? n-6? lo, tetrahydro-1, 4-t? az? n-2-? lo, tetrah? dro-1, 4-t? az? n-3-? lo, tetrah? dro- 1, 4-oxaz? N-2-? Lo, tetrahydro- 1, 4-oxaz? N-3-? Lo, tetrahydro-1, 2-oxaz? N-3-? Lo, tetrah? Dro-1 , 2-oxaz? N-4-? Lo, tetrah? Dro-1, 2-oxaz? N-5-? Lo, tetrah? Dro-1, 2-oxaz? N-6-? O Rings saturated of 5 members N-linked tetrahydro-tetrahydroimidazole, tetrahydroimidazole, tetrahydroimidazole, tetrahydroimidazole, tetrahydroimidazole, tetrahydroimidazole, tetrahydroimidazole, tetrahydroimidazole, tetrahydroimidazole, tetrahydroimidazole, tetrahydroimidazole, tetrahydroimidazole, tetrahydroimidazole, tetrahydroimidazole. - 1 -yl, tetrahydrooxazole-3-? Lo, tetrahydroth? Azole-3-? O Rings saturated with 6 members joined by N as P? Pepd? N-1?, Hexah? Drop? Pm? d? n-1-? lo, hexah? drop? raz? n-1 -? lo, hexah? dro-p? pdaz? n-1 -? lo, tetrah? dro-1, 3- oxaz? n-3 -? lo, tetrah? dro-1, 3-t? az? n-3-? lo, tetrah? dro-1, 4-t? az? n-4-? lo, tetrah? dro-1, 4- oxaz? n-4-? lo, tetrah? dro-1, 2-oxaz? n-2-? lo Partially unsaturated rings of 5 members bound by C as 2,3-d? h? drofuran-2-? lo, 2,3-d? H? Drofuran-3-? Lo, 2,5-d? H? Drofuran-2-? Lo 2.5-d? - h? drofuran-3-? lo, 4,5-d? h? drofuran-2-? lo, 4,5-d? h? drofuran-3-? lo, 2,3-d? h? dro? t ? in-2-? lo, 2,3-d? h? drot? in-3-? lo, 2,5-d? h? drot? in-2-? lo, 2,5-d? h? drot? en-3-? lo, 4,5-d? h? drot? en-2-? lo, 4,5-d? h? drot? en-3-? lo, 2,3-d? h 1-Hydro-2-, 2,3-d-hydro-1-Hydro-3-, 2,5-d-hydro-1-2-2-1 It, 2,5-d? h? dro-1 Hp? rrol-3-yl, 4,5-d? h? dro-1 Hp? rrol-2-? lo, 4,5-d? h? dro-1 Hp? rrol-3-? lo, 3,4-d? h? dro-2H-p? rrol-2-? lo, 3,4-
d? h? dro-2H-p? rrol-3-? lo, 3,4-d? h? dro-5H-p? rrol-2-? lo, 3,4-d? h? dro-5H- pyrrol-3-? lo, 4,5-d? h? dro-1 Hp? razol-3-? lo, 4,5-d? h? dro-1 Hp? razol-4-? lo, 4 , 5-d? H? Dro-1 Hp? Razol-5-? Lo, 2,5-d? H? Dro-1 Hp? Razol-3-? Lo, 2,5-d? H? Dro-1 Hp? Razol-4-? Lo, 2,5-d? H? Dro-1 Hp? Razol-5-? Lo, 4,5-d? H? Dro? Soxazol-3-yl, 4,5-d Soxazol-4-? lo, 4,5-d? h? d? soxazol-5-? lo, 2,5-d? h? dro? soxazol-3-? lo, 2.5-? d? h? dro? soxazol-4-? lo, 2,5-d? h? dro? soxazol-5-? lo, 2,3-d? h? dro? soxazol-3-? lo, 2,3 -d? h? dro? soxazol-4-? lo, 2,3-d? h? dro? soxazol-5-? lo, 4,5-d? h? dro? sot? azol-3-? lo, 4,5-d? H? Dro? Sot? Azol-4-? Lo, 4,5-d? H? Dro? Sot? Azol-5-? Lo, 2,5-d? H? Dro? Sot? azol-3-? lo, 2,5-d? h? dro? sot? azol-4-? lo, 2,5-d? h? dro? sot? azol-5-? lo, 2,3-d H? dro? s? azol-3-? lo, 2,3-d? h? dro? s? azol-4-? lo, 2,3-d? h? dro? sot? azol-5-? what,? 3-1, 2-d? t? ol-3-? lo,? 3-1, 2-d? t? ol-4-? lo,? 3-1, 2-d? t? ol -5-? Lo, 4,5-d? H? Dro-1 H-? M? Dazol-2-? Lo, 4,5-d? H? Dro-1 H-? M? Dazol-4-? it, 4,5-d? h? dro-1 H-? m? dazol-5-? lo, 2,5-d? h? dro-1 H-? m? dazol-2-? lo, 2, 5-d? H? Dro-1 H-? M? Dazol-4-? Lo, 2,5-d? H? Dr o-1 H-? m? dazol-5-? lo, 2,3-d? h? dro-1 H-? m? dazol-2-? lo, 2,3-d? h? dro-1 H -? m? dazol-4-? lo, 4,5-d? h? dro-oxazol-2-? lo, 4,5-d? h? drooxazol-4-? lo, 4,5-d? h Drooxazole-5-? lo, 2,5-d? -hydro-oxazol-2-? lo, 2,5-d? h? droxazole-4-? lo, 2,5-d? h? drooxazol- 5-? Lo, 2,3-d? H? Dro-oxazol-2-? Lo, 2,3-d? H? Drooxazol-4-? Lo, 2,3-d? H? Drooxazol-5-? it, 4,5-d? h? dro-t? azol-2-? lo, 4,5-d? h? drot? azol-4-? lo, 4,5-d? h? dr? otol? 5-? Lo, 2,5-d? H? Dro-t? Azol-2-? Lo, 2,5-d? H? Drot? Azol-4-? Lo, 2,5-d? H? Drot azol-5-? lo, 2,3-d? h? dro-t? azol-2-? lo, 2,3-d? h? drot? azol-4-? lo, 2,3-d? hydroxyl-5-? lo, 1,3-d? oxol-2-? lo, 1,3-d? oxol-4-? lo, 1,3-d? t? ol-2-yl , 1, 3-d? T? Ol-4-? Lo, 1, 3-oxat? Ol-2-? Lo, 1, 3-oxat? Ol-4-? Lo, 1, 3-oxat? Ol- 5-?, 1, 2,3-? 2-oxad? Azole-4-? Lo, 1, 2,3-? 2-oxad? Azole-5-? Lo, 1, 2,4 -? 4-Oxad? Azole-3-? Lo, 1, 2,4-? 4-oxad? Azole-5-? Lo, 1, 2,4-? 2-oxad? Azole? 3-1, 1, 2,4-? 2-oxad? Azole-5-? Lo, 1, 2,4-? 3-oxad? Azole-3-? Lo, 1, 2,4 -? 3-oxa-d? Azole-5-? Lo, 1, 3,4-? 2-oxad? Aolol-n-2?, 1, 3,4-? 2-oxad? Azole? n-5-? lo, 1, 3,4-? 3-oxad? azole-2-yl, 1, 3,4-oxad? Azole-2-? Lo, 1, 2,4-? 4-t? Ad? Aolol-n-3-? Lo, 1, 2,4-? 4-t? ad-azole-5-? lo, 1, 2,4-? 3- t? ad? azole-3-? lo, 1, 2,4-? 3-t? ad? azole? n- 5-1, 1, 2,4-? 2-t? Ad? Azole-3-? Lo, 1, 2,4-? 2-t? Ad? Azole-5-yl, 1, 3,4-? 2-t? Ad? Aolol-n-2-? Lo, 1, 3,4-? 2-t? Ad? Aolol? N-5-? Lo, 1, 3,4-? 3 -t? ad? azol? n-2-? lo, 1, 3,4-t? ad? azol? n-2-? lo, 1, 2,3-? 2-tpazol? n-4-? lo , 1, 2,3-? 2-tr? Azole-5-? Lo, 1, 2,4-? 2-tr? Azole? -3? -lo, 1, 2,4-? 2- trololone-5, 1, 2,4-? 3-tpazol? n-3-? lo, 1, 2,4-? 3-tr? azol? n-5-? lo, 1 , 2,4-? 1-tpazol? N-2-? Lo, 1, 2,4-tr? Azol? N-3-? Lo, 3H-1, 2,4-d? T? Azol-5- 1, 2H-1, 3,4-d? t? azol-5? lo, 2H-1, 3,4-oxat? azole-5? o The partially unsaturated rings of 6 members bound by C as 2H- 3.4- d? H? Drop? -6? Lo ?, 2H-3,4-d? H? Drop? 5-? Lo, 2H-3,4-d? H? Drop? Ran-4- It, 2H-3,4-d? h? drop? ran? 3-? lo, 2H-3,4-d? h? drop? 2-? lo, 2H-3,4-d? h ? drot? op? ran-6-? lo, 2H-3,4-d? h? drot? op? ran-5-? lo, 2H-3,4-d? h? drot? op? ran-4 -? lo, 2H-3,4-d? h? drot? op? ran-3-? lo, 2H-3,4-d? h? drot? op? ran-2-? lo, 1, 2, 3,4-tetrah? Drop? R? D? N-6-? Lo, 1, 2,3, 4-tetrah? Drop? R? D? N-5-? Lo, 1, 2,3,4-tetrah? Drop? R? D? N-4-? Lo, 1, 2,3,4-tetra h? drop? r? d? n-3-? lo, 1, 2,3,4-tetrah? drop? r? d? n-2-? lo, 2H-5,6-d? h? drop? ran-2-? lo, 2H-
,6-d? H? Drop? 3-? Lo, 2H-5,6-d? H? Drop? 4-? Lo, 2H-5,6-d? H? Drop? Ran- 5-? Lo, 2H-5,6-d? H? Drop? Ran-6? Lo, 2H-5,6-d? H? Drot? Op? Ran-2-? Lo, 2H-5,6 -d? h? dro? t? op? ran? 3-? lo, 2H-5,6-d? h? drot? op? ran-4-? lo, 2H-5,6-d? h? drot ? op? ran-5-? lo, 2H-5,6-d? h? drot? op? ran-6-? lo, 1, 2,5,6-tetrah? drop? pd? n-2-? what, 1, 2,5,6-tetrah? drop? pd? n-3-? lo, 1, 2,5,6-tetrah? drop? pd? n-4-? lo, 1, 2,5, 6-tetrahydro-p? R? D? N-5-? Lo, 1, 2,5,6-tetrah? Drop? R? D? N-6-? Lo, 2,3,4,5- tetrah? drop? r? d? n-2-? lo, 2,3,4,5-tetrah? drop? r? d? n-3-? lo, 2,3,4,5-tetrah? drop? r? d? n-4-? lo, 2,3,4,5-tetrah? drop? r? d? n-5-? lo, 2,3,4,5-tetrah? drop? r? d? n-6-? lo, 4H-p? ran-2-? lo, 4H-p? ran -3? lo, 4H-p? ran-4-? lo, 4H-Th? op? ran-2- What, 4H-Th? op? ran-3-? lo, 4H-Th? op? ran? 4-? lo, 1, 4-d? h? drop? r? d? n? 2-? it, 1, 4-d? H? Drop? Pd? N-3-? Lo, 1, 4-d? H? Drop? R? D? N-4-? Lo, 2H-p? Ran-2-? , 2H-p? Ran-3-? Lo, 2H-p? Ran-4-? Lo, 2H-p? Ran-5-? Lo, 2H-p? Ran-6-yl, 2H-Th? Op? Ran? 2-? Lo, 2H-Th? Op? Ran? 3-? Lo, 2H-Th? Op? Ran? 4-? Lo, 2H-Th? Op? Ran-5-? Lo, 2H-Th? Op? Ran-6-? Lo, 1, 2-d? H? Drop? R? D? N-2-? Lo, 1, 2 -d? h? dro-p? r? d? n-3-? lo, 1, 2-d? h? drop? pd? n-4-? lo, 1, 2-d? h? drop? r ? d? n-5-? lo, 1, 2-d? h? dro? p? r? d? n-6-? lo, 3,4-d? h? drop? pd? n-2-? what, 3,4-d? h? drop? r? d? n-3-? lo, 3,4-d? h? dro? p? r? d? n-4-? lo, 3,4- d? h? drop? r? d? n-5-? lo, 3,4-d? h? drop? pd? n-6-? lo, 2,5-d? h? dro-p? pd? n-2-yl, 2,5-d? h? drop? pd? n-3-? lo, 2.5-d? h? drop? r? d? n-4-? lo, 2.5- d? h? dro? p? r? d? n-5-? lo, 2.5-d? h? drop? pd? n-6-? lo, 2,3-d? h? drop? r? d? n-2-? lo, 2,3-d? h? dro-p? pd? n-3-? lo, 2,3-d? h? drop? pd? n-4-? lo, 2 , 3-d? H? Dro-p? R? D? N-5-? Lo, 2,3-d? H? Dro-p? Pd? N-6-? Lo, 2H-5,6-d H? dro-1, 2-oxaz? n-3-? lo, 2H-5,6-d? h? dro-1, 2-oxaz? n-4-? lo, 2H-5,6-d H? dro-1, 2-oxaz? n-5-? lo, 2H-5,6-d? h? dro-1, 2-oxaz? n-6-? lo, 2H-5,6-d H-dro-1, 2-t? az? n-3-? lo, 2H-5,6-d? h? dro-1, 2-t? az? n-4-? lo, 2H-5 , 6-d? H? Dro-1, 2-t? Az? N-5-? Lo, 2H-5,6-d? H? Dro-1, 2-t? Az? N-6-? Lo , 4H-5,6-d? H? Dro-1, 2-oxaz? N-3-? Lo, 4H-5,6-d? H? Dro-1, 2-oxaz? N-4-? Lo , 4H-5,6-d? H? Dro-1, 2-oxaz? N-5-? Lo, 4H-5,6-d? H? Dro-1, 2-oxaz? N-6? Lo, 4H-5,6-d? H? Dro-1, 2-t? Az? N-3-yl, 4H-5,6-d? H? Dro-1, 2-t? Az? N-4-? Lo, 4H-5,6-d? H? Dro -1, 2-t? Az? N-5-? Lo, 4H-5,6-d? H? Dro-1, 2-t? Az? N-6-? Lo, 2H-3,6-d H-dro-1, 2-oxaz? n-3-? lo, 2H-3,6-d? h? dro-1, 2-oxaz? n-4-? lo, 2H-3,6-d Hydro-1, 2-oxaz-n-5-? lo, 2H-3,6-d? -hydro-1, 2-oxaz? n-6-? lo, 2H-3,6-d H? dro-1, 2-t? az? n-3-? lo, 2H-3,6-d? h? dro- 1, 2-t? az? n-4-? lo, 2H-3 , 6-d? -h? Dro-1, 2-t? Az? N-5-? Lo, 2H-3,6-d? H? Dro-1, 2-t? Az? N-6-? it, 2H-3,4- d? h? dro-1, 2-oxaz? n-3-? lo, 2H-3,4-d? h? dro-1, 2-oxaz? n-4-? lo, 2H-3,4-d? H? Dro-1, 2-oxaz? N-5-? Lo, 2H-3,4-d? H? Dro-1, 2-oxaz? N-6-? Lo, 2H-3,4-d? H? Dro-1, 2-t? Az? N-3-? Lo, 2H-3,4-d? H? Dro-1, 2-t? Az? N-4 - ilo, 2H-3,4-d? h? dro-1, 2-t? az? n-5-? lo, 2H-3,4-d? h? dro-1, 2-t? az? n-6-? lo, 2,3,4,5-tetrah? drop? r? daz? n-3-? lo, 2,3,4,5-tetrah? drop? r? daz? n-4- What, 2,3,4,5-tetrah? drop? r? daz? n-5-? lo, 2,3,4,5-tetrah? drop? r? daz? n-6-? lo, 3 , 4,5,6-tetrah? Drop? Pdaz? N-3-? Lo, 3,4,5,6-tetrah? Drop? R? Daz? N- 4-? Lo, 1, 2,5,6 -tetrah? drop? r? daz? n-3-? lo, 1, 2,5,6-tetrah? d rop? pdaz? n-4-? lo, 1, 2,5,6-tetra? h? drop? r? daz? n-5-? lo, 1, 2,5,6-tetrah? drop? r? daz? n-6-? lo, 1, 2,3,6-tetrah? dro-p? r? daz? n-3-? lo, 1, 2,3,6-tetrah? drop? r? daz? n-4-? lo, 4H-5,6-d? -hydro-1, 3-oxaz? n-2-? lo, 4H-5,6-d? h? dro-1, 3-oxaz? n-4-? lo, 4H-5,6-d? h? dro-1, 3-oxaz? n-5-? lo, 4H-5,6-d? h? dro-1, 3-oxaz? n-6-? lo, 4H-5,6-d? h? dro-1, 3-
T? az? n-2-? lo, 4H-5,6-d? h? dro-1, 3-t? az? n-4-? lo, 4H-5,6-d? h? dro- 1, 3-t? Az? N-5? Lo, 4H-5,6-d? H? Dro-1, 3-t? Az? N-6-? Lo, 3,4,5-6- tetrah? drop? r? m? d? n? 2-? lo ?, 3,4,5,6-tetrah? drop? r? m? d? n-4-? lo, 3,4,5,6- tetrah? drop? r? m? d? n? 5-? lo, 3,4,5,6-tetrah? drop? r? m? d? n-6-? lo, 1,2,3,4- tetrah? drop? raz? n-2-? lo, 1, 2,3,4-tetrah? drop? raz? n-5-? lo, 1, 2,3,4-tetrah? dro-p? r? m? d? n-2-? lo, 1, 2,3,4-tetrah? drop? r? m? d? n-4-? lo, 1,2,3,4-tetrah? drop? r? m? d? n-5-? lo, 1,2,3,4-tetrah? drop? r? m? d? n-6-? lo, 2,3-d? h? dro-1, 4- T? az? n-2-? lo, 2,3-d? h? dro-1,4-t? az? n-3-? lo, 2,3-d? h? dro-1,4- T? az? n-5-? lo, 2,3-d? h? dro-1,4-t? az? n-6-? lo, 2H-1,2-oxaz? n-3-? lo , 2H-1,2-oxaz? N-4-? Lo, 2H-1,2-oxaz? N-5-? Lo, 2H-1,2-oxaz? N-6-? Lo, 2H-1.2- T? az? n-3-? lo, 2H-1,2-t? az? n-4-? lo, 2H-1,2-t? az? n-5-? lo, 2H-1, 2 -t? az? n-6? lo, 4H-1,2-oxaz? n-3-? lo, 4H-1,2-oxaz? n-4-? lo, 4H-1,2-oxaz? n-5-? lo, 4H-1,2-oxaz? n-6-? lo, 4H-1,2-t? az? n-3-? lo, 4H-1.2-t? az? n-4 -? lo, 4H-1,2-t? az? n-5-? lo, 4H-1,2-t? az? n-6-? lo, 6H-1,2-oxaz? n-3- It, 6H-1,2-oxaz? n-4-? lo, 6H-1,2-oxaz? n-5-? lo, 6H-1,2-oxaz? n -6-? Lo, 6H-1,2-t? Az? N-3-? Lo, 6H-1, 2-t? Az? N-4-? Lo, 6H-1,2-t? Az? n-5-? lo, 6H-1,2-t? az? n-6-? lo, 2H-1,3-oxaz? n-2-? lo, 2H-1,3-oxaz? n-4 -? lo, 2H-1,3-oxaz? n-5-yl, 2H-1,3-oxaz? n-6? lo, 2H-1,3-t? az? n-2-? lo, 2H-1,3-t? Az? N-4-? Lo, 2H-1,3-t? Az? N-5-? Lo, 2H-1,3-t? Az? N-6-? Lo , 4H-1,3-oxaz? N-2-? Lo, 4H-1,3-oxaz? N-4-? Lo, 4H-1,3-oxaz? N-5-? Lo, 4H-1, 3-oxaz? N-6-yl, 4H-1,3-t? Az? N-2-? Lo, 4H-1,3-t? Az? N-4-? Lo, 4H-1,3- T? az? n-5-? lo, 4H-1,3-t? az? n-6? lo, 6H-1,3-oxaz? n-2-? lo, 6H-1,3-oxaz n-4-? lo, 6H-1,3-oxaz? n-5-? lo, 6H-1,3-oxaz? n-6-? lo, 6H-1,3-t? az? n- 2-yl, 6H-1,3-oxaz? N-4-? Lo, 6H-1,3-oxaz? N-5-? Lo, 6H-1,3-t? Az? N-6-? Lo , 2H-1,4-oxaz? N-2-? Lo, 2H-1,4-oxaz? N-3-? Lo, 2H-1,4-oxaz? N-5-? Lo, 2H-1, 4-oxaz? N-6? Lo, 2H-1,4-t? Az? N-2-? Lo, 2H-1,4-t? Az? N-3-? Lo, 2H-1,4 -t? az? n-5-? lo, 2H-1,4-t? az? n-6-? lo, 4H-1,4-oxaz? n-2-? lo, 4H-1,4- oxaz? n-3-? lo, 4H-1,4-t? az? n-2-? lo, 4H-1,4-t? az? n-3-? lo, 1,4-d? h drop? pdaz? n-3-? lo, 1,4-d? h? drop? r? daz? n-4-? lo, 1,4? d? h? drop? pdaz? n-5-? what, 1, 4-d? h? drop? pdaz? n-6-? lo, 1, 4-d? h? drop? raz? n-2-? lo, 1, 2-d? h? dr op? raz? n-2- ilo, 1,2-d? h? drop? raz? n-3-? lo, 1,2-d? h? drop? raz? n-5-? lo, 1, 2-d? H? Drop? Raz? N-6-? Lo, 1,4? D? H? Drop? R? M? D? N? 2-? Lo, 1,4-d? H? Drop? r? m? d? n-4-? lo, 1,4-d? h? drop? r? m? d? n? 5-? lo, 1,4? d? h? drop? r? m? d? n-6-? lo, 3,4-d? h? drop? r? m? d? n-2-? lo, 3,4-d? h? drop? r? m? d? n- 4-? Lo, 3,4- d? H? Drop? Pm? D? N-5-? Lo 3,4-d? H? Drop? Pm? D? N-6-? Lo Partially unsaturated rings of 5 N-linked members such as 2,3-d? h? dro- 1 Hp? rrol-1-? lo, 2,5-d? h? dro-1 Hp? rrol-1 -lio, 4,5-d? h? dro-1 Hp? razol-1-? lo, 2,5-d? h? dro-1H-p? razol-1 -ilo, 2,3-d? h? dro-1 Hp? razol-1 -yl, 2,5-d? -hydro? -soxazole-2-? lo, 2,3-d? -hydro? -soxazole-2-? lo, 2,5-d? h? d? sot? azole -2-? Lo, 2,3-d? H? Dro? Soxazol-2-? Lo, 4,5-d? H? Dro-1H-? M? Dazol-1-? Lo, 2,5- d H-dro-1H-? m? dazol-1-? lo, 2,3-d? h? dro-1H-? m? dazol-1-? lo, 2,3-d? h? drooxazol-3 -? lo, 2,3- d? h? drot? azole-3-? lo, 1,2,4-? 4-oxad? azole-2-? lo, 1,2,4-? 2- oxad? azole-4-? lo, 1,2,4-? 3-oxad? azole-2-? lo, 1, 3,4-? 2-oxad? azole-4? , 1, 2,4-? 5-t? Ad? Azole-2-yl, 1, 2,4-? 3-t? Ad? Azole-2-yl, 1, 2,4- ? 2-t? Ad? Azol? N-4-? Lo, 1, 3,4-? 2-t? Ad? Aolol-4-? Lo, 1,2,3-? 2-tr? Aolol? N-1-? Lo, 1,2,4-? 2-
trololone-1α, 1, 2,4-? 2-tr? azole-4-? lo, 1, 2,4-? 3-tr? azol? n-1 -? lo , 1, 2,4-? 1-tr? Azol? N-4-? Lo Partially unsaturated rings of 6 members bound by N as 1, 2,3,4-tetrah? Drop? R? D? N-1 - What, 1, 2,5,6-tetrah? drop? r? d? n-1 -? lo, 1, 4-d? h? dro-p? r? d? n-1 -? lo, 1 , 2-d? H? Drop? Pd? N-1-yl, 2H-5,6-d? H? Dro-1, 2-oxaz? N-2-? Lo, 2H-5,6-d? H-dro-1, 2-t? az? n-2-? lo, 2H-3.6-d? h? dro-1, 2-oxaz? n-2-? lo, 2H-3,6-d? H-dro-1, 2-t? az? n-2-? lo, 2H-3,4-d? h? dro-1, 2-oxaz? n-2-? lo, 2H-3,4- d? h? dro-1, 2-t? az? n-2-? lo, 2,3,4,5-tetrah? drop? r? daz? n-2-? lo, 1, 2,5, 6-tetrah? Drop? R? Daz? N-1-? Lo, 1, 2,5,6-tetrah? Drop? Pdaz? N-2-? Lo, 1, 2,3,6-tetrah? Drop? r? daz? n-1 -ilo, 3,4,5,6-tetrah? drop? r? m? d? n-3-? lo, 1, 2,3,4-tetrah? drop? raz? n -1-? Lo, 1, 2,3,4-tetrah? Drop? R? M? D? N-1 -? Lo, 1, 2,3,4-tetrah? Drop? Pm? D? N-3 -? lo, 2,3-d? hdro-1, 4-t? az? n-4-? lo, 2H-1, 2-oxaz? n-2-? lo, 2H-1, 2-t? az? n-2-? lo, 4H-1, 4-oxaz? n-4-? lo, 4H-1, 4-t? az? n-4-? lo, 1, 4-d? h? drop ? r? daz? n-1 -? lo, 1, 4-d? h? drop? raz? n-1 -? lo, 1, 2-d? H? Drop? Raz? N-1-? Lo, 1, 4-d? H? Drop? R? M? D? N-1 -? Lo 3,4-d? H? drop? r? m? d? n-3-? Heteroaromatic rings of 5 members joined by C with usually 1, 2, 3 or 4 nitrogen atoms or a heteroatom selected from oxygen and sulfur and, if appropriate, 1 , 2 or 3 nitrogen atoms as cyclic members such as 2-furol, 3-furol, 2-t? In? Lo, 3-t? In? Lo, p? Rrol-2-? Lo, p? Root-3-? lo, raz-3-? lo, raz-4-? lo,? soxazol-3-? lo,? soxazol-4-? lo,? soxazol-5-? lo,? sot-azole-3-? lo,? sot-azole-4-? lo,? sot-azole-5-? lo,? m? dazol-2-? lo,? m? dazol-4-? lo, oxazole -2-? Lo, oxazole-4-? Lo, oxazole-5? Lo, t? Azole-2-? Lo, t? Azole-4-? Lo, t? Azole-5-? Lo, 1, 2 , 3-oxad? Azole-4-? Lo, 1, 2,3-oxad? Azole-5-? Lo, 1, 2,4-oxad? Azole-3-? Lo, 1, 2,4, -oxad Azole-5-? lo, 1, 3,4-oxad? azole-2-yl, 1, 2,3-t? ad? azole-4-? lo, 1, 2,3-t? ad? azole -5-? Lo, 1, 2,4-t? Ad? Azole-3-? Lo, 1, 2,4-t? Ad? Azole-5-? Lo, 1, 3,4-t? Ad? azole-2?, 1, 2,3-tr? azole-4-? lo, 1, 2,4-tr? azole-3-? lo, tetrazole-5-? lo 6-membered heteroaromatic rings joined by C with usually 1, 2, 3 or 4 nitrogen atoms as cyclic members such as p? r? d? n-2-? lo, p? r? d? n-3-? lo, p? pd? n-4 - what, why, what will you do, what will you do, what will you do, what will you do, what will you do, what will you do? d? n-4-? lo, p? r? m? d? n-5-? lo, p? raz? n-2-? lo, 1, 3,5-tr? az? n-2- It, 1, 2,4-tr? az? n-3-? lo, 1, 2,4-tr? az? n-5-? lo, 1, 2,4-tpaz? n-6-? 1, 2,4,5-tetraz? n-3-yl 5-membered heteroaromatic rings attached by N with generally 1, 2, 3 or 4 nitrogen atoms as cyclic members such as pyrrol-1? lo, p? razol-1-? lo,? m? dazol-1-yl, 1, 2,3-tpazol-1-? lo, 1, 2,4-tpazol-1-? lo, tetrazol-1 - or a bicyclic heterocycle, which has one of the previously indicated 5- or 6-membered heterocyclic rings and another saturated, saturated, aromatic, saturated carbocycle, for example a benzene, cyclohexane, cyclohexene or cyclohexadiene ring or other heterocyclic ring 5 or 6 members joined by condensation, where the latter can also be saturated, unsaturated or aromatic
A sulfur atom in the aforementioned heterocycles can be oxidized to S = O or S (= O) 2 Correspondingly, heptaplo or heterolalk substitute a 5 or 6 membered heteroaromatic moiety, which has 1, 2, 3 or 4 heteroatoms equal or different, selected from the group oxygen, sulfur or nitrogen, as cyclic members, which can be linked through C or N and which can form with another ring benzene bound by condensation or with another heteroaromatic of 5 to 6 members a system of bicyclic ring Examples of hetanlo are the aforementioned heteroaromatic rings linked by C, the aforementioned heteroaromatic rings bonded by C, the 5-membered heteroaromatic rings and the bicyclic heteroaromatic moieties such as quinolinyl, iso-nyl, quinazolinyl, quinoxahnil, indolyl, benzothienyl, benzofupl , benzoxazole, benzthiazole, benzimidazolyl, benzpyrazole, benzothipazole, indolizmile, 1,4-tr? azolo [1,5-a] p? r? m? d? n ?, 1, 2,4-tr? azolo [4.3-a] p? R? d? n? lo, p? razolo [3,4-b] p? r? d? n? lo, 1, 2,4-tpazolo [1, 5-a] p? pd? n? lo,? m ? dazo [1, 2-a] p? r? d? lo,? m? dazo [3,4-a] p? r? m? d? n? lo, and similar Aplo mono or polynuclear aromatic carbocycle, p eg, mono- or dinuclear aromatic carbocycle or a tpnuclear aromatic carbocycle with 6 to 14 ring members, such as, for example, phenyl, naphthyl or anthracenyl Aplakyl an attached residue through an alkylene group, especially through a methylene group, , 1-ethylene or 1, 2-ethylene, eg benzyl, 1-phenol and 2-phenylethyl Heterocyclylalkyl as well as hetaplakyl, a heterocyclyl or hetaplo group linked through an alkylene group, especially at Through a methylene, 1, 1-ethylene or 1, 2-ethylene group In a special embodiment, variables of the compounds of formula I have the following meanings, where these, whether considered by themselves or combined with each other, represent special conformations of the compounds of formula I R1 is hydrogen, amino, cyano, CC alkenyl alkyl CC alkynyl phenyl alkyl (CC), heterocyclyl-alkyl (C) or COR21, where R21 has the meanings mentioned above and especially substitutes CC alkyl alkoxy phenyl, phenylamino or heterocyclic, wherein the parts The aforementioned cyclic, aromatic or aromatic substituents of the substituents may be partially or fully halogenated. Particularly preferably, R 1 has the meanings hydrogen or alkyl.
CC especially methyl R2 is amino, cyano, CC alkenyl C3-C6 alkynyl alkyl, phenyl-alkyl (CC), heterocyclyl-alkyl (CrC6) or COR21, where R2 the meanings mentioned above and especially substituted CC alkoxy CC phenyl, phenylamino or heterocyclyl, where the aforementioned fatic, cyclic or aromatic parts of the substituents may be partially or fully halogenated. Particularly preferably, R2 has the meaning CC alkyl especially methyl R3 is a radical R26 or an OR27 group, where R 26 and R 27 have the meanings previously indicated and especially independently of each other signify hydrogen, CC alkyl alkylcarbonyl, CC phenyl-CC alkyl or phenylcarbonyl, where the mentioned aromatic or aliphatic portions of the substituents may be partially or fully halogenated, or mean S02R31, wherein R3 means CC alkyl or phenyl, and wherein the phenyl substituent on R31 may be partially or fully halogenated It is possible to carry one or three CC alkyl groups. Especially preferably, R3 has the meanings hydrogen, CCalkyl? -alkoxy? -CC6 or alkylsulfonyl CC R4, R5 and / or R6 hydrogen R3 and R4 can also mean together a keto group Preferably, then R5 and / or R6 replace hydrogen R7 and R8 preferably independently of each other meaning hydrogen or methyl, especially hydrogen A1, A2 independently substituting each other for aplo or heterolalk, selected from the group phenyl, naphthyl, fuplo , thienyl, pyrrolyl, pyrazolyl, thiazolyl, isothiazole, oxazolyl, isoxazole, thiazolyl, tetrazolyl, pipdinyl, pipdazinyl, pipmidinyl, pyrazinyl, triazinyl or tetrazinyl, especially selected from the group phenyl, fupyl, thienyl, triazole, tetrazolyl or pipdinyl. Particularly preferred, A1 has the meaning phenyl or pindinyl, especially phenyl. Particularly preferred is A2, meaning phenyl or thienyl, especially phenyl. According to the invention, A1 has one to three substituents Ra, Rb, Rc other than hydrogen, where Ra is attached ortho to the site of binding of A1 to an N atom or a C atom of A1, where Ra preferably has one of the following meanings
halogen, cyano, nitro, C3-C6 cycloalkyl, C2-C6 alkenyl, alkynyl
C2-C6, [Tr? -alk? L- (CrC6) -s? L? L] -alk? N? Lo (C2-C6), alkylthio CC alkylsulfinyl CrC6, aplo, heterocyclyl, especially heterocycly of 5 to 6 members , where aplo and heterocyclic are unsubstituted or may have one or two residues, which were selected from CC alkyl haloalkyl CC alkoxy CC haloalkoxy CC CN, phenyl and halogen, Z1P (O) (OR9) 2, where Z1 means a bond or - CH2- and R9 where appropriate means hydrogen or CC Z3COR11 alkyl, where Z3 signifies a bond and R1 has the meanings previously indicated and especially signifies hydrogen, CC hydroxy alkyl, C3-C6 alkenyloxy CC alkoxy, C3-C6 alkynyloxy, amino , alkylamino CrC6, [di- (C? -C6)] amine, alkoxyamino CrC6, N-alkoxy CCN-alkylamino CrC6, [di- (CrC6) -alcox?] amine, alkylsulfonylamino C C6, alkylamine CrC6 -sulfon? lam? no, [di-alkylamino (CC6)] sulfon? lam? no, phenyl, phenoxy, phenylamino, naphthyl or heterocyclyl, especially heteroaplo of 5 or 6 members joined by C, - Z4NR 2R13, where Z4 s denotes a bond or -CH 2 - and R 2 and R 13 have the meanings mentioned above and in particular independently of each other hydrogen, CC, CC-cycloalkyl, C 3 -C 6 alkenyl, C 6 -C 6 alkylcarbonyl, [di-alkylamino (CC) carbonyl, alkoxycarbonyl CrC6, alkylsulfonyl CrC6, alkylaminosulfonyl CrC6, [di-alkylamino (CrC6)] sulfonyl, C3-C6 cycloalkylcarbonyl, phenylcarbonyl, phenylammocarbonyl, phenylsulfonyl, phenylsulfonylaminocarbonyl or heterocyccarbonyl, especially 5- or 6-membered heteroaphenylcarbonyl with C, Z5CH = NO-R14, where Z5 means a bond and R4 means hydrogen or C6 alkyl, or -Z6OR15, where Z6 means a bond or -CH2- and R15 has the meanings that were previously mentioned and especially may mean C3-C6 alkenyl CC, C3-C6 alkynyl, alkylcarbonyl CrC6, alkoxycarbonyl-CrC6-alkyl (C? -C6) cycloalkyl, d? - (alkoxy? CCcarbon (I)) -alkyl C 6, phenylcarbonyl, phenyl or phenyl-alkyl (CrC 6), R 15 can also mean hydrogen or CC or -Z 7 SO 2 R 16 alkyl, where Z 7 means a bond or CH 2 and R 16 is C 6 alkyl or phenyl, where the mentioned aforementioned cyclic, aromatic or aromatic portions of the substituents Ra can be halogenated in partial or total form Rb, Rc, Rd, Re and Rf preferably replace hydrogen or have
independently of each other a meaning that is indicated as preferential for Ra. As long as Ra is attached to a nitrogen atom, Ra is preferably other than halogen, alkylthio CC alkylsulfinyl CC Z1P (0) (OR9) 2, where Z1 represents a bond A preferred embodiment of the invention, Ra is attached to a C atom. In particular, Ra has one of the following meanings halogen, cyano, nitro, alkylthio, CC, alkylsulfmyl, CC, heterocyclyl, where the two residues mentioned in the last term are not substituted or may have one or two moieties that were selected from CC alkyl haloalkyl CC alkoxy CC haloalkoxy CrC4, CN, phenyl and halogen, -C2-C6 alkenyl, C2-C6 alkynyl, Z1P (O) (OR9) 2, where Z1 means a bond or -CH2- and R9 where appropriate means hydrogen or C, or Z3COR11 alkyl, where Z3 means a bond and R11 means hydrogen, CC hydroxy alkyl, CrC6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, amino, alkylamino CrC6, [di-a alkyl (CrC6)] amine, alkoxyamino CrC6, N-alkoxy C C6-N-alkylamine C Ce, alkylsulfonylamino C? -C6, alkylamino CrC6-sulfon? lam? no, [di-alkylamino (C C6 )] sulfonamide, phenyl, phenoxy, phenylamino, naphthyl or heterocyclyl, in particular 5 or 6 membered heterolayl bonded with C, or Z4NR12R13, where Z4 means a bond or -CH2- and R12 and R13 independently of each other mean hydrogen, C3-C6 cycloalkyl, C3-C6 alkenyl, C3-C6 alkenyl, CrC6 alkylcarbonyl, [di-alkylamino (CrC6)] carbonyl, C6 alkoxycarbonyl, CrC6 alkylsulfonyl, phenylcarbonyl, phenylsulfonyl, or heterocyclylcarbonyl, especially 5- or 6-membered heterocarbonyl bonded with C, o -Z5CH = NO-R14, where Z5 means a bond and R4 means hydrogen or C6 alkyl, or Z6OR15, where Z6 means a bond or -CH2- and R15 is hydrogen, CrC6 alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl, alkynyl CC alkylcarbonyl C Ce, alkoxycarbonyl-CrC6-alkyl (CrC6), phenyl or phenyl-alkyl (CrC6), or - Z7SO2R16, where Z7 means a bond or CH2 and R16 is CrC6 alkyl or phenyl, and where the mentioned aliphatic, cyclic or aromatic moieties of the Ra substituents may be partially or fully halogenated. Special preference, Ra substitutes a moiety which is selected from halogen ,
cyano, nitro, C2-C4 alkenyl and C2-C4 alkynyl, NH-C (0) -alkyl CrC6, NH-S (O) 2-alkyl Cr C6 and heteroaryl of 5 members, eg oxazo lo, thiazole, isoxazolyl, isothiazolyl, where the heteroaplo moieties mentioned previously, may present one or two moieties which were selected from CC alkyl haloalkyl CC and halogen and which is especially bound in one of the ortho positions of A1 Rb, Rc, Rd , Re and Rf especially represent hydrogen or independently of each other have a meaning indicated for Ra as being particularly preferred or are substituents of CC haloalkyl CC C3-C6 cycloalkyl, which may be partially or completely halogenated, C2-C6 alkenyl, which it may be partially or completely halogenated, [Tr? -alk? l- (CC) -s? l? l] -alk? n (C2-C6), or a group Z6OR15, where Z6 means a bond and R15 means hydrogen, CC alkyl or haloalkyl In particular, the radicals Rb, Rc, Rd, Re and R1 were independently selected from hydrogen , halogen, CC alkenyl alkyl C2-C4 alkynyl, alkoxy CC haloalkyl CrC4 and haloalkoxy CC where two groups Rb, Rc, Rd, Re or Rf linked to adjacent C atoms A1 or A2, can also be substituents of a group 0-CH2 -O In particular, Rb is a non-hydrogen moiety. Preferably, R is a moiety joined in one of the ortho positions of A1, ie, when Ra is also attached in the ortho position, Rb is in the second ortho position While one or both of the radicals Rb, Rc are equivalent to a different substituent of hydrogen, the following were selected especially among the substituents indicated as being preferred, and especially halogen, CCalkoxyalkyl-haloalkyl-CCalkenyl-C2-C4alkynyl-C2-C4alkyl or haloalkoxy-CCalkyl or Rb and Rc together correspond to a group O-CH2-O In particular, A2 is unsubstituted or is one or two of the substituents Rd, Re or Rf equals a substituent other than hydrogen On either 1 or 2 of the substituents Rd, Re and Rf are different of hydrogen, are selected especially from halogen, CC alkoxy CC haloalkyl CC and haloalkoxy CC The meaning that a substituent may have within the framework of the invention, is completely independent of the meaning that another substituent may adopt within the framework of the invention. of the invention are the piperazine compounds of general formula I, wherein A1 and A2 are phenyl, R represents methyl and R2 is hydrogen, CrC6 alkyl, C2-C6 alkynyl CC alkenyl, aplo or CC alkoxy, especially hydrogen or
methyl, the substituents R a and R b are independently equivalent to hydrogen, hydroxy, C 2 -C 6 alkenyl CC alkynyl alkyl or C 2 alkoxy, which are arranged on the two phenyl ring ortho positions A1, R 3, R 4, R 5, R 6, R 7, R8 means hydrogen and Rc, Rd, Re and Rf also mean hydrogen. Among them are preferably those compounds, where Ra is substituent of CC alkenyl or C2-C6 alkynyl. Another object of the invention are the piperazm compounds of formula I, which they are different from the compounds of the above-mentioned special object, ie, compounds of the general formula I, with the exception of those compounds of the formula I, wherein R 1 replaces methyl and R 2 is a substituent of hydrogen, C 2 -C 8 alkenyl alkyl C2-C6 alkynyl, aplo or CC alkoxy especially of hydrogen or methyl, the substituents R a and R b independently of each other in each case substitute hydrogen, hydroxy, CC alkyl alkenyl C2-C6 alkynyl or CC alkoxy qu e were disposed in the two ortho positions of the phenyl ring A1, R3, R4, R5, R6, R7, R8 mean hydrogen and RG, Rd, Re and Rf also mean hydrogen Another preferred object of the invention are those compounds of formula I ( S, S), which present S configurations in the identified positions (1) and (2) in each case
Preference is given to compounds of formula I 1, in which R 3, R 4, R 5, R 6, R 7 and R 8 are hydrogen and R 2 is CH 3, particularly preferably compounds (S, S) -I 1, which in the positions identified (1) and (2) in each case have an S configuration. Examples of preferred compounds I 1 are those, wherein A1, Ra, Rb and Rc have the meanings indicated in Table 1
The compounds I 2 to I 252 indicated below are considered by themselves to be preferred embodiments of the invention. Table 1
Also preferred are compounds of formula 12, particularly preferably compounds 121 - I 22922, especially compounds (S, S) - \ 21 - I 22922 which are distinguished from the corresponding compounds 111 - 112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 2-chlorophenol It is also preferred to use the compounds of formula I 3, especially preferred compounds 131-I 32922, especially compounds (S, S) -I 31-I 32922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2R ReRf represents 3-chlorophenol It is also preferred to use the compounds of formula 14, especially preferred compounds 141 - I 42922 especially the compounds (S, S) -I 41 - I 42922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReR (represents 4 chlorinated compounds are also preferably the compounds of formula I 5 of particular preference compounds 151 - I 52922, especially compounds (S, S) - \ 51 - I 52922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-tr? -fluoromethalin? Preferably, the compounds of formula 16 are also particularly preferred compounds 161-I 62922, especially compounds (S, S) -I 61- I 62922 which are distinguished from the corresponding compounds 111 112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 3-tr? Fluoromet? Lf? Also, the compounds of formula 17 are especially preferably compounds 171 - I 72922 especially the compounds (S, S) -I 71 -
I 72922 which are distinguished from the corresponding compounds 111-112922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 4-tpfluoromet? Lfl Also, the compounds of formula I 8 are especially preferred. compounds 181-I 82922 especially compounds (S, S) - \ 81 -I 82922 which are distinguished from the corresponding compounds 111-112922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 2-methox Also preferred are compounds of formula 19, especially preferably compounds 191-I 92922 especially compounds (S, S) - \ 91 -I 92922 which are distinguished from the corresponding compounds 111-112922 or (cf. SS) -I 11 -112922 in which the group A2RdReRf represents 3-methoxyphenol The compounds of formula 110 are also preferred, especially preferably compounds I 10.1-I 10.2922 especially compounds ( S, S) -I 10.1 -I 10.2922 which are distinguished from the corresponding compounds 111 - 112922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 4-methoxyphenol. Preferably also compounds of formula 111 are especially preferred compounds 1111-I 112922 especially compounds (S, S) -I 111 -I 112922 which are distinguished from the corresponding compounds 111-112922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 2-fluorophenone The compounds of formula 112 of the compounds 1121-1122922, especially the compounds (S), are particularly preferred, S) - \ 121 -I 122922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 3-fluorophenone. formula 113 is especially preferred compounds 1131 -1132922 especially compounds (S, S) - \ 131-1132922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 dadurch unterscheiden, dass A2 represents 4-fluorophenol. Preferably, the compounds of formula I 14 are also especially preferred compounds 1141 -1142922 especially compounds (S, S) -I 141 - I 142922 which are distinguished from the corresponding compounds 111-112922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 2-methanol Also preferred are compounds of formula 115, especially preferred compounds 1151-I 152922 especially compounds (S, S ) -I 151 - I 152922 which are distinguished from the corresponding compue these 111 - 112922 or
(S, S) -I 11 -112922 in which the group A2RdReRf represents 3-methanol Also preferably the compounds of formula 116 are especially preferred compounds 1161 -1162922 especially compounds (S, S) -I 161 - I 162922, which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReR 'represents 4-methanol. Likewise, the compounds of formula 117 is especially preferred compounds 1171 -1172922 especially compounds (S, S) -I 171 - I 172922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-chloro-3-methylene. Preferably also compounds of formula 118 are especially preferred compounds 1181 -1182922 especially compounds (S, S) -I 181-I 182922 which are distinguished of the corresponding compounds 111-112922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 2-cl Gold-4-methanol Also preferred are compounds of formula 119, especially preferred compounds 1191-I 192922, especially compounds (S, S) -I 191 -I 192922 which are distinguished from the corresponding compounds 111 112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 2-chloro-5-methylene. Preferably, the compounds of formula I 20 are also preferred, particularly preferably compounds I 20 , 1 - I 20.2922 especially the compounds (S, S) -I 20.1 -I 20.2922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in the that the group A2RdReRf represents 2-chloro-6-methanol It is also preferred to use the compounds of formula I 21, particularly preferably the compounds I 211-I 212922, especially the compounds (S, S) - \ 211 - I 212922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 23-d? Chlorophen? It also are of preferential to the compounds of formula I 22, especially preferably compounds I 221-I 222922, especially compounds (S, S) - \ 221-I 222922 which are distinguished from the corresponding compounds 111-112922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 24-d? Chlorophenol. Preferably, the compounds of formula I 23 are also particularly preferred compounds I 231-I 232922 especially compounds (S, S) - \ 231 - I 232922 which are distinguished from the corresponding compounds 111 -112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 25-d? Chlorophen?
Preference is likewise given to compounds of formula I 24, particularly preferably compounds I 241 - I 242922, especially compounds (S, S) -I 241 -I 242922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 26-d? Chlorophenol It is also preferred to use the compounds of formula I, particularly preferably compounds I 251-I 252922, especially compounds (S, S) -I 251 -I 252922 which are distinguished from the corresponding compounds 111-112922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 2-chloro-3-fluorophenol. Also preferably are the compounds of formula I 26, especially preferably the compounds I 261 - I 262922, especially the compounds (S, S) - \ 261-I 262922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in those which the group A2RdReRf represents 2-chloro-4-fluorophenone are also preferably the compounds of f I 27, particularly preferably compounds I 271-I 272922, especially compounds (S, S) -I 271 -I 272922 which are distinguished from the corresponding compounds 111-112922 or (SS) -I 11 -112922 in the that the group A2RdReRf represents 2-chloro-5-fluorophenone. Preferably, the compounds of formula I 28 are also particularly preferably compounds I 281 - I 282922 especially compounds (S), S) -I 281 -I 282922 which are distinguished from the corresponding compounds 111 -112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 2-chloro-6-fluorophen? Preference is given to compounds of formula I 29, particularly preferably compounds I 291-I 292922, especially compounds (S, S) -I 291-I 292922 which are distinguished from the corresponding compounds 111-112922 or (S, S) - I 11-112922 in which the group A2RdReRf represents 23-d? Fluorophenol The compounds of formula I 30 are also preferred, especially compounds I 30.1-I 30.2922 especially compounds (S, S) -I 30.1-I 30.2922 which are distinguished from the corresponding compounds 111 -112922 or (SS) -I 11 -112922 in which the group A2RdReR 'represents 24-d? Fluorophen? Preference is given to compounds of formula I 31, especially preferably compounds I 311 - I 312922, especially compounds (S, S) - 311 - I 312922, which are distinguished from Corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 25-d? fluorophenone. Also preferably are the compounds of formula I 32 of special
Preference is given to compounds I 321 - I 322922, in particular compounds (S, S) - 321 - I 322922, which are distinguished from the corresponding compounds 111 - 112922 or (SS) - I 11 -112922 in which the group A2RdReRf represents 26-d? Fluorophenol The compounds of formula I 33 are also preferably of particular preference the compounds I 331 - I 332922 especially the compounds (S, S) -? 331 - I 332922 which are distinguished from the corresponding compounds 111 - 112922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 2-fluoro-3-chlorophenol. Preferably, the compounds of formula I 34 are also particularly preferably compounds I 341 - I 342922 in particular the compounds (S, S) -I 341 -I 342922 which are distinguished from the corresponding compounds 111 -112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 2-fluoro-4-chlorophen? Preferably, the compounds of formula I are also particularly preferably compounds I 351 - I 352922 in especially the compounds (S, S) - \ 351-I 352922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 2-fluoro-5-chlorophen Preferably, the compounds of formula I 36 are also particularly preferably compounds I 361 - I 362922, especially compounds (S, S) -I 361 -I 362922 which are distinguished from the corresponding compounds 111-112922 or (cf. S, S) -I 11 -112922 in which the group A2RdReRf represents 34-d? Fluorophenol It is also preferred to use the compounds of formula I 37, particularly preferably compounds I 371-I 372922, especially compounds (S, S) -I 371 - I 372922 which are distinguished from the corresponding compounds 111 -112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 35-d? Fluorophen? of formula I 38, especially preferred compounds I 381 - I 382922 especially compounds (S, S) -I 381 - I 382922 qu e are distinguished from the corresponding compounds 111 -112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 34-d? chlorophenol It is also preferred to use the compounds of formula I 39, especially preferred compounds I 391 - I 392922, in particular the compounds (S, S) -I 391 - I 392922 which are distinguished from the corresponding compounds 111 -112922 or (S, S) -I 11-112922 in which the group A2RdReR ' It also represents preferably compounds of formula 140, especially preferably compounds I 40.1-I 40.2922 especially compounds (S, S) -I 40.1-
I 40,2922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 3-fluoro-4-chlorophenol. Also preferably are the compounds of formula 141 particularly preferred are compounds I 411-I 412922, especially compounds (S, S) -I 411 -I 412922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in the that the group A2RdReRf represents 4-fluoro-3-chlorophenol. Preferably, the compounds of formula 142 are also particularly preferred compounds I 421 - I 422922 especially compounds (S, S) -I 421 -I 422922 which are distinguish from the corresponding compounds 111-112922 or (SS) -I 11 -112922 in which the group A2R ReR (represents 3-fluoro-5-chlorophenol) are also preferably compounds of formula 143 of special preference the compounds I 431 - I 432922 in particular the compounds (S, S) - \ 431-I 432922 which are distinguished from the corresp Compound Nos. 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents p? pd? n-2-? lo Likewise, the compounds of formula 144 are especially preferably compounds I 441 - I 442922 especially the compounds (S, S) -I 441 -I 442922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 3-chlorop Also, preferably compounds of formula 145 are especially preferred compounds I 451 - I 452922, especially compounds (S)., S) -I 451 -I 452922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 4-chlorop? Pd? N-2-? Preference is likewise given to compounds of formula 146, especially preferred compounds I 461 - I 462922, especially compounds (S, S) -I 461 - I 462922 which are distinguished from the corresponding compounds 111-112922 or (SS) - I 11 -112922 in which the group A2R ReRf represents 5-chlorop? R? D? N-2-? E Likewise preferably the compounds of formula 147 are especially preferred compounds I 471 - I 472922 especially compounds ( S, S) -I 471 - I 472922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 6-chlorop? R? D? N-2 Preferably, the compounds of formula 148 are also particularly preferred compounds I 481 - I 482922, especially compounds (S, S) - \ 481 - I 482922 which are distinguished from the compounds Composite sponsors 111 - 112922 or
(SS) -I 11-112922 in which the group A2RdReRf represents 3-tpfluoromet? Lp? R? D? N-2-? Lo Likewise preferably the compounds of formula 149 are especially preferred compounds I 491 - I 492922 especially the compounds (S, S) - \ 491-I 492922 which are distinguished from the corresponding compounds 111-112922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 4-tr? fluoromet? lp? Also preferably are the compounds of formula I 50, especially preferably compounds I 50.1 - I 50.2922 especially compounds (S, S) - \ 50.1 - I 50,2922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 5-tr? Fluoromet? Lp? Pd? N-2-? Preferably, the compounds of formula 151 are particularly preferably compounds I 511-I 512922, especially compounds (S, S) - 5 511 -I 512922 which are distinguished from the corresponding compounds 111-112922 or (SS) -I 11 -112922 in which the group A2R R8Rf represents 6-tr? fluoromet? lp? pd? n-2-? lo Also preferred are compounds of formula I 52, particularly preferably compounds I 521 - I 522922 especially compounds (S) , S) -I 521 -I 522922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 3-methox? P? R? D? N- 2- Also preferred are compounds of formula I 53, especially preferably compounds I 531 - I 532922, especially compounds (S, S) -I 531 - I 532922 which are distinguished from corresponding compounds 111-112922 or well (S, S) -I 11 -112922 in which the group A2RdReRf represents 4-methox? p? r? d? n-2-? It is also preferred to use the compounds of formula I 54, particularly preferably compounds I 541 - I 542922 especially the compounds (S, S) -I 541 - I 542922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represses It is also preferred to use compounds of formula I 55, especially compounds I 551 - I 552922, especially compounds (S, S) -I 551- I 552922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 6-methox? P? Pd? N-2-? It is also preferably the compounds of formula I 56, especially preferably compounds I 561 - I 562922 especially compounds (S, S) -I 561 - I 562922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 3-fluorop? R? D? N-2-?
Preference is likewise given to compounds of formula I 57, especially preferably compounds I 571-I 572922, especially compounds (S, S) -I 571-I 572922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReR (represents 4-fluorop? Pd? N-2-? E Likewise preferably the compounds of formula I 58 are especially preferred compounds I 581 - I 582922 especially those compounds (S, S) -I 581 -I 582922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 5-fluorop? pd? n-2 Also preferred are compounds of formula I 59, especially preferably compounds I 591 - I 592922, especially compounds (S, S) - \ 591-I 592922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 6-fluorop? Pd? N-2-? Lo Likewise, the compounds of formula I 60, especially preferred compounds I 60.1 - I 60.2922 especially compounds (S, S) - \ 60.1 -I 60.2922 which are distinguished from the corresponding compounds 111-112922 or ( S, S) -I 11 -112922 in which the group A2RdReRf represents p? Pd? N-3-? Lo Likewise, the compounds of formula I 61 are especially preferred, especially compounds I 611 - I 612922 especially compounds (S, S) - I-612922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 2-chloropr? R? D? N-3- Preferably, the compounds of formula I 62 are also particularly preferably compounds I 621-I 622922 especially compounds (S, S) -I 621-I 622922 which are distinguished from the corresponding compounds 111-112922 or ( S, S) -I 11 -112922 in which the group A2RdReR (represents 4-chlorop? R? D? N-3-? E Likewise preferably the compounds of formula I 63 are especially preferred compounds I 631 - I 632922 especially the compounds (S, S) -I 631- I 632922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 5-chloropyr Also preferred are compounds of formula I 64, particularly preferably compounds I 641 - I 642922, especially compounds (S, S) -I 641 - I 642922 which are distinguished from corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RReRf represents 6-chlorop? r? d? n-3-? lo. Also preferably are the compounds of formula I 65 of special
Preference is given to the compounds I 651 - I 652922, in particular the compounds (S, S) -I 651-I 652922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in which the group ARdReRf represents 2-tr? Fluoromet? Lp? R? D? N-3-? Lo. Preferably also compounds of formula I 66 are especially preferred compounds I 661 - I 662922 especially compounds (S, S) - I 661-I 662922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RReRf represents 4-tr? Fluoromet? Lp? R? D? N -3 Preferably, the compounds of formula I 67 are also particularly preferably compounds I 671-I 672922 especially compounds (S, S) -I 671 -I 672922 which are distinguished from the corresponding compounds 111-112922 or ( S, S) -I 11 -112922 in which the group A2RdReRf represents 5-tr? Fluoromet? Lp? R? D? N-3-? Lo Likewise, the compounds of formula I 68 are especially preferred; these I 681 - I 682922 especially the compounds (S, S) - \ 681-I 682922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 6-tpfluoromet? Lp? R? D? N-3-? Lo Preferably also compounds of formula I 69 are especially preferred compounds I 691 - I 692922 especially compounds (S, S) -I 691 -I 692922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 2-methox? P? Pd? N-3-? Lo Likewise the compounds are preferably of formula I 70, especially preferably compounds I 70.1-I 70.2922 especially compounds (S, S) - \ 70.1-I 70.2922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 4-methox? P? Pd? N-3-? E Also preferably the compounds of formula I 71 are especially preferred compounds I 711 - I 712922 in spice l the compounds (S, S) - \ 711 - I 712922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 5-methox? p? pd Also preferred are compounds of formula I 72, particularly preferably compounds I 721 - I 722922, especially compounds (S, S) -I 721 - I 722922 which are distinguished from corresponding compounds 111 112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 6-methox? P? Pd? N-3-? The compounds of formula I 73 are also preferably the compounds of special preference. I 731 - I 732922 especially compounds (S, S) -I 731 -
I 732922 which are distinguished from the corresponding compounds 111-112922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 2-fluorop? R? D? N-3-? It is also preferably the compounds of formula I 74, particularly preferably compounds I 741 - I 742922, especially compounds (S, S) -I 741 -I 742922, which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 wherein the group A2RdReRf represents 4-fluorop? pd? n-3-? e Also preferred are compounds of formula I 75, especially preferably compounds I 751 - I 752922 especially compounds (S, S) -? 751 -I 752922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 5-fluorop? Pd? N -3? compounds of formula I 76, especially preferred compounds I 761 - I 762922, especially compounds (S, S) - \ 761-I 762922, which are distinguished from those corresponding to Compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 6-fluorop? r? d? n-3-? i In addition, the compounds of formula I 77 are especially preferred. Preference is given to the compounds I 771-I 772922, in particular the compounds (S, S) -I 771 -I 772922 which are distinguished from the corresponding compounds 111 -112922 or (SS) -I 11 -112922 in which the group A2RdReRf represents Also, preference is given to compounds of formula I 78, particularly preferably compounds I 781-I 782922, especially compounds (S)., S) -I 781- I 782922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-fluorop? Pd? N-4-? Also preferred are compounds of formula I 79, especially preferably compounds I 791 - I 792922, especially compounds (S, S) -I 791 - I 792922, which are distinguished from the corresponding compounds 111-112922 or (SS) -I 11-112922 in which the group A2RdReRf represents 3-fluorop? R? D? N-4-? Lo Also preferably are the compounds of formula I 80, especially preferably compounds I 80.1-I 80, 2922 especially the compounds (S, S) -I 80.1-I 80.2922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2 The compounds of formula I 81 are also preferred, especially compounds I 811 - I 812922, especially compounds (S, S) - 811 - I 812922 which are distinguish from corresponding compounds 111-112922 or
(S, S) -I 11 -112922 in which the group A2RdReRf represents 3-methox? P? Pd? N-4-? Lo Likewise, the compounds of formula I 82 are especially preferably compounds I 821-I 822922 especially the compounds (S, S) - \ 821-I 822922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 2-tpfluoromet? Lp Also preferred are compounds of formula I 83, especially preferably compounds I 831 - I 832922, especially compounds (S, S) - I 831 - I 832922, which are distinguished from the corresponding compounds compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 3-tpfluoromet? lp? pd? n-4-? lo Likewise preferably the compounds of formula I 84 are especially preferred the compounds I 841 - I 842922 especially the compounds (S, S) -I 841 -I 842922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 2-chloropr? d? n-4-? lo Also preferably compounds of formula I 85 are especially preferred compounds I 851 - I 852922 especially compounds (S, S) -I 851- I 852922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 3-chlorop? Pd? N-4-? formula I 86, especially preferred are compounds I 861 - I 862922 especially compounds (S, S) - \ 861 -I 862922 which are distinguished from the corresponding compounds 111-112922 or (SS) -I 11 -112922 in the that the group A2RdReRf represents t-ofen-2-yle. Preferably also compounds of formula I 87 are especially preferred compounds I 871-I 872922 especially compounds (S, S) -I 871-I 872922 which are distinguish from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 3-chlorot? ofen-2-? Preferably, the compounds of formula I 88 are especially preferred compounds I 881-I 882922 especially compounds (S, S) - 881-I 882922 which are distinguished from the corresponding compounds 111-112922 or (SS) - I 11 -112922 in which the group A2RdReRf represents 4-chlorot? Ofen-2-yl The compounds of formula I 89 are also preferably of special preference the compounds I 891-I 892922 especially the compounds (S, S) -I 891- I 892922 which are distinguished from the corresponding compounds 111-112922 or (SS) -I 11-112922 in which the group A2RdReRf represents 5-chlorot? Ofen-2-?
Preference is likewise given to compounds of formula I 90, particularly preferably compounds I 90.1-I 90.2922, especially compounds (S, S) -I 90.1 -I 90.2922 which are distinguished from the corresponding compounds compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 3-tr? fluoromet? lt? ofen-2-? lo. Preferably also compounds of formula I 91 are especially preferred. the compounds I 911 - I 912922 especially the compounds (S, S) -I 911 -I 912922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 4-tr? -fluoromet? lt? ofen-2-yl Also preferred are compounds of formula I 92, especially preferably compounds I 921-I 922922 especially compounds (S, S) - \ 921-I 922922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 5-tr? fluoromet? lt? ofen-2? reference compounds of formula I 93, especially preferably compounds I 931 - I 932922 especially compounds (S, S) -I 931 -I 932922 which are distinguished from the corresponding compounds 111-112922 or (S, S) - I 11-112922 in which the group A2RdReRf represents 3-methox? T? Ofen-2-? E Likewise preferably the compounds of formula I 94 are especially preferred compounds I 941 - I 942922 especially compounds (S, S) -I 941 -I 942922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 4-methox? T? Ofen-2? Preference is likewise given to compounds of formula I 95, especially preferably compounds I 951 - I 952922, especially compounds (S, S) -I 951 -I 952922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 5-methox? T? Ofen-2-? E Likewise, the compounds of formula I 96 are particularly preferably compounds I 961 - I 962922 especially compounds (S, S) -I 961 - I 962922 which are distinguished from the corresponding compounds 111-112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 3-fluorot? Ofen-2-? Preference is likewise given to compounds of formula I 97, particularly preferably compounds I 971-I 972922, especially compounds (S, S) -I 971-I 972922, which are distinguished from corresponding compounds 111 -112922 or (S.S) -I 11 -112922 in which the group A2RdReRf represents 4-fluorot? ofen-2-? lo. Also preferably are the compounds of formula I 98 of special
Preference is given to the compounds I 981-I 982922, in particular the compounds (S, S) -I 981 -I 982922 which are distinguished from the corresponding compounds 111-112922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 5-fluorot? Ofen-2-? E Also preferred are compounds of formula I 99, especially preferred compounds I 991 - I 992922, especially compounds (S, S) -I 991 -I 992922, which are distinguished from corresponding compounds 111-112922 or (SS) -l 11-112922 in which the group A2RdReRf represents t-ofen-3-yl Also preferred are compounds of formula I 100, particularly preferably compounds I 100.1 - I 100.2922 especially the compounds (S, S) -I 100.1 - I 100.2922 which are distinguished from the corresponding compounds 111 - I 12922 or (SS) - I 11 - 112922 in which the group A2RdReRf represents 2-chlorot? Ofen-3-? Lo. Preferably also compounds of formula I 101 are especially preferred compounds I 1011-I 1012 922 especially the compounds (S, S) -I 1011-I 1012922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 4-chlorot? Also preferred are compounds of formula I 102, particularly preferably compounds 11021-11022922, especially compounds (S, S) -I 1021-I 1022922, which are distinguished from the corresponding compounds 111-I 12922 or (SS) -I 11-112922 in which the group A2RdReRf represents 5-chlorot? ofen-3-yl Also preferred are compounds of formula I 103, especially preferred compounds 11031-11032922 especially compounds ( S, S) - I 1031 - I 1032922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2- fluorot? Ofen-3-? Preference is likewise given to compounds of formula I 104, especially preferred compounds 11041 - 11042922, especially compounds cough (S, S) - I 1041 - I 1042922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 4- fluorot? ofen-3- Likewise, the compounds of formula I 105 of special
Preference is given to the compounds 11051-11052922, in particular the compounds (S, S) -11051-11052922 which are distinguished from the corresponding compounds 111-I 12922 or (SS) -I 11-112922 in which the group A2RdReRf represents 5-fluorot Also preferred are compounds of formula I 106, particularly preferably compounds 11061-11062922, especially compounds (S, S) -I 1061-I 1062922, which are distinguished from corresponding compounds 111-I. 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-methox? T? Ofen-3-yle. Preferably also compounds of formula I 107 are especially preferred compounds 11071 - 11072922 especially the compounds (S, S) -I 1071-I 1072922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReR 'represents 4-methox? The compounds of formula I 108 are also preferably preferentially preferred compounds 11081 11082922 especially the compounds (S, S) -I 1081-I 1082922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 5-methox Also preferred are compounds of formula I 109, particularly preferably compounds 11091-11092922, especially compounds (S, S) -I 1091-1 1092922, which are distinguished from corresponding compounds 111. - I 12922 or (S, S) -I 11 - 112922 in which the group A2RdReRf represents 2-tr? Fluoromet? Lt? Ofen-3-? Lo. Also preferred are compounds of formula 1110, especially preferred compounds 1110.1 - 1110.2922, especially compounds (S, S) - I 110.1 - I 110.2922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 wherein the group A2RdReRf represents 4- tr? fluoromet? lt? ofen-3-? lo Also preferred are compounds of formula 1111, especially preferred compounds 11111 - 111129 22 especially the compounds (S, S) - 11111 - 11112922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) -I 11 - 112922 in which the group A2RdReRf represents 5-
Also preferred are compounds of formula 1112, especially preferred compounds 11121 - 11122922, especially compounds (S, S) - 11121 - 11122922, which are distinguished from the corresponding compounds of formula I and II. -I 12922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents furan-2-? Lo Likewise, the compounds of formula 1113 are especially preferred, especially compounds 11131-11132922, especially compounds ( S, S) - I 1131 - I 1132922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in which the group A2RdReRf represents 3-chlorofuran-2? Preferably the compounds of formula 1114 are especially preferred compounds 11141 - 11142922, especially compounds (S, S) - 11141 - 11142922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in which the group A2RdReRf represents 4-chlorofuran-2? The compounds of formula 1115 are especially preferred compounds 11151 - 11152922, especially compounds (S, S) - I 1151 - I 1152922 which are distinguished from the corresponding compounds 111 - I 12922 or (SS) - I 11 - 112922 in which the group A RdReRf represents 5-chlorofuran-2-yle The compounds of formula 1116 are also particularly preferably compounds 11161-11162922, especially the compounds (S, S) - I 1161-I 1162922 which are they distinguish from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 3-fluorofuran-2-yle. Preferably, the compounds of formula 1117 are also especially preferred compounds 11171-11172922 especially the compounds (S, S) -I 1171-I 1172922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 4- fluorofuran-2-? lo Also preferably are the compounds of mule 1118, especially preferred compounds 11181 - 11182922, especially compounds (S, S) - I 1181 - I 1182922, which are distinguished from the corresponding compounds I 11 -
I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 5-fluorofuran-2-yle. Preferably, the compounds of formula I 119 are also particularly preferably compounds 11191-11192922, especially those compounds (S, S) -I 1191-I 1192922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents furan-3? Preferably the compounds of formula I 120, especially preferably the compounds I 120.1-I 120.2922 especially the compounds (S, S) -I 120.1-I 120.2922 which are distinguished from the corresponding compounds 111 -112922 or (SS) -I 11-112922 in which the group A2RdReRf represents 2-chlorofuran-3-yle. Preferably, the compounds of formula I 121 are also particularly preferably compounds I 1211-I 1212922, especially those compounds (S, S) - I 1211 - I 1212922 which are distinguished from the corresponding compounds 111 -112922 or (S, S) -I 11 - 112922 wherein the group A2RdReRf represents 4-chlorofuran-3-yl. Preferably, the compounds of formula I 122 are also particularly preferred compounds 11221 - 11222922 especially compounds (S, S) - I 1221 - I 1222922 which are they distinguish from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 5-chlorofuran-3-yle. Preferably, the compounds of formula I 123 are also particularly preferred. Compounds 11231 - 11232922 especially the compounds (S, S) - I 1231 - I 1232922 which are distinguished from the corresponding compounds 111 - I 12922 or (SS) - I 11 - 112922 in which the group A2RdReRf represents 2- fluorofuran The compounds of formula I 124 are also preferred, especially preferred are compounds 11241-11242922, especially compounds (S, S) -I 1241-I 1242922, which are distinguished from the corresponding compounds 111-I 12922 or well (S, S) -I 11 - 112922 in which the group A2RdReRf represents 4-fluorofuran-3-yl Also preferred are compounds of formula I 125, especially preferred compounds 11251 - 11252922 especially compounds (S, S) - I 1251 - I 1252922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 5-fluorofuran-3-yl. formula I 126, especially preferred are compounds 11261 - 11262922, especially compounds (S, S) - I 1261 - I 1262922, which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in The group A2RdReRf represents 5-fluorofuran-3-yl. Preferably, the compounds of formula I 127 are also preferred, especially compounds 11271 - 11272922, especially compounds (S, S) -I 1271-I 1272922, which are distinguished from each other. of the corresponding compounds 111-I 12922 or (S, S) -I 11 -112922 in which R1 is CH3 Also preferred are compounds of formula I 128, especially preferred compounds 11281 - 11282922, especially compounds (S, S) -I 1281 - I 1282922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 2-chlorophenol and R1 is CH3 Also preferred are compounds of formula I 129, especially preferred compounds 11291 - 11292922 in especially the compounds (S, S) -I 1291-11292922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11 -112922 in which the group A2RdReR 'represents 3-chlorophenol and R1 is CH3 Also preferred are compounds of formula I 130, especially preferably compounds I 130.1 - I 130.2922, especially compounds (S, S) - I 130.1 - I 130.2922 which are distinguished of the corresponding compounds 111-I 12922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 4-chlorophenol and R1 is CH3 Likewise preferably the compounds of formula I 131 are especially preferred compounds I 1311-I 1312922 especially compounds (S, S) -I 1311-I 1312922 which are distinguished from the corresponding compounds 111-I 12 922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-tpfluoromethylphenyl and R 1 is CH 3 Likewise, the compounds of formula I 132 are especially preferred.
Preference is given to the compounds 11321 - 11322922, in particular the compounds (S, S) - I 1321 - I 1322922, which are distinguished from the corresponding compounds 111 - I 12922 or (SS) - I 11 - 112922 in which the group A2RdReRf represents 3. -tpfluoromethylphenyl and R1 is CH3 Also preferred are compounds of formula I 133, especially preferred compounds 11331 - 11332922, especially compounds (S, S) - I 1331 - I 1332922 which are distinguished from corresponding compounds 111 - I 12922 or (S, S) -I 11 - 112922 in which the group A2RdReRf represents 4-tpfluoromethylphenyl and R1 is CH3 Likewise, the compounds of formula I 134 are especially preferably compounds 11341 - 11342922, especially compounds (S , S) -I 1341 - I 1342922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-methoxyphenyl and R 1 is CH 3 Likewise they are preferably the compounds of formula I 135 of special Preference is given to compounds 11351 - 11352922, in particular compounds (S, S) - I 1351 - I 1352922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in which the group A2RdReRf represents 3-methoxyphenyl and R1 is CH3 Also preferred are compounds of formula I 136, especially preferred compounds 11361 - 11362922, especially compounds (S, S) - I 1361 - I 1362922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 4-methoxyphenyl and R1 is CH3 Also preferred are compounds of formula I 137, especially preferred compounds 11371-11372922 especially compounds (S, S) - I 1371 - I 1372922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-fluorophenyl and R 1 is CH 3 They are also preferably the compounds of formula I 138 of special preference Compounds 11381 - 11382922 especially compounds (S, S) - I 1381 - I 1382922 which are distinguished from the corresponding compounds 111 - I 12922 or (SS) - I 11 - 112922 in which the group A2RdReRf represents 3 -
fluorophenyl and R1 is CH3 Also preferably compounds of formula I 139 are especially preferred compounds 11391 - 11392922 especially compounds (S, S) - I 1391 - I 1392922 which are distinguished from the corresponding compounds 111-I 12922 or well (S, S) -I 11-112922 in which the group A2RdReRf represents 4-fluorophenyl and R1 is CH3 Likewise preferably the compounds of formula I 140, especially preferably compounds I 140.1 - I 140.2922, are preferred. in particular the compounds (S, S) - I 140.1 - I 140.2922 which are distinguished from the corresponding compounds 111 -112922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 2- Methanol and R1 is CH3 Also preferred are compounds of formula I 141, particularly preferably compounds I 1411 - I 1412922, especially compounds (S, S) - I 1411 - I 1412922 which are distinguished from the corresponding compounds compounds 111 -112922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 3-met? lf and R1 is CH3. Preferably, the compounds of formula I 142 are also particularly preferred compounds 11421 - 11422922, especially compounds (S, S) - I 1421 - I 1422922 which are distinguished from the corresponding compounds 111 - I 12922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 4-met? Lfen? Lo and R1 is CH3 Likewise preferably the compounds of formula I 143 are especially preferred compounds 11431-11432922 especially those compounds (S, S) - I 1431 - I 1432922 which are distinguished from the corresponding compounds 111 - I 12922 or (SS) - I 11 - 112922 in which the group A2RdReRf represents 2-chloro-3-methylphenyl and R 1 is CH3 Preference is likewise given to the compounds of formula I 144, especially preferred compounds 11441 - 11442922, especially compounds (S, S) - I 1441 - I 1442922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-chloro-4- methylphenyl and R1 is CH3 Also preferred are compounds of formula I 145, especially preferred compounds 11451 - 11452922, especially compounds (S, S) -
I 1451 - I 1452922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-chloro-5-methylphenyl and R1 is CH3 likewise are preferably the compounds of formula I 146, especially preferably compounds 11461 - 11462922, especially compounds (S, S) - I 1461 - I 1462922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in which the group A2RdReRf represents 2-chloro-6-methylphenyl and R1 is CH3 Also preferred are compounds of formula I 147, especially preferred compounds 11471 - 11472922, especially compounds (S, S) - I 1471 - I 1472922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in which the group A2RdReRf represents 23-dichlorophenyl and R 1 is CH 3 Likewise preferably the compounds of formula I are particularly preferred compounds 11481 - 11482922 especially compounds (S, S) - I 1481 - I 1482922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 24-dichlorophenyl and R 1 is CH 3 Likewise are Preferably the compounds of formula I 149 are especially preferred compounds 11491 - 11492922, especially compounds (S, S) - I 1491 - I 1492922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11-112922 in which the group A2RdReRf represents 25-dichlorophenyl and R1 is CH3 Likewise preferably the compounds of formula I 150, especially preferably the compounds I 150.1-I 150.2922 especially the compounds (S, S) - I 150.1 - I 150.2922 which are distinguished from the corresponding compounds 111 - I 12922 or (SS) -I 11 - 112922 in which the group A2RdReRf represents 26-dichlorophenyl and R1 is CH3 Likewise are from Preference is given to compounds of formula I 151, especially preferably compounds I 1511-I 1512922, especially those omitted (S, S) - I 1511 - I 1512922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-chloro-3-fluorophenyl and R1 is CH3
Preference is likewise given to compounds of formula I 152, especially preferably compounds 11521 - 11522922, especially compounds (S, S) - I 1521 - I 1522922 which are distinguished from the corresponding compounds 111 - I 12922 or (SS) - I 11-112922 in which the group A2RdR ° Rf represents 2-chloro-4-fluorophenyl and R1 is CH3 Likewise preferably the compounds of formula I 153 are particularly preferably compounds 11531 - 11532922 especially compounds (S, S ) - I 1531 - I 1532922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) -I 11 - 112922 in which the group A2RdReRf represents 2-chloro-5-fluorophenyl and R1 is CH3 They are also Preferably the compounds of formula I 154, especially preferably compounds 11541 - 11542922, in particular compounds (S, S) - I 1541 - I 1542922, which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11-112922 in which the group A2RdReRf represents 2-chloro-6-fluorofe nyl and R1 is CH3 Also preferred are compounds of formula I 155, especially preferred compounds 11551 - 11552922, especially compounds (S, S) - I 1551 - I 1552922 which are distinguished from the corresponding compounds 111 - I 12922 or well (S, S) -I 11-112922 in which the group A2RdReRf represents 23-difluorophenyl and R1 is CH3 Likewise preferably the compounds of formula I 156 are especially preferred compounds 11561 - 11562922 especially compounds (S, S) - I 1561 - I 1562922 which are distinguished from the corresponding compounds 111-I 12922 or (SS) -I 11-112922 in which the group A2RdReRf represents 24-difluorophenyl and R 1 is CH 3 Likewise preferably the compounds of formula I 157, especially preferred compounds 11571 - 11572922, especially compounds (S, S) - I 1571 - I 1572922 which are distinguished from the corresponding compounds 111 - I 12922 or (SS) - I 11 - 112922 in which the group A2RdReRf represents 25-difluo Rophenyl and R1 is CH3 Also preferred are compounds of formula I 158, especially preferred compounds 11581 - 11582922, especially compounds (S, S) - I 1581 - I 1582922 which are distinguished from the corresponding compounds I 11 -
I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 26-difluorophenyl and R1 is CH3 Also preferred are compounds of formula I 159, especially preferred compounds 11591 - 11592922 especially compounds (S, S) -I 1591-I 1592922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 2-fluoro-3-chlorophenyl and R 1 is CH3 Also preferred are compounds of formula I 160, especially preferred compounds I 160.1 - I 160.2922 especially compounds (S, S) -I 160.1 - I 160.2922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 2-fluoro-4-chlorophenyl and R1 is CH3 Likewise preferably the compounds of formula I 161 are especially preferred the compounds I 1611 - I 1612922 especially the compounds (S, S) -I 1611 - I 1612922 which are distinguished from the corresponding compounds omitted 111-I 12922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 2-fluoro-5-chlorophenyl and R 1 is CH 3 Likewise preferably the compounds of formula I 162 are especially preferred compounds 11621 - 11622922 especially the compounds (S, S) - I 1621 - I 1622922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) -I 11 - 112922 in which the group A2RdReRf represents 34- difluorophenyl and R1 is CH3 Also preferred are compounds of formula I 163, especially preferably compounds 11631-11632922, especially compounds (S, S) -I 1631-I 1632922, which are distinguished from the corresponding compounds 111-I 12922 or well (S, S) -I 11 - 112922 in which the group A2RdReRf represents 35-difluorophenyl and R1 is CH3 Likewise preferably the compounds of formula I 164 are especially preferred compounds 11641 - 11642922 especially compounds (S, S) - I 1641 - I 1642922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 34-dichlorophenyl and R 1 is CH 3 Likewise preferably the compounds of formula I 165 of special
Preference is given to the compounds 11651-11652922, in particular the compounds (S, S) -I 1651-I 1652922, which are distinguished from the corresponding compounds 111-I 12922 or (SS) -I 11-112922 in which the group A2RdReRf represents -dichlorophenyl and R1 is CH3 Also preferred are compounds of formula I 166, especially preferred compounds 11661 - 11662922, especially compounds (S, S) - I 1661 - I 1662922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents 3-fluoro, 4-chlorophenyl and R1 is CH3 Likewise preferably the compounds of formula I 167 are especially preferably compounds 11671 - 11672922 in particular the compounds (S, S) -I 1671-I 1672922 which are distinguished from the corresponding compounds 111-I 12922 or (SS) -I 11 -112922 in which the group A2RdReRf represents 4-fluoro, 3-chlorophenyl and R 1 is CH3 Also preferably are the compounds of formula I 168 of speci to the preference the compounds 11681 - 11682922 especially the compounds (S, S) -I 1681-I 1682922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf for 3-fluoro, 5-chlorophenyl and R1 is CH3 Also preferred are compounds of formula I 169, especially preferred compounds 11691 - 11692922, especially compounds (S, S) - I 1691 - I 1692922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11 -112922 in which the group A2RdReR 'represents p? r? d? n-2-? lo and R1 is CH3 Likewise preferably the compounds of formula I 170, especially preferred compounds I 170.1 - I 170.2922 especially compounds (S, S) - I 170.1 - I 170.2922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) -I 11-112922 where the group A2RdReRf represents 3- chlorop? Pd? N-2-? Lo and R1 is CH3 Also preferred are compounds of formula I 171 of special preference is given to compounds I 1711-I 1712922, in particular compounds (S, S) -I 1711-I 1712922 which are distinguished from the corresponding compounds 111-I 12922 or (SS) -I 11-112922 in which the group A2RdReRf represents 4-
chloropr? d? n-2-? lo and R1 is CH3 Likewise preferably the compounds of formula I 172 are especially preferred compounds 11721 - 11722922 especially compounds (S, S) - I 1721 - I 1722922 which they are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 5-chlorop? r? d? n-2-? lo and R1 is CH3. Preference is given to compounds of formula I 173, especially preferably compounds 11731 - 11732922, especially compounds (S, S) - I 1731 - I 1732922 which are distinguished from the corresponding compounds 111 -112922 or (SS) -I 11 - 112922 wherein the group A2RdReR (represents 6-chloropr? r? d? n-2-? lo and R1 is CH3 Likewise preferably compounds of formula I 174 are especially preferred compounds 11741 - 11742922 especially compounds (S , S) - I 1741 - I 1742922 which are distinguished from the corresponding compounds 111 -112922 or (SS) -I 11-112922 in which the group A2RdReRf represents nt 3-tr? fluoromet? lp? r? d? n? 2-? lo and R1 is CH3 Likewise preferably compounds of formula I 175 are especially preferred compounds 11751 - 11752922 especially compounds (S, S) - I 1751 - I 1752922 which are distinguished from the corresponding compounds 111-I 12922 or (SS) -I 11-112922 in which the group A2RdReRf represents 4-tpfluoromet? Lp? R? D? N-2-? and R1 is CH3. Preferably, the compounds of formula I 176 are also especially preferred compounds 11761 - 11762922, especially compounds (S, S) - I 1761 - I 1762922 which are distinguished from the corresponding compounds 111 - I 12922 or (SS) -I 11-112922 in which the group A2R ReRf represents 5- tpfluoromet? Lp? R? D? N-2-? Lo and R1 is CH3 Likewise preferably the compounds of formula I 177 are especially preferred. compounds 11771 - 11772922, in particular compounds (S, S) - I 1771 - I 1772922 which are distinguished from the corresponding compounds 111 - I 12922 or (SS) - I 11 - 112922 wherein the group A2RdReRf represents 6- tr? fluoromet? lp? r? d? n? 2-? lo and R1 is CH3 Likewise preferably the compounds of formula I 178 are especially preferred compounds 11781 - 11782922 especially those compounds (S, S) - I 1781 - I 1782922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 3-methox? P? R? D? N-2-? it and R1 is CH3 Also preferred are compounds of formula I 179, especially preferred compounds 11791 - 11792922, especially compounds (S, S) - I 1791 - I 1792922 which are distinguished from the corresponding compounds 111 - I 12922 or well (S, S) -I 11-112922 in which the group A2RdReRf represents 4-methox? p? r? d? n-2-? lo and R1 is CH3 Likewise preferably the compounds of formula I 180 of special Preference is given to compounds I 180.1-I 180.2922, especially compounds (S, S) -I 180.1-I 180.2922 which are distinguished from the corresponding compounds 111-I 12922 or (SS) -I 11 - 112922 in which the group A2RdReRf represents 5-methox? P? Pd? N-2-? Lo and R1 is CH3 Likewise preferably the compounds of formula I 181 are especially preferably compounds I 1811 - I 1812922 especially s compounds (S, S) - I 1811 - I 1812922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in which the group A2RdReRf represents 6-methoxypyr ? d? n-2-? lo and R1 is CH3 Also preferred are compounds of formula I 182, especially preferred compounds 11821 - 11822922, especially compounds (S, S) - I 1821 - I 1822922 which are distinguished from the corresponding compounds 111-I 12922 or (SS) -I 11-112922 in which the group A2RdReRf represents 3-fluorop? r? d? n-2-? lo and R1 is CH3. Also preferably are the compounds of formula Especially preferred are the compounds 11831 - 11832922, in particular the compounds (S, S) - I 1831 - I 1832922 which are distinguished from the corresponding compounds 111 - I 12922 or (SS) - I 11 - 112922 in which the group A2RdReRf represents 4- fluorop? pd? n-2-? lo and R1 is CH3 Likewise preferably compounds of formula I 184 are of special preference compounds 11841 - 11842922 especially the compounds (S, S) - I 1841 - I 1842922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in which the group A2R ReRf represents 5- fluorop? pd? n-2-? lo and R1 is CH3
Preference is likewise given to compounds of formula I 185, especially preferred compounds 11851 - 11852922, especially compounds (S, S) - 11851 - 11852922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11-112922 in which the group A2RdReRf represents 6-fluorop? R? D? N-2-? Lo and R1 is CH3 Likewise preferably compounds of formula I 186 are especially preferred compounds 11861 - 11862922 especially those compounds (S, S) - I 1861 - I 1862922 which are distinguished from the corresponding compounds 111-I 12922 or (SS) -I 11 -112922 in which the group A2RdReRf represents p? r? d? n -3 and R1 is CH3. Preferably, the compounds of formula I187 are especially preferred compounds 11871 - 11872922, especially compounds (S, S) - I 1871 - I 1872922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) -I 11 - 112922 in which the group A2RdReRf represents 2-chlorop? r? d? n-3-? lo and R1 is CH3 Preference is likewise given to compounds of formula I 188, especially preferred compounds 11881 - 11882922, especially compounds (S, S) - I 1881 - I 1882922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) ) -I 11 - 112922 in which the group A2RdReRf represents 4-chloropr? D? N? 3-? Lo and R1 is CH3 Likewise preferably the compounds of formula I 189 are especially preferred compounds 11891 - 11892922 in especially the compounds (S, S) - I 1891 - I 1892922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in which the group A2RdReRf represents 5- chloropyr? d? n-3-? lo and R1 is CH3 Also preferred are compounds of formula I 190, especially preferably compounds I 190.1 - I 190.2922, especially compounds (S, S) - I 190, 1 - I 190,2922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 6- chlorop? Pd? n-3-? lo and R1 is CH3 Also preferred are compounds of formula I 191, especially preferably compounds I 1911 - I 1912922, especially compounds (S, S) - I 1911 - I 1912922 which are distinguished from corresponding compounds I 11 -
I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-tpfluoromet? Lp? Pd? N-3-? Lo and R1 is CH3 Likewise preferably the compounds of formula I 192 are compounds 11921-11922922 especially compounds (S, S) -I 1921-I 1922922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11 -112922 in which the group A2RdReRf 4-tr? Fluoromet? Lp? Pd? N-3-ylo R1 is CH3 Also preferred are compounds of formula I 193, particularly preferably compounds 11931- 11932922, especially compounds (S, S) -I 1931- I 1932922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 5-tr? Fluoromet? Lp? Pd? N-3-? Lo and R1 is CH3 Also preferred are compounds of formula I 194, particularly preferably compounds 11941-11942922, especially compounds (S, S) -I 1941-I 1942922, which are distinguished from the corresponding compounds. compounds 111-I 12922 or (S, S) -I 11-112922 in which the group ARdReRf represents 6-tpfluoromet? lp? r? d? n-3-? lo and R1 is CH3 Likewise preferably the compounds are of formula I 195, especially preferred compounds 11951 - 11952922, especially compounds (S, S) - I 1951 - I 1952922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 wherein the group A2RdReRf represents 2-methox? p? r? d? n-3-? lo and R1 is CH3 Likewise preferably the compounds of formula I 196 are especially preferred compounds 11961-I 1962922 especially the compounds (S, S) - I 1961 - I 1962922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 4-methox? P? R? D Also, the compounds of formula I 197 are particularly preferably compounds 11971 - 11972922, especially compounds (S, S) - I 1971 - I 1972922 which are distinguished from each other. of the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 5-methox? p? pd? n-3-? lo and R1 is CH3. compounds of formula I 198 of special
Preference is given to compounds 11981-11982922, especially compounds (S, S) -I 1981-I 1982922, which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 6-methox? p? r? d? n-3-? lo and R1 is CH3 Also preferred are compounds of formula I 199, especially preferred compounds 11991 - 11992922 especially compounds (S, S) -I 1991 - I 1992922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-fluorop? R? D? N-3-? Lo and R1 is CH3 Also preferred are compounds of formula I 200, especially preferably compounds I 200.1-I 200.2922 especially compounds (S, S) -I 200.1-I 200.2922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 4-fluorop? r? d? n-3-? lo and R1 is CH3 Likewise preferably the compounds are of formula 120 1 of particular preference are the compounds I 2011 - I 2012922, especially the compounds (S, S) -I 2011 - I 2012922 which are distinguished from the corresponding compounds 111 -I 12922 or (S, S) -I 11 - 112922 in those which the group A2R ReRf represents 5-fluorop? r? d? n-3-? lo and R1 is CH3 Likewise preferably the compounds of formula I 202 are of particular preference the compounds I 2021-I 2022922 especially the compounds ( S, S) - I 2021 - I 2022922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) -I 11 - 112922 in which the group A2RdReRf represents 6- fluorop? R? D? N- 3-? Lo and R1 is CH3 Also preferred are compounds of formula I 203, especially preferably compounds I 2031-I 2032922, especially compounds (S, S) -I 2031-I 2032922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents p? Pd? N-4-? Lo and R1 is CH3 Likewise preferably the compounds of mule I 204, especially preferably compounds I 2041 - I 2042922, especially compounds (S, S) - I 2041 - I 2042922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in which the group A2RdReRf represents 2-
fluorop? r? d? n-4-? lo and R1 is CH3 Also preferred are compounds of formula I 205, particularly preferably compounds I 2051-I 2052922, especially compounds (S, S) -I 2051-I 2052922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 3-fluorop? R? D? N-4-? Lo and R1 is CH3 Preferably, the compounds of formula I 206 are particularly preferably compounds I 2061-I 2062922, especially compounds (S, S) -I 2061-I 2062922 which are distinguished from the corresponding compounds 111 -112922 or (SS) - I 11-112922 in which the group A2RdReRf represents 2-methox? P? R? D? N-4-? Lo and R1 is CH3 Likewise preferably the compounds of formula I 207 are especially preferably compounds I 2071-I 2072922 especially the compounds (S, S) - I 2071 - I 2072922 which are distinguished from the corresponding compounds 111 -112922 or (S, S) -I 11-112922 in which the group A2RdReR f represents 3-methox? p? r? d? n-4-? lo and R1 is CH3 Likewise preferably compounds of formula I 208 are especially preferred compounds I 2081-I 2082922 especially compounds (S, S ) - I 2081 - I 2082922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in which the group A2RdReRf represents 2- tr? Fluoromet? Lp? R? D? N -4-? Lo and R1 is CH3 Also preferred are compounds of formula I 209, especially preferably compounds I 2091-I 2092922 especially compounds (S, S) - I 2091-I 2092922 which are distinguished from the corresponding compounds compounds 111-I 12922 or (SS) -I 11-112922 in which the group A2RdReRf represents 3- tr? fluoromet? lp? r? d? n-4-? lo and R1 is CH3 Likewise preferably the compounds are of formula I 210, especially preferred compounds 1210.1-1210.2922 especially compounds (S, S) -1210.1-1210.2922 which are distinguished from the corresponding compounds 111-I 12922 or (SS) -I 11-112922 in which the group A2RdReRf represents 2-chloropyridine-4-? Lo and R1 is CH3 Likewise, the compounds of formula 1211 are especially preferably compounds 12111-12112922, especially compounds ( H.H)-
12111 -. 12111-12112922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 3-chlorop? R? D? N-4-? Lo and R1 is CH3 Preferably also compounds of formula I 212 are especially preferred compounds 12121-12122922 especially compounds (S, S) - 12121-12122922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents t? Ofen-2-? Lo and R1 is CH3 Likewise preferably the compounds of formula I 213 are especially preferred compounds 12131-12132922 especially the compounds (S, S ) - 12131 - 12132922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 3-chlorot? Ofen-2-? Lo and R1 is CH3 Preferably, the compounds of formula I 214 are especially preferred compounds 12141 - 12142922, especially compounds (S, S) - 12141 - 12142922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 4-chlorot? Ofen-2? Lo and R1 is CH3. compounds of formula I 215 are especially preferred compounds 12151-12152922 especially compounds (S, S) - 12151-12152922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in those which the group A2RdReRf represents 5- chlorot? ofen-2-? lo and R1 is CH3 Likewise preferably compounds of formula 1216 are especially preferred compounds 12161-12162922 especially compounds (S, S) - 12161-12162922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 3- tr? fluoromet? lt? ofen-2? lo and R1 is CH3 Likewise are Preferably the compounds of formula I 217 are especially preferred compounds 12171-12172922 especially compounds (S, S ) - 12171 - 12172922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in which the group A2RdReRf represents 4- tpfluoromet? Lt? Ofen-2-? Lo and R1 is CH3
Also preferred are compounds of formula 1218, especially preferably compounds 12181-12182922, especially compounds (S, S) - 12181-12182922 which are distinguished from the corresponding compounds 111-I 12922 or (SS) -I 11 - 112922 in which the group A2RdReRf represents 5-tpfluoromet? Lt? Ofen-2? Lo and R1 is CH3 Likewise preferably the compounds of formula I 219 are especially preferred compounds 12191-12192922 especially compounds (S, S ) - 12191 - 12192922 which are distinguished from the corresponding compounds 111-I 12922 or (SS) -I 11-112922 in which the group A2RdReRf represents 3-methox? T? Ofen-2? Lo and R1 is CH3 Preferably, the compounds of formula I 220, especially preferred are compounds I 220.1-I 220.2922, especially compounds (S, S) -I 220.1-I 220.2922, which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) -I 11 - 112922 dadurch unterscheiden, dass Gruppe A2RdReRf represents 4 -metox? t? ofen-2-? lo and R1 is CH3 Likewise preferably the compounds of formula I 221 are especially preferred compounds I 2211-I 2212922 especially compounds (S, S) - I 2211 - I 2212922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 5-methox? t? ofen-2-? lo and R1 is CH3 likewise are preferably the compounds of formula I 222, especially preferably compounds I 2221-I 2222922, especially compounds (S, S) -I 2221-I 2222922, which are distinguished from the corresponding compounds 111-I 12922 or (S, S) - I 11-112922 in which the group A2RdReRf represents 3-fluorot? Ofen-2? Lo and R1 is CH3 Also preferred are compounds of formula I 223, particularly preferably compounds I 2231-I 2232922, especially compounds ( S, S) - I 2231 - I 2232922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in which the group A2Rd ReRf represents 4- fluorot? Ofen-2-? Lo and R1 is CH3 Likewise preferably the compounds of formula I 224 are especially preferred compounds I 2241-I 2242922 especially compounds (S, S) - I 2241 - I 2242922 which are distinguished from the corresponding compounds I 11 -
I 12922 or (SS) -I 11-112922 in which the group A2RdReRf represents 5-fluorot? Ofen-2? Lo and R1 is CH3 Likewise preferably the compounds of formula I 225 are especially preferred compounds I 2251 - I 2252922 especially the compounds (S, S) -I 2251-I 2252922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11 -112922 in which the group A2RdReRf represents t? ofen-3-? lo and
R1 is CH3 Also preferred are compounds of formula I 226, particularly preferably compounds I 2261-I 2262922 especially compounds (S, S) -12261-I 2262922 which are distinguished from corresponding compounds 111-I 12922 or (SS) -I 11-112922 in which the group A2RdReRf represents 2-chlorot? Ofen-3-? Lo and R1 is CH3 Likewise preferably the compounds of formula I 227 are especially preferably compounds I 2271-I 2272922 in especially the compounds (S, S) -12271-I 2272922 which are distinguished from the corresponding compounds 111-I 12922 or (SS) -I 11-112922 in which the group A2RdReRf represents 4-chlorot? ofen-3? it and R1 is CH3 Also preferred are compounds of formula I 228, particularly preferably compounds I 2281-I 2282922, especially compounds (S, S) -I 2281-I 2282922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 5- chlorot? Of In-3-? lo and R1 is CH3 Also preferred are compounds of formula I 229, particularly preferably compounds I 2291 - I 2292922, especially compounds (S, S) - I 2291 - I 2292922 which are distinguished from corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-fluorot? ofen-3-yl and R 1 is CH 3 Also preferred are compounds of formula I 230, particularly preferably compounds I 230.1 - I 230.2922, in particular compounds (S, S) - I 230.1 - I 230.2922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) ) -I 11 - 112922 in which the group A2RdReRf represents 4- fluorot? Ofen-3-? Lo and R1 is CH3 Likewise preferably the compounds of formula I 231 of special
Preference is given to the compounds I 2311-I 2312922, in particular the compounds (S, S) -I 2311-I 2312922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 5-fluorot? ofen-3-? lo and R1 is CH3 Also preferably compounds of formula I 232 are especially preferred compounds I 2321-I 2322922 especially compounds (S, S) -I 2321- I 2322922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-methox? T? Ofen-3-? Lo and R1 is CH3 Likewise are Preferably the compounds of formula I 233, especially preferably compounds I 2331-I 2332922, especially compounds (S, S) -I 2331-I 2332922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) ) -I 11 - 112922 in which the group A2RdReRf represents 4-methox? T? Ofen-3-? Lo and R1 is CH3 Also preferably are the compounds of formula I 234 d Particular preference is given to compounds I 2341-I 2342922, in particular compounds (S, S) -I 2341-I 2342922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in the that the group A2RdReRf represents 5-methox? t? ofen-3-? lo and R1 is CH3 Likewise preferably the compounds of formula I 235 are particularly preferably compounds I 2351-I 2352922 especially the compounds (S, S) - I 2351 - I 2352922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2- tr? Fluoromet? Lt? Ofen-3? and R1 is CH3. Preferably, the compounds of formula I 236 are also particularly preferably compounds I 2361-I 2362922, especially compounds (S, S) -I 2361-I 2362922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 4- tr? fluoromet? lt? ofen-3-? lo and R1 is CH3 Likewise they are preferably the compounds of formula I 237, especially preferably compounds I 2371-I 2372922, especially compounds (S, S) -I 2371-I 2372922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) - I 11-112922 in which the group A2RdReRf represents 5-
tr? fluoromet? lt? ofen-3-? lo and R1 is CH3 Also preferred are compounds of formula I 238, especially preferably compounds I 238 1-I 238 2922 especially compounds (S, S) -I 238 1 - I 238 2922 which are distinguished from the corresponding compounds 1 1 1 -I 1 2922 or (S, S) -I 1 1 - 1 1 2922 in which the group A2RdReRf represents furan-2-? Lo and
R1 is CH3 Also preferably compounds of formula I 239 are especially preferred compounds I 239 1 - I 239 2922 especially compounds (S, S) - I 239 1 - I 239 2922 which are distinguished from the corresponding compounds 1 1 1 -1 1 2922 or (S, S) -I 1 1 - 1 1 2922 in which the group A2RdReRf represents 3-chlorofuran-2-? Lo and R1 is CH3 Also preferred are compounds of formula I 240 , especially preferably the compounds I 240.1 - I 240.2922 especially the compounds (S, S) - I 240.1 - I 240.2922 which are distinguished from the corresponding compounds 1 1 1 -1 1 1 2922 or (S, S) -I 1 1 - 1 1 2922 in which the group A2RdReRf represents 4-chlorofuran-2α and R 1 is CH 3 Likewise preferably the compounds of formula I 241 are especially preferably compounds I 241 1 - I 241 2922, in particular the compounds (S, S) - I 241 1 - I 241 2922, which are distinguished from the corresponding compounds 1 1 1 - I 1 2922 or (S, S) -I 1 1 - 1 1 2922 in which group A 2RdReRf represents 5-chlorofuran-2-yl and R1 is CH3 Also preferred are compounds of formula I 242, particularly preferably compounds I 242 1-I 242 2922 especially compounds (S, S) -I 242 1 - I 242 2922 which are distinguished from the corresponding compounds 1 1 1 - I 1 2922 or (S, S) -I 1 1 - 1 1 2922 in which the group A2RdReRf represents 3-fluorofuran-2α and R 1 is CH3 Preference is likewise given to compounds of formula I 243, especially preferably compounds I 243 1 - I 243 2922, especially compounds (S), S) - I 243 1 - I 243 2922 which are distinguished from the corresponding compounds 1 1 1 - I 1 2922 or (S, S) -I 1 1 - 1 1 2922 in which the group A2RdReRf represents 4- fluorofuran -2-? Lo and R1 is CH3 Also preferred are compounds of formula I 244, especially preferably compounds I 244 1 - I 244 2922 especially compounds (S, S) -
I 2441 - I 2442922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 5-fluorofuran-2-? Lo and R1 is CH3. preference is given to the compounds of formula I 245, particularly preferably compounds I 2451-I 2452922, especially compounds (S, S) - I 2451 - I 2452922 which are distinguished from the corresponding compounds 111 - I 12922 or (SS) -I 11 -112922 in which the group A2RdReRf represents furan-3-? Lo and
R1 is CH3 Also preferred are compounds of formula I 246, particularly preferably compounds 12461-I 2462922, especially compounds (S, S) -I 2461-I 2462922 which are distinguished from the corresponding compounds 111-I 12922 or (S, S) -I 11 - 112922 in which the group A2RdReRf represents 2-chlorofuran-3-yl and R 1 is CH 3 Also preferred are compounds of formula I 247, especially preferably compounds 12471-I 2472922 in particular the compounds (S, S) - I 2471 - I 2472922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in which the group A2RdReRf represents 4-chlorofuran-3? it and R1 is CH3 Also preferred are compounds of formula I 248, especially preferably compounds I 2481 - I 2482922, especially compounds (S, S) - I 2481 - I 2482922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 5-chlorofuran -3-? Lo and R1 is CH3 Also preferred are compounds of formula I 249, especially preferably compounds I 2491 - I 2492922, especially compounds (S, S) - I 2491 - I 2492922 which are distinguished from the corresponding compounds compounds 111-I 12922 or (S, S) -I 11-112922 in which the group A2RdReRf represents 2-fluorofuran-3-yl and R 1 is CH 3 Likewise preferably the compounds of formula I 250 are especially preferred compounds I 250.1 - I 250.2922 in particular the compounds (S, S) - I 250.1 - I 250.2922 which are distinguished from the corresponding compounds 111 - I 12922 or (S, S) - I 11 - 112922 in which the group ARdReRf represents 4- fluorofuran-3-? Lo and R1 is CH3
Also preferred are compounds of formula I 251, particularly preferably compounds I 251 1-I 251 2922, especially compounds (S, S) -I 251 1-I 251 2922 which are distinguished from the corresponding compounds 1 1 1 - I 1 2922 or (SS) -I 1 1 - 1 1 2922 in which the group A2RdReRf represents 5-fluorofuran-3-? Lo and R1 is CH3 Likewise preferably the compounds of formula I 252 are especially preferred compounds I 252 1 - I 252 2922 in particular the compounds (S, S) -I 252 1 - I 252 2922 which are distinguished from the corresponding compounds 1 1 1 -I 1 2922 or (S, S) -I 1 1 - 1 1 2922 in which the group A RdReRf represents 5-fluorofuran-3-? Lo and R1 is CH3 The piperazine compounds of formula I can be prepared according to standard methods of the synthesis of organic compounds in different ways, for example according to the procedures explained in more detail below Procedure A The compounds of formula I can be prepared for example in analogy with procedures known in the literature by the cyclization of corresponding prior dipeptide steps of formula II, for example in analogy to the method described by T Kawasaki et al, Org Lett 2 (19) (2000), 3027-3029, Igor L Rodionaov et al., Tetrahedrona 58 (42) (2002), 8515-8523 or AL Johnsona et al, Tetrahedrona 60 (2004), 961-965 The cyclization of the dipeptides of formula II in compounds of the invention is hereinafter referred to as procedure A and it was outlined in the following scheme
In formula II, the variables A1, A2, R1-R8, Ra, R, Rc, Rd, Re and Rf have the meaning for formula I The group OR * represents a suitable leaving group bonded through oxygen R * is here , for example, CrC alkyl, especially methyl, ethyl or phenyl-alkyl CC p. benzyl The dipeptides of general formula II are new and also object of the present invention
The cyclization can be carried out, for example, by the transformation of a dipeptide of formula II, either in the presence of acid or base (acid or basic cyclization) or by heating the reaction mixture (thermal cycling). The bases or acids are used either in equimolar amounts with respect to dipeptide II or in excess In a special embodiment of the process of the invention, the bases or acids in excess are used with respect to the dipeptide The transformation of dipeptide II in the presence of a base is usually carried out at temperatures in the range of 0 ° C up to the boiling point of the reaction mixture, preferably from 10 ° C to 50 ° C, especially preferably from 15 ° C to 35 ° C. The reaction is generally carried out in a solvent, preferably in a solvent Inert Organic Suitable inert organic solvents include aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and mixtures of CC alkanes aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and chlorobenzene, ether such as diethylether, dnsopropyl ether, tert-butylmethylether, dioxane, anisole and tetrahydrofuran, nitplos such as acetonitoplo and propionitoplo, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, water as well as dimethylsulfoxide, dimethylformamide and dimethylacetamide as well as morfohne and N-methylmorpholino. Mixtures of the mentioned solvents can also be used. In a preferred embodiment of The reaction is carried out in a tetrahydrofuran-water mixture, for example with a mixing ratio of 10 to 10 1 (parts by volume). General inorganic compounds such as alkali and alkaline earth metal hydroxides such as lithium hydroxide are included as bases. , sodium hydroxide, potassium hydroxide or calcium hydroxide, an aqueous solution of ammonia , alkali metal or alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, hydride of alkali metals and alkaline earth metals such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, amides of alkali metals such as lithium amide, for example lithium dnsopropylamide, sodium amide and potassium amide, carbonates of alkali metals and alkaline metals, such as lithium carbonate, potassium carbonate, cesium carbonate and calcium carbonate, alkali metal hydrocarbonates, such as sodium hydrocarbonate, organic metal compounds, especially
alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride as well as alkali metal alcoholates and alkaline earth metal alcoholates such as sodium methanolate, sodium ethanolate, potassium ethanolate, potassium tert-butanolate, ter-pentanolate of potassium and dimethoxymagnesium, also organic bases, p. ex. tertiary amines such as t-methylamine, triethylamine, diisopropylethylamine 2-hydroxypyridine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine, as well as bicyclic amines. Of course, a mixture of different bases can also be used. In one embodiment of the process of the invention the reaction of II is carried out in the presence of bases, preferably in the presence of the bases ter-butanolate potassium, 2-hydroxypyridine or an aqueous solution of ammonia or a mixture of these bases. Preferably only one of these bases is used. In a particularly preferred embodiment, the reaction is carried out in the presence of an aqueous solution of ammonia, which, for example, can be from 10 to 50% v / w. The transformation of II in the presence of an acid is usually carried out at temperatures in the range of 10 ° C up to the boiling point of the reaction mixture, preferably from 50 ° C to the boiling point, especially preferably at the boiling point. boiling under reflux. The reaction is usually carried out in a solvent, preferably in an inert organic solvent. As a solvent, in principle, those which can also be used for basic cyclization, especially alcohols, are used. In a preferred embodiment the reaction is carried out in n-butanol. Acids for the cyclization of II basically use Brondostedt acids, as well as Lewis acids. In particular, inorganic acids, e.g. ex. hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, inorganic oxo acids such as sulfuric acid and perchloric acid, as well as inorganic Lewis acids such as boric trifluoride, aluminum trichloride, iron chloride III, tin chloride IV, titanium chloride IV and chloride Zinc II, as well as organic acids, for example carboxylic and hydroxycarboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and trifluoroacetic acid, as well as organic sulfonic acids such as toluenesulfonic acid, benzenesulfonic acid, camphor sulfonic acid and the like . Of course, a mixture of different acids can also be used.
In one embodiment of the process of the invention the reaction is carried out in the presence of organic acids, for example in the presence of carboxylic acids such as formic acid, acetic acid or tnfluoroacetic acid or a mixture of these acids
Preferably only one of these acids is used. In a preferred embodiment the reaction is carried out in acetic acid. In a particularly preferred embodiment, the acid cyclization is carried out in the presence of n-butanol, N-methyl-morpholine and acetic acid under reflux conditions. In another embodiment of the invention, the reaction is carried out exclusively by heating the reaction mixture (thermal cycling). The transformation is carried out here generally at temperatures in the range of 10 C to the boiling point of the reaction mixture, preferably 50 ° C up to the boiling point of the reaction mixture, especially preferably at the boiling point of the reaction mixture under reflux. The reaction is generally carried out in a solvent, preferably in an inert organic solvent. As solvents in principle those used in basic cycling are used Preferably, polar aprotic solvents are used p eg dimet ilsulfoxide or dimethylformamide or their mixtures In a preferred embodiment the reaction is carried out in dimethylsulfoxide. The reaction mixtures obtained according to one of the processes of the invention A can, for example, be processed in the usual way. This can be carried out, eg when mixed with water, Separating the phases and, where appropriate, purification by chromatography of the raw products The intermediate and final products are partly generated in the form of thick oils, from which the volatile particles can usually be removed or purified by reducing the pressure and increasing slightly the temperature. As long as the intermediate and final products are obtained as solids the purification can also be carried out by recrystallization or digestion. Process B The compounds of formula I with R 1? hydrogen can be prepared according to another process of the invention (method B) by reacting a piperazine compound of formula I, wherein R 1 represents h idrogene with an alkylation medium or an acylation medium, containing the R1 moiety other than hydrogen Such transformations can be carried out in analogy to procedures known in the literature, for example according to the methods described in I O Donkor et al, Bioorg
Med Chem Lett 1 1 (19) (2001), 2647-2649, BB Snider et al, Tetrahedrona 57 (16) (2001), 3301-3307, I Yasuhiro et al, J Am Chem Soc 124 (47) (2002) , 14017-14019, or M Falomi et al, Europ J Org Chem (8) (2000), 1669-1675
(I) { R1 = H.}.
According to process B, a piperazine compound of formula I is transformed with R 1 = hydrogen with a suitable alkylation medium, hereinafter the compound X 1 -R 1, or an acylation medium, hereinafter compound X 2 -R 1, wherein obtains a piperazine compound of formula I with R1? hydrogen. In the alkylation means X -R1, X1 can mean halogen or 0-S02-Rm with R in the meaning of CC alkyl or aplo, which in their case are substituted with Halogen, CC alkyl or haloalkyl-CC In an acylation medium X2-R1, X2 can mean halogen, especially Cl In that case R1? hydrogen and has the meaning as previously indicated and represents especially CC alkyl cycloalkyl CC alkenyl CC cycloalkenyl CC alkynyl CC cycloalkynyl CC phenyl-alkyl (CC), heterocyclyl, heterocyclyl-alkyl (CrC6), phenol- [alkoxycarbon? C6 C6] -alkyl (CrC6) or phenylheterocyclyl-alkyl (CC), or COR21 or S02R25, where the mentioned aliphatic, cyclic or aromatic parts of R1 may be partially or fully halogenated and / or may carry one to three of the following cyanohydroxy groups, CC alkyl haloalkyl CC cycloalkyl CC alkoxy CC alkylthio CC [D? -alkyl- (CC)] - amino, alkylcarbonyl CrC4, hydroxycarbonyl, alkoxycarbonyl CrC4, aminocarbonyl, alkylaminocarbonyl CC [D? -alkyl- (CrC4)] aminocarbonyl or alkylcarbonyloxy CrC4 The transformation is usually carried out at temperatures in the range of -78 ° C to the boiling point of the reaction mixture, preferably from -50 ° C to 65 ° C, especially preferably from -30 ° C to 65 ° C. The reaction is generally carried out in a solvent, preferably in an inert organic solvent. Suitable solvents are the compounds mentioned in procedure A, between
other toluene, dichloromethane, tetrahydrofuran or dimethylformamide or their mixtures In a preferred embodiment of the invention the reaction is carried out in tetrahydrofuran. In a preferred embodiment, the compound I is reacted with R1 = H with the alkylation medium or a medium of acylation in the presence of a base The compounds cited in process A are suitable bases The bases are generally used in an equimolar way They can also be used in excess or themselves as solvents In a preferred embodiment of the process of the invention the base is it is added in an equimolar quantity or in an essentially equimolar amount. In another preferred embodiment, sodium hydride is used as the base. The processing is generally carried out in analogy with the procedure described in procedure A Procedure C In analogy with the form If the procedure described in procedure B was described, the compound I, wherein R2 represents hydrogen, with alkylation means R2-X1 or acylation means R2-X2, where the compound of formula I is obtained with R2 = hydrogen (process C) The reaction conditions of the process of the invention C correspond to those of process B Process D The compounds of formula I can be prepared according to the procedure indicated in the following scheme, by transforming the substituent Ra, for example in analogy to the methods described in J TSUJI, Top Organomet Chem. (14 ) (2005), 332 pp, or J TSUJI, Organic Synthesis with Palladium Compounds (1980), 207 pp and Organikum, 21st edition, 2001, Wiley and the literature quoted there
(the I)
For this, a piperazine compound of formula la is transformed, which in place of the substituent Ra has a suitable leaving group L, by transformation
with a coupling partner, which contains a group Ra (compound Ra-X3), which converts it into another piperazine derivative of formula I The transformation is usually carried out in the presence of a catalyst, preferably in the presence of a metal catalyst of In general, the reaction is carried out in the presence of a base. That reaction sequence is represented below with the Example of the substituent Ra and can, of course, be used analogously for the transformation of the substituents Rb and Rc. used, for example, halogen, especially chlorine, bromine or iodine, or S (0) nRk, with n = 0, 1, 2 and Rk in the meaning of alkyl-haloalkyl (C) alkyl or, optionally, halogenated or substituted with CC alkyl As counterpart of X3-Ra coupling those compounds may be used especially, where X3 in the case of Ra in the meaning of C2-C6 alkenyl CC alkyl, aplo or heterolalk represents one of the following group s - Zn-R1 with R1 in the meaning of halogen, CC alkenyl alkyl aplo or heterolalk, B (ORm) 2, with Rm in the meaning of H or CC alkyl where two alkyl substituents together can form an alkylene chain CC or SnRn3 with Rn has the meaning of CC alkyl or aplo As long as Ra represents alkynyl CC X3 can also mean hydrogen For the preparation of compound I, wherein Ra represents CN, the compound la can also be transformed, where L represents bromine or iodine, with copper cyanide in analogy with known procedures (see, for example, Organikum, 21st edition, 2001, Wiley, page 404 and the literature cited therein) According to one of the embodiments of preference, there L or Ra, where the compound of Formula I is attached in an ortho position to the binding site of A1, they are attached to a C atom of A1 This reaction is usually carried out at temperatures in the range of -78 ° C to the boiling point of the reaction mixture. n, preferably from -30 ° C to 65 ° C, especially preferably at temperatures from 30 ° C to 65 ° C. The reaction is generally carried out in an inert organic solvent in the presence of a base. The above-mentioned compounds are suitable solvents. in the process A In one embodiment of the process of the invention, tetrahydrofuran is used with an amount
Water catalytic, in another embodiment, only tetrahydrofuran is used. Suitable compounds are the compounds mentioned in process A The bases are generally used in an equimolar way They can also be used in excess or themselves as solvents In a preferred embodiment of the process of the invention is added in an equimolar amount In another preferred embodiment, tetylamine or cesium carbonate is used as the base, preferably special cesium carbonate. As catalysts for the process of the invention, the compounds of the metals of the invention are in principle suitable. transition Ni Fe Pd or Cu It is possible to use organic or inorganic compounds Pd (PPh3) 2CI2, Pd (OAc) 2, PdCI2, or Na2PdCI4 Ph in this case represents phenyl The various catalysts can be used alone as also in the form of mixtures In a preferred embodiment of the invention, Pd (PPh3) 2Cl2 is used. it can be carried out analogously to the procedure described in process A Process E The piperazine compounds of formula I, wherein one of the groups Ra, Rb or Rc represents COOH, can be prepared in addition to the piperazine compounds of formula I where Ra , Rb or Rc represent COORz with Rz in the meaning alkyl, eg CH3, by saponification of the ester group Saponification is achieved eg by transformation with (H3C) 3SnOH, for example according to KC Nicolaou et al, Angew Chem Int Ed Engl (44) (2005), 1378 The carboxylic acid thus obtained can then be transformed according to standard methods of the organic synthesis, where appropriate after conversion to the acid chloride by transformation with an amine HNRURV or an alcohol HORw in the corresponding ester or amide, Organikum, Autorenkollektiv, Leipzig 1993 19th edition, page 424-429. That reaction sequence is represented below with the Example of the substituent Ra and may be R supposedly used analogously for the transformation of substituents Rb and R ° Step 1
(I) { Ra = COORz} (I) { Ra = COOH} Step 2
(lll) Step 3
In this scheme the variables A1, A2, R1-R8, R, Rc, Rd, Re and Rf have the meanings that were previously mentioned Ru and Rv independently of each other represent hydrogen, C2-C6 alkenyl C2-C6 alkyl, C2-C6 alkynyl, CrC6 alkoxy, C6 alkylsulphonyl, C-C6 alkylammosulfonyl, [Di-alkylamino (CC)] sulfonyl or substituted phenyl Rw represents C3-C6 alkenyl alkyl or C3-C6 alkynyl In a first step, the ester group in the piperazine compound I. { Ra = COORz} Saponification is achieved, for example, by transformation with (H3C) 3SnOH, where the free acid of I is obtained. { Ra = COOH} The reaction to free acid is usually carried out with an excess of (H3C) 3SnOH. The reaction is usually carried out in an inert organic solvent. Especially suitable dichloroethane is included in the solvents. In general, the transformation is carried out at elevated temperature, example at approx 80 ° C
In a second step, the acid I is transformed. { Ra = COOH} in its acid chloride of formula III The transformation to acid chloride is usually carried out at temperatures of 10 ° C to 50 ° C, preferably at room temperature, for example at 25 ° C. The reaction is usually carried out in a solvent Inert organic Suitable dichloromethane is included in suitable solvents In a preferred embodiment the transformation is carried out in dichloromethane and catalytic amounts of dimethylformamide. A number of reagents, for example, oxalyl chloride or thionyl chloride, are suitable for chlorination. Equimolar amounts of the chlorination reagent, especially oxa chloride, The conversion with an NHRURV amine in the successive reaction is usually carried out by adding an excess of the respective amine. The reaction can be carried out in a temperature range from 0 ° C to 40 ° C. ° C, preferably at room temperature, for example at 25 ° C. The transformation with an alcohol HORw in the successive reaction is usually carried out by adding an excess of both the respective alcohol, as well as of tetylamine. The reaction can be carried out in a range of temperature from 0 ° C to 40 ° C, preferably at room temperature, for example at 25 ° C. Processing can be carried out analogously to the procedure described in process A Process F The compounds of formula I can be prepared in accordance with synthesis indicated below by the coupling of piperazine compounds of general formula IV with the compound in V The coupling of IV with V is achieved in analogy with procedures known in the literature, for example according to G Porzi et al, Tetrahedrona Asymmetry 9 (19). ), (1998), 341 1-3420, or CI Harding et al, Tetrahedrona 60 (35), (2004), 7679-7692, or CJ Chang et al, J Chem Soc Perk T 1 (24), (1994) , 3587-35 93
(IV) (I) In the Scheme, A1, A2, R1-R8, Ra, Rb, Rc Rd, Re and R 'have the meanings indicated above L represents a suitable leaving group, such as halogen or OS02Rm, with Rm in the meaning of CC alkyl aplo, or an aplo substituted one to three times with CC alkyl The reaction is generally carried out at temperatures in the range of -78 ° C up to the boiling point of the reaction mixture, preferably in the the range from -78 ° C to 40 ° C, particularly preferably in the range from -78 ° C to 30 ° C. The reaction is usually carried out in an inert organic solvent in the presence of a base. The above-mentioned compounds are suitable solvents. in process A In a preferred embodiment of the process of the invention, tetrahydrofuran is used. Suitable bases are the compounds mentioned in process A In another preferred embodiment, lithium dnsopropylamide is used, particularly preferably an essentially equimolar amount, especially An equimolar quantity as a base The compounds of formula V can be obtained on the market or they can be prepared by means of transformations that are described in the literature of the corresponding precursor products that are commercially available. Processing can be carried out analogously to the procedure described in process A The precursors and intermediates necessary for the preparation of the compounds of formula I can be obtained commercially, are known from the literature or can be prepared according to procedures known in the literature. The dipeptide compounds of formula II can be prepared by example from N-protected dipeptides of general formula VI in analogy with procedures known in the literature, for example according to Glenn L Stahl et al, J Org Chem 43 (11), (1978), 2285-6 or
A K Ghosh et al, Org Lett 3 (4), (2001), 635-638
In formulas II and VI, the variables A1, A2, R1 - R8, Ra, Rb, Rc, Rd, Re and Rf have the meaning indicated for formula I, SG means a nitrogen protection group such as Boc (= tert-butoxycarbonyl ) and ORx represents a leaving group bound through an oxygen atom Naturally the preferred meanings for the compounds of formula I apply in each case for the compounds of formula II or IV With respect to the leaving group OR * the above is applied for dipeptides of formula II Thus, for example, a dipeptide of formula VI, where SG represents Boc and ORx is a suitable leaving group, in which R * is eg CC alkyl especially methyl, ethyl or benzyl in the presence of an acid is transformed in a compound of formula II The transformation is usually carried out at temperatures in the range of -30 ° C and the boiling point of the reaction mixture, preferably from 0 ° C to 50 ° C, especially preferably 20 ° C at 35 ° C The reaction can be carried out abo in a solvent, especially in an inert organic solvent. As solvents, the compounds mentioned for basic cyclization, especially tetrahydrofuran or dichloromethane or their mixtures, are used in principle. In a preferred embodiment the reaction is carried out in dichloromethane. As acids, the acids cited in process A In one embodiment of the process of the invention the reaction is carried out in the presence of organic acids, for example in the presence of strong organic acids, such as formic acid, acetic acid or tpfluoroacetic acid or their mixtures. In an embodiment of preference the reaction is carried out in the presence of trifluoroacetic acid. The processing can be carried out analogously to the procedure described in process A The protected dipeptides of formula VI can be prepared analogously to processes known in the literature, for example according to Wilford L. Mendelson et al. .,
Int J Peptide & Protein Research 35 (3), (1990), 249-257 A typical access is the amidation of an amino acid VIII protected with a Boc group, with an amino acid ester of formula VII as shown in the following scheme
In this scheme, the variables have the meanings that were previously mentioned. In place of Boc, other ammo protection groups can also be used.
In general, the transformation of Vil is carried out with VIII at temperatures ranging from -30 ° C to the boiling point of the reaction mixture, preferably from 0 ° C to 50 ° C, preferably from 20 ° C. at 35 ° C The reaction can be carried out in a solvent, preferably in an inert organic solvent. The solvents indicated in relation to the basic cyclisation in process A are suitable. In general, the transformation requires the presence of an activation reagent. They are reactive of suitable activation the condensation agents, such as p. eg dicyclohexylcarbodiimide with polystyrene linkage or without polystyrene linkage (DCC), diisopropylcarbodnmide, 1 -et? l-3- (d? met? lam? noprop? l) carbod? m? da (EDAC), carbonildnmidazole, chlorocarbonic acid such as methylchloroformate, ethyl chloroformate, isopropylchloroformate, isobutylchloroformate, sec-butylchloroformate or ahlchloroformate, pivaloyl chloride, polyphosphocitic acid, propanephosphonic acid anhydride, b? s chloride (2-oxo-3-oxazole? d? n) - phosphoyl (BOPCI) or sulfonyl chlorides, such as methanesulfonyl chloride, toluenesulfonyl chloride or benzenesulfonyl chloride According to one embodiment, preferably EDAC or DCC are used as activation reagents. Preferably the transformation of Vil is carried out with VIII in Presence of a base The compounds mentioned in process A are suitable bases. In one embodiment, tetylamine or N-ethylene isopropylamine or mixtures thereof are used as a base.
special preference N-ethylene isopropylamine The processing can be carried out analogously to the procedure described in process A The compounds of formula VII can in turn be prepared by deprotection of correspondingly protected amino acid compounds IX, in analogy with known processes in the literature, for example according to Glenn L Stahl et al, J Org Chem 43 (11), (1978) 2285-6 or AK Ghosh et al, Org Lett 3 (4), (2001), 635-638 The preparation of Vil from an amino acid compound IX protected by Boc, is represented in the following scheme. In place of the Boc group other amino protecting groups can also be used.
(IX) (VID) The transformation of the compound of formula IX into the compound VII is typically carried out in the presence of an acid at temperatures in a range from -30 ° C to the boiling point of the reaction mixture of preferably 0 ° C. at 50 ° C, especially preferably 20 ° C to 35 ° C. The reaction can be carried out in a solvent, preferably in an inert organic solvent. As a solvent, in principle the aforementioned compounds are used for basic cyclization, especially tetrahydrofuran or dichloromethane or Their mixtures In a preferred embodiment the reaction is carried out in dichloromethane. As acids and acid catalysts, the substances mentioned in process A are used. In an embodiment of the process of the invention, the reaction is carried out in the presence of organic acids, for example in the presence of strong organic acids, such as formic acid, acetic acid or tnfluoroacetic acid or mixtures thereof In one embodiment, preferably the reaction s It is carried out in the presence of tpfluoroacetic acid. The processing can be carried out analogously to the procedure described in process A The compounds of formula IX can be prepared according to the reaction depicted in the following scheme The transformation of compound V with the protected amino acid compounds X can be done in analogy with known procedures in
the literature, for example according to I Ojima et al, J Am Chem Soc, 109 (21), (1987), 6537-6538 or J M Mclntosh et al, Tetrahedrona 48 (30), (1992), 6219-6224
In this scheme, the variables have the meanings that were previously mentioned L represents a leaving group, eg a leaving group mentioned during procedure F Other amino protection groups can also be used instead of Boc The conversion of V to X is usually carried out in the presence of a base. Suitable bases are the compounds mentioned in Process A In another preferred embodiment, lithium dnsopropylamide is used, especially preferably an essentially equimolar amount, especially an equimolar amount as base. Usually the reaction is carried out at temperatures in the range of -78 °. C up to the boiling point of the reaction mixture, preferably from -78 ° C to the boiling point, preferably from -78 ° C to 30 ° C. The reaction can be carried out in a solvent, preferably in a Inert organic solvent As solvents, the solvents indicated for basic cyclization, in particular dichloromethane or tetrahydrofuran or their mixtures, are used in principle. In a preferred embodiment, the reaction is carried out in tetrahydrofuran. The processing can be carried out in analogy with the procedure described in process A. The compounds of formula V can be partly commercially available or can be prepared by transformations described in literature of the corresponding precursor products that are commercially available The amino acid derivatives of formula VIII, X or the XV derivative described below, are also partly commercially available, known from the literature or can be prepared according to known methods in the literature. literature The compounds of formula IV with R1? Hydrogen can be prepared by reacting a piperazine compound of formula IV, wherein R 1 represents hydrogen, with an alkylation medium or an acylation medium, which contains the R 1 residue different from
hydrogen Analogously, compound IV can be prepared with R2? hydrogen by reacting a piperazm compound of formula IV, wherein R 2 represents hydrogen, with an alkylation medium or an acylation medium, containing the R 2 residue other than hydrogen Such transformations can be carried out in analogy to procedures known in the literature, example according to the methods described in IO Donkor et al, Bioorg Med Chem Lett 1 1 (19) (2001), 2647-2649, BB Snider et al, Tetrahedrona 57 (16) (2001), 3301-3307, I Yasuhiro et al, J Am Chem Soc 124 (47) (2002), 14017-14019, or M Falomi et al, Europ J Org Chem (8) (2000), 1669-1675
(IV). { R2 = H.}. (IV) Regarding the means of alkylation or the means of acylation, the same applies as stated for procedure B and C Regarding the reaction conditions of these transformations, the same applies as indicated for the procedure B and C The compounds of formula IV can also be prepared by intramolecular cyclization of the compound of general formula XIII in analogy with other methods known in the literature, for example according to T Kawasaki et al, Org Lett 2 (19) (2000), 3027- 3029, 3027-3029, Igor L Rodionaov et al, Tetrahedron 58 (42)
(2002), 8515-8523 or A L Johnsona et al, Tetrahedrona 60 (2004) 961-965
In that case OR * is a suitable leaving group, R * is here eg CC alkyl especially methyl, ethyl or benzyl
(XIII) (IV) In formula XIII, the variables Rx, A2, R1, R2, R5, R6, R7, R8, Rd, Re and Rf have the meaning indicated for formula II The OR * group represents an appropriate leaving group Oxygen-linked R * is in this case, eg CC alkyl especially methyl, ethyl or phenyl-CC alkyl p-benzyl The cyclization of the compound of formula XIII can be carried out in the presence of a base The reaction is then usually carried out at temperatures in the range from 0 ° C to the boiling point of the reaction mixture, preferably from 10 ° C to 50 ° C, especially preferably from 15 ° C to 35 ° C. The transformation can be carried out in a solvent, preferably in an inert organic solvent As solvents are used in principle, the compounds mentioned for thermal cycling, especially a mixture of tetrahydrofuran-water with a mixing ratio of 1 10 to 10 1 are suitable bases, the bases indicated for the cyclization basic in procedure A, spice potassium tert-butanolate, 2-hydroxy pyridine or an aqueous solution of ammonia or a mixture of these bases. Preferably only one of these bases is used. In a particularly preferred embodiment, the reaction is carried out in the presence of an aqueous solution of ammonia, which for example can be 10 to 50%
v / p The compounds of formula XIII can in turn be prepared according to the synthesis represented in the following scheme in analogy with procedures known in the literature, for example according to Wilford L. Mendelsona et al, Int J Peptide & Protein Research 35 (3), (1990), 249-257, Glenn L Stahl et al, J Org Chem 43 (11), (1978), 2285-2286 or AK Ghosh et al, Org Lett 3 (4), (2001), 635-638
In the Scheme the variables R *, A2, R1, R2, R5, R6, R7, R8, Rd, Re and Rf have the meanings indicated for formula II or XIII The synthesis includes, in a first step, the coupling of compounds of amino acids XV with amino acids VIII protected with Boc in the presence of an activation reagent The transformation of a compound of formula XV with a compound of formula VIII is usually carried out at temperatures ranging from -30 ° C to the boiling point of the mixture of reaction, preferably from 0 ° C to 50 ° C, especially preferably from 20 ° C to 35 ° C The reaction can be carried out in a solvent, preferably in an inert organic solvent. For more details reference is made to the preparation of compound VI by the amidation of amino acid compound VIII with the compound VII In general, the transformation requires the presence of an activation reagent. Suitable activation reagents are condensation agents, such as p. eg dicyclohexylcarbodnmide with polystyrene bond or without polystyrene bond (DCC), diisopropylcarbodnmide, 1-et? l-3- (d? met? lam? noprop? l) carbod? m? da (EDAC), carbonildnmidazole, chlorocarbonic acid such as methylchloroformate, ethylchloroformate, isopropylchloroformate, isobutylchloroformate, sec-butylchloroformate or allyl chloroformate, pivaloyl chloride, phosphorus po acid, propanephosphonic acid anhydride, b? s chloride (2-oxo-3-oxazole? d? n) -phosphorus (BOPCI) or sulfonyl chlorides, such as methanesulfonyl chloride, toluene sulfonyl chloride or
Benzenesulfonyl According to one embodiment, EDAC or DCC are preferably used as activating reagents. Preferably the transformation of XV is carried out with VIII in the presence of a base. The compounds mentioned in process A are suitable bases. In one embodiment they are used as base tethylamine or N-ethylene isopropylamine or mixtures thereof, especially N-ethylene isopropylamine The processing can be carried out in analogy with the procedure ribed in process A The deprotection of compound XIV in compound XIII is typically carried out by treatment with an acid The transformation is usually carried out at temperatures in the range from -30 ° C to the boiling point of the reaction mixture, preferably from 0 ° C to 50 ° C, especially preferably from 20 ° C to 35 ° C. It can be carried out in a solvent, preferably in an inert organic solvent. Solvents are used in principle as solvents indic for the basic cyclization, especially dichloromethane or tetrahydrofuran or mixtures thereof In a preferred embodiment, the reaction is carried out in dichloromethane. As acids, the acids mentioned for process A are used. For more details reference is made to the deprotection of VI in compound II The reaction conditions indicated therein are also suitable for the deprotection of compound XIV. In one embodiment of the process of the invention the reaction is carried out in the presence of organic acids, especially strong organic acids, for example in the presence of acid. formic, acetic acid or tnfluoroacetic acid or mixtures thereof In a preferred embodiment the reaction is carried out in the presence of tnfluoroacetic acid The processing can be carried out analogously to the procedure ribed in process A Preparation examples Example 1-benzyl -6- (2-et? N? L-benc? L) -1, 4-d? Met? Lp? Peraz? N-2, 5-d? Ona
1, 1) Ethyl ester of 2- (tert-butoxycarbonyl-methylene-amine) -3- (2-iodophene) -propionic acid
It was added to the acid ester (tert-butoxycarbon? L-met? L-ammo) -acetic acid (7.4 g, 34 mmol) in tetrahydrofuran (abs, 50 ml) slowly dropwise at -78 ° C. C a solution of lithium dnsopropylamide (2 M in THF / n-heptane, 17 ml, 34 mmol). Stirring was continued for 2 h at this temperature. Then 1-bromomet-l-2-iodo-benzene was slowly added dropwise. (10.0 g, 46 mmol) and stirring continued for 1 h at -78 ° C. The reaction solution was heated slowly (12 h) to room temperature and then concentrated on the rotary evaporator. The residue was taken up in ethyl ester of ethyl acetate. acetic acid, washed, dried and concentrated The residue thus obtained was then purified by column chromatography (S? 02, hexane / acetic acid ethyl ester) 6.4 g (43%) of the meta compound M + Na were obtained (m / z) 456 1, 2) Ethyl ester of 3- (2-iodophene?) -2-met? lam? no-prop? on?
A 2- (tert-butoxycarbonyl-methyleneamino) -3- (2-iodo-phenol) -propionic acid ethyl ester (6.4 g, 15 mmol) CH2CI2 (35 mL) was added tpfluoroacetic acid (25 mL). Stirring was continued for 2 h at room temperature The reaction solution was concentrated on a rotary evaporator, the residue was added to ethyl acetate, washed (NaHC03 sat), dried and concentrated. The residue thus obtained (3.9 g, 79%) was further processed as crude product
M + 1 (m / z) 334 1, 3) Ethyl ester of 2- acid. { [2- (tert-butox? Carbon? L-met? L-am? No) -3-phen? L-prop? On? Ll-met? L-am? No} 3- (2-iodophene?) -prop? On?
Ethyl ester of 3- (2-iodo-phenol) -2-methylamino-propyonic acid (3 94 g, 12 mmol), 2- (tert-butoxycarbonyl) acid was stirred. -met? l-am? no) -3-phen? l-prop? on? co (3 7 g, 13 mmol), N-ethyldiisopropyl-amine (7.8 g, 61 mmol) and EDAC (4.6 g, 24 mmol) in THF (abs, 50 ml) for 16 h. The reaction solution was concentrated on a rotary evaporator. The residue was taken up in ethyl acetate, washed, dried and concentrated after purification by chromatography. in column (S? 02, hexane / acetic acid ethyl ester) 4.0 g (56%) of the meta compound M + Na (m / z) 617 1, 4) Ethyl ester of 3- (2-iodophene? l) -2- [met? l- (2-met? lam? no-3-phen? l-prop? on? l) -am? nol-propionic
It was added to 2- ethyl ester. { [2- (tert-butox? Carbon? L-met? L-am? No) -3-phen? L-prop? On? L] -met? L-am? No} 3- (2-iodo-phen?) -prop? On? Co (2.5 g, 4.2 mmol) in CH2Cl2 (10 ml) tnfluoroacetic acid (10 ml) The mixture was stirred for 2 h at room temperature and then was concentrated on the rotary evaporator. The residue was purified by column chromatography (S? 02, hexane / acetic acid ethyl ester) M + 1 (m / z) 495 1.5) 3-benzyl-6- (2- iodobenzyl) -1,4-d? met? lp? peraz? n-2,5-d? ona
Ethyl ester of 3- (2-iodophene?) -2- [met? L- (2-met? Lam? No-3-phen? L-prop? On? L) -am? No] -prop was added ? on? co (2.1 g, 4.2 mmol) to THF (30 ml) and diluted with NH4OH (25% v / w in H20, 20 ml). Stirring was continued for 12 h at room temperature and then concentrated in the rotary evaporator The residue thus obtained was purified by column chromatography (S? 02, hexane / ethyl ester of acetic acid). Thus, 0.4 g (21%) of a non-polar isomer and 0.6 g ( 31%) of a polar isomer M + 1 (m / z) 449 1, 6) 3-benzyl-1, 4-d? Met? L-6- (2-tr? Met? Ls? Lan? Let ? n? l-benc? l) -p? peraz? n-2,5-d? ona
3-benzyl-6- (2-iodobenzyl) -1,4-d? Met? Lp? Peraz? Na-2 5-d? Ona (polar isomer of 1, 5, 100 mg, 0.22 mmol) were added together with dnsopropylamide (0 5 ml), tpmethylsilylacetylene (40 mg, 0.4 mmol), Pd (PPh3) 4 (60 mg, 0.05 mmol) and Cul (10 mg 0.05 mmol) in DMF ( abs, 5 ml) under argon for 12 h at 80 ° C. After cooling and addition of H20 it was extracted with methyl tert-butylether, the organic phases were dried and concentrated. After purification by column chromatography, 21 mg were obtained ( 23%) of the meta compound as a colorless oil M + 1 (m / z) 419 1.7) 3-benzyl-6- (2-et? N? L-benc? L) -1, 4-d? Metabolite-2,5-dione Was added to 3-benzyl-1, 4-d? met? l-6- (2-tr? met? ls? lan? let? n ? -benz?) -p? peraz? n-2,5-dione (140 mg, 0.22 mmol) in THF (abs, 5 ml) dropwise at 0 ° C tetrabutylammonium fluoride (1 mM in THF, 0.5 ml, 0.5 mmol) The mixture was stirred for 1 h at this temperature. After the addition of NH4Cl solution (saturated, ac), it was extracted with ethyl ester from the acid. acetic, the organic phases were dried and concentrated
After purification by column chromatography, 50 mg (65%) of the meta compound was obtained as a yellow oil. M + 1 (m / z). 346. 1 H-NMR (CDCl 3): d = 2.41 (d, 2H), 2.72 (s, 3H), 2.87 (s, 3H), 3.00 (dm, 1 H), 3.12 (dm, 1 H), 3.31 (s, 1 H), 4.16 (m, 2H), 6.94 (dm, 1 H), 7.14-7.31 (brm, 5H), 7.35 (m, 2H), 7.45 (m, 1 H). In a similar manner, other compounds of formula I were prepared in which the structural elements of the following Table II are used as legend for the following Tables A.1 to A 4.
Table
Table A.1
CD O CNI
Table A.3
Table A.4
Analogously, other compounds of formula I are prepared which are indicated in the following Table A 5 Table A.5
The products were characterized by HPLC / MS (High Performance Liquid Chromatography combined with mass spectrometry), by NMR or through its melting point HPLC Column RP-18 column (Chromo th Speed ROD from Merck KgaA
Germany) Eluent acetonitoplo + 0.1% acid tpfluoroacetico (TFA) / water + 0 1% TFA in a gradient of 5 95 to 95 5 in 5 minutes at 40 ° C MS ionization by electrospray Quadrupol, 80 V (positive mode) Compounds I and their acceptable salts for agpula use are suitable - both as mixtures of isomers, and also in the form of pure isomers - as herbicides. They are suitable as such or as a correspondingly formulated medium. The herbicidal agents, which contain the compound I or the , have great utility to combat the growth of plants on surfaces that are not special crops with high amounts of application In crops such as wheat, Rice, maize, soybeans and cotton they act against weeds and harmful grasses without causing significant crop plants damage This effect occurs above all with low application Regarding respetivo application method, the compounds I or the or the agents containing them, may be used in a variety of other crop plants for eliminating undesirable plants include, for example, the following crops Alhum strain, Ananas comosus, Arachis hypogaea Asparagus officinalis, Avena sativa, Beta vulgans spec altissima Beta vulgans spec rapa, Brassica napus var napus, Brassica napus napobrassica var, Brassica rapa var silvestps, Brassica oleracea, Brassica nigra, camellia sinensis, Carthamus tmctopus, Carya ilhnoinensis, hmona Citrus, smensis Citrus, Coffea arabica (Coffea canephora, Coffea libepca ), Cucumis sativus, Cynodona dactilona, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum , Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasi ensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens cu naps, Linum usitatissimum, Lycopersicona lycopersicum, Malus spec, Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacum (N rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgans, Picea abies, Pinus spec, Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis and Prunus domestica , wild Ribes, Ricinus communis, Saccharum officinarum Secale cereale Smapis alba, Solanum tuberosum, Sorghum bicolor (s vulgare), Theobroma cacao, Tpfolium pratense, Tnticale, Tpticum aestivum, Tpticum durum, Vicia faba, Vitis vinifera Zea also mays compounds I They can also be used in crops, which due to breeding including genetic engineering methods, are tolerant to the action of
herbicides In addition, compounds I can also be used in crops, which due to breeding including genetic engineering methods, are insect-tolerant or fungal infection. It was further found that the compounds of formula I are also suitable for defoliation and / or dried plant parts, which include crop plants such as cotton, potatoes, rapeseed, sunflower, soybean or beans, especially cotton. In this regard were found agents for desiccation and / or defoliation of plants, procedures for the preparation of these media and methods for desiccation and / or defoliation of plants with the compounds of formula I The compounds of formula I are suitable as desiccants, especially for the drying of the above-ground parts of crop plants such as potatoes, rapeseed, sunflower and soybeans, but also cereals With this it is possible to harvest in a completely mechanical way these important crop plants. economic interest the facilitation of the harvest that is made possible by the temporary concentration of the detachment of the trees or the reduction of the fixation to the tree of citrus fruits, olives, or of other species or types of stone fruit, of seed and with peel. the same mechanism, that is, the fomentation of the formation of separating tissues between the parts of the fruit or the leaf and the bud of the plants, is also essential for a good control of the defoliating of useful plants, especially of the cotton. Besides the shortening of the interval of time in which the different cotton plants mature, produces a higher quality of the fibers after harvest The compounds I or, the herbicidal agents that contain them, can for example be applied in the form of aqueous solutions of direct spray, powders suspensions, also suspensions or dispersions, emulsions, aqueous dispersions, pastes, spraying agents, dispersing agents rsión or granules of high concentration, aqueous, oily or others, by spraying, nebulized, pulverized, dispersed, poured or the treatment of the sowing material or mixing with the sowing material The forms of application are according to the intended uses, in each case should ensure the finest possible distribution of the active principles of the invention. The herbicidal agents contain an effective amount as a herbicide of
less one of the compounds of formula I or of a salt acceptable for agricultural use of I and of customary adjuvants for the formulation of plant protection agents are examples of usual adjuvants for the formulation of herbicides, inert adjuvants, solid carriers, surfactants ( as dispersing agents, protective colloids, emulsifiers, wetting agents and adhesive agents), organic and inorganic thickeners, bactericides, antifreezes, defoamers, where appropriate dyes and adhesives for the formulations intended for the planting material. Examples of thickeners (ie the compounds, which give a different flow behavior, ie a high viscosity at rest and low viscosity in movement) the po sacapdos as xanthan gum (Kelzan® from the company Kelco), Rhodopol® 23 (Rhone Poulenc ) or Veegum® (company RT Vanderbilt) as well as minerals in organic and inorganic layers such as Attaclay® (company Engelhard) t) Examples of antifoaming agents are silicone emulsions (such as, for example, Silikon® SRE, Wacker company or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and their mixtures. Bactericides can be added for the stabilization of aqueous herbicidal formulations Examples of bactericides are those based on dichlorophen and hemiformal benzyl alcohol (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) as well as isotiazo nona derivatives such as alkylthiazole and benzisothiazolinones (Acticide MBS from Thor Chemie) are examples of antifreeze, ethylene glycol, propylene glycol, urea og cepna are examples of dyes, both pigments poorly soluble in water, as well as water soluble dyes are indicated as examples, which are included in the names Rhodamm B, C l Pigment Red 1 12 and C l Solvent Red 1 bekannten Farbstoffe, as well as pigment blue 15 4, pigment blue 15 3 pigment blue 15 2, pigment blue 15 1, pigment blue 80, pigment yellow 1, pigment yellow 13 pigment red 1 12, pigment red 48 2 , pigment red 48 1, pigment red 57 1, pigment red 53 1, pigment orange 43 pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49 , acid network 51, acid network 52, acid network 14, acid blue 9, acid yellow 23 basic network 10, basic network 108
Examples of adhesives are polyvinyl alcohol, vinylpyrrolidone, and polyvinyl alcohol. Examples of inert adjuvants include, for example, fractions of mineral oils with a medium to high boiling point, such as kerosene or diesel oil, as well as coal tar oils, as well as petroleum oils. of vegetable or animal origin, aromatic, aliphatic or cyclic hydrocarbons eg paraffin, tetrahydronaftahna, alkylated naphthalenes or their alkylated benzoyl derivatives or their derivatives, alcohols such as methanol, ethanol, propanol butanol, cyclohexanol, ketones such as cyclohexanone or very polar solvents, eg amines such as N-methylpyrrolidone or water Solid vehicles are mineral earths such as silicas, silicates, silicic gels, talc, kaolin, limestone, lime, chalk, clay, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, Magnesium oxide, milled plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate ureas and products vegetables such as cereal flour, tree bark flour, wood and nut shell, cellulose powder or other solid vehicles As surfactants (adjuvants wetting agents, adhesives, dispersants, as well as emulsifiers) alkaline alkaline earth salts are included, and of ammonium of aromatic sulfonic acids, eg ligninsulphonic acids (eg Borrespers, Borregaard types), phenolsulfonic acids, naphtha n-sulfonic acids (Morwet types, Akzo Nobel) and dibutylnaphthalenesulfonic acids (Nekal BASF AG types) as well as fatty acids, sulfonates alkyl and alkyl, sulphonated hexapols, heptanoles and octadecanoles, as well as fatty alcohol glycol ethers, sulfonated naphthalene condensation products and their derivatives with formaldehyde, naphthalene condensation products or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene-pentylene ether, isooctyl phenol, octylphenol or nonylphenol ethoxylates, alkylphenylpolyg coleter, tpbutylphenylpolyglycol ether, alkylaryl ether alcohols, isotencyl alcohol, condensates ethylene oxide of fatty alcohol, ethoxylated castor oil, polyoxyethylenealkylether or poxypropylenealkylether, polybuterol acetate, sorbitol ester, lyes gnin-sulfite as well as proteins, denatured proteins, pohsacapdos (eg methylcellulose) hydrophobic modified starches, polyvinylalcohol (Mowiol Clapant types) polycarboxylates (BASF AG, Sokalan types), polyalkoxylates, polyvinylamine (BASF AG, Lupamm types) polyethyleneimine (BASF AG types Lupasol), polyvinylpyrus dona and its copohmeros
Spraying, dispersing and spraying agents can be prepared by mixing or grinding together the active substances with a solid carrier Granules, eg wrapping granules, impregnating granules and homogeneous granules, can be prepared by linking the active ingredients with solid carriers. prepare aqueous application forms from emulsified concentrates, suspensions, pastes, wettable powders or granules dispersible in water, by the addition of water. To obtain emulsions, pastes or oily dispersions, the compounds of formula I or the can be dissolved as such in a oil or in solvents, can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. But also concentrates can be prepared which are composed of active substance, wetting agents, adhesives, dispersion or emulsifiers and eventually solvents or oil, which are suitable for its dilution with water The concen The compounds of formula I in the ready-to-use preparations can be varied over wide ranges. The formulations usually contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active principle. Active ingredients are used in those with a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum). The compounds I of the invention can, for example, be formulated as follows
1 Products to be diluted in water A Water-soluble concentrates 10 parts by weight of active substance are dissolved with 90 parts by weight of water or a water-soluble solvent Alternatively, wetting agents or other adjuvants are added. When diluting in water, the active substance is dissolved. thus obtaining a formulation with 10% by weight of active ingredient content B Dispersible concentrates 20 parts by weight of active ingredient are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersing agent eg polyvinylpyrrolidone When diluting in water, a dispersion results. The content of active principle is 20% by weight C Emulsifiable concentrates 15 parts by weight of active principle are dissolved in 75 parts by weight of a
organic solvent (eg aromatic alkyl) with the addition of Ca-Dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight) When diluting in water an emulsion results The formulation has 15% by weight of active ingredient content D Emulsions 25 parts by weight of active ingredient are dissolved in 35 parts by weight of an organic solvent (eg aromatic alkyl) with the addition of Ca-dodecylbenzene sulfonate and castor ethoxylate oil (each 5 parts by weight). mixture is added by an emulsifying machine (eg Ultraturax) 30 parts by weight of water and brought to a homogeneous emulsion When diluting in water an emulsion results The formulation has an active substance content of 25% by weight E Suspensions 20 parts in Weight of active ingredient are comminuted with the addition of 10 parts by weight of dispersing agents and wetting agents and 70 parts by weight of water or an organic solvent in a ball mill with water system. for a fine suspension of active ingredient When diluting in water, a stable suspension of the active principle results The content of active principle in the formulation is 20% by weight F Water-soluble and water-dispersible granules 50 parts by weight of active principle they are finely milled with the addition of 50 parts by weight of dispersing and wetting agents and are transformed by means of technical devices (eg by extrusion spray tower fluidized layer) into water-dispersible or water-soluble granules. When diluting in water, a dispersion results or stable solution of the active principle The formulation has an active substance content of 50% by weight G Water-soluble and water-dispersible powders 75 parts by weight of active ingredient are ground with the addition of 25 parts by weight of dispersing agents and moisturizers as well as silicic acid gel in a Rotor-Strator mill When diluted in water, a dispersion or solution results active ingredient stable The formulation has an active substance content of 75% by weight H Gel formulations In a ball mill, 20 parts by weight of active ingredient, 10 parts by weight of dispersing agent, 1 part by weight are milled of gelling agent and 70 parts by weight of water or of an organic solvent to obtain a fine suspension When diluting with
water results in a stable suspension with 20% by weight of active ingredient content
2 Products for direct application I Powders 5 parts by weight of active ingredient are finely milled and mixed well with 95 parts by weight of kaolin in fine particles A spray agent is thus obtained with 5% by weight of active substance content J Granules (GR, FG, GG, MG) 0.5 parts by weight of active ingredient are ground finely and mixed well with
99.5 parts by weight of vehicles The usual procedures for this are extrusion, spray drying or fluidized bed. A granulate is thus obtained for direct application with 0.5% by weight of active ingredient content K ULV solutions ( UL) 10 parts by weight of active ingredient are dissolved in 90 parts by weight of an organic solvent, eg xylene. In this way, a product is obtained for direct application with 10% by weight of active ingredient content. Specific formulations are given below. I 20 parts by weight of the compound of formula I are dissolved in a mixture, which is composed of 80 parts by weight of alkylated benzene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide in 1 mole of N-monoethanolamide of oily acid, 5 parts by weight of calcium salt of the Dodecylbenzenesulfonic acid and 5 parts by weight of the addition product of 40 moles of ethylene oxide in 1 mole of castor oil By pouring and fine distribution of the solution in 100,000 parts by weight of water an aqueous dispersion is obtained, containing 0, 02% by weight of the active ingredient II 20 parts by weight of the compound of formula I are dissolved in a mixture, which is composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 moles of ethylene oxide in 1 mole of isooctylphenol and 10 parts by weight of the addition product of 40 moles of ethylene oxide in 1 mole of castor oil. By pouring and fine distribution of the solution in 100 000 parts by weight of water is obtains an aqueous dispersion, containing 0.02% by weight of active ingredient III 20 parts by weight of the compound of formula I are dissolved in a mixture, which is composed of 25 parts by weight of cyclohexanone, 65 parts by weight of a fraction of mineral oil from boiling point 210 to 280 ° C and 10 parts by weight
of the addition product of 40 moles of ethylene oxide in 1 mole of castor oil By pouring and fine distribution of the solution in 100 000 parts by weight of water an aqueous dispersion is obtained, which contains 0.02% by weight of the active ingredient IV 20 parts by weight of the compound of formula I are mixed with 3 parts by weight of the sodium salt of duboisyl naphthalene sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulphonic acid of a residual sulphite liquor are mixed well. parts by weight of silicic acid gel powder and milled in a hammer mill By means of the fine distribution of the mixture in 20,000 parts by weight of water, a spray mixture is obtained, which contains 0.1% by weight of the Active V 3 parts by weight of the compound of formula I are mixed with 97 parts by weight of kaolin in fine particles A spray agent is thus obtained, which contains 3% by weight of the active ingredient VI 20 parts by weight of the active compound. The compound of formula I is intensively mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of polyglycol ether of fatty acid, 2 parts by weight of sodium salt, a condensate of formaldehyde-phenol-carbamate and 68 parts by weight. weight of a paraffin mineral oil A stable oil dispersion is obtained. V 1 part by weight of the compound of formula I is dissolved in a mixture, which is composed of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight. cast ethoxylated castor oil weight A stable emulsion concentrate VIII is obtained 1 part by weight of the compound of formula I is dissolved in a mixture, which is composed of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol ®
EM 31 (nonionic emulsifier based on ethoxylated castor oil) A stable emulsion concentrate is obtained Application of the compounds I or of the herbicidal agents containing them can be carried out in preemergence, in the post-emergence procedure or together with the seeds of a crop plant There is also the possibility of applying the herbicidal agents or active ingredients when using planting material from a crop plant, previously treated with herbicidal agents or active principles. In case the active ingredients are less tolerable for certain crop plants,
other application techniques can be used, with which the herbicidal agents are sprayed in such a way by means of the spraying equipment, that as far as possible the leaves of the delicate cultivation plants are not included, while the active principles reach the leaves of the plants. unwanted plants growing below, or reaching the surface without covering the soil (post-directed, lay-by) In another embodiment, the application of the compounds of formula I or of the herbicidal agents can be carried out by means of the treatment of sowing material The treatment of sowing material includes essentially all techniques known to the specialist ("seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed drippmg, and seed pelleting" ) based on the compounds of the invention of formula I or the agents prepared therefrom. In that case, the herbicidal agents can be applied dilui two or undiluted The material planting concept includes sowing material of all kinds, such as grains, seeds, fruits, bulbs, segments and similar forms. Preferably, the material concept of harvest refers in this case to grains and seeds. Harvesting material can be used for harvesting the previously mentioned useful plants, but also the harvest material of transgenic plants or obtained by usual cultivation methods. The amounts of application of active principle amount according to the objective to be fought, the time of year, the goal plants and the growth stages of 0, 001 to 3 0, Preferably 0.01 to 1.0 kg / ha of active substance (a S) For the treatment of seeds, the compounds I are generally applied in amounts from 0.001 to 10 Kg per 100 Kg of Seeds In order to broaden the spectrum of action and achieve smergistic effects, the compounds of formula I can be mixed with numerous representatives of other groups of herbicidal active ingredients or growth regulators and applied together. For example, they can be used as mixture add-ons 1, 2 , 4-thia-diazoles, 1,3-t-ad? Azoles, amides, aminophosphate acid and its derivatives, aminotpazoles, anilides, acido (het) -aplox? Alcan? Co and its benzoic acid derivatives and their derivatives , benzothiadiazinones, 2-aro? l-1, 3-c? clohexand? onas, 2-hetaro? l-1, 3-c? clohexand? onas, hetanl-apl-ketones, benzisoxazolidinones, derivatives of meta-CF3-phen Carbamate, quinolinecarboxylic acid and its derivatives, chloroacetanilides, ether derivatives of cycloh-
exenone oxime, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, d? h? drofuran-3-one, dinitroani nas, dinitrophenols, diphenylether, dipipdiles, halocarboxylic acid and its derivatives, ureas, 3-phenoluracites, imidazole , imidazolinones, N-phenol-3, 4,5,6-tetrahydroftalaimides, oxadiazoles, oxiranes, phenols, esters of aploxy- or heteroa-ploxyphenoxypropionic acid, phenylacetic acid and its derivatives, phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pindazines, pipdincarboxylic acid and its derivatives, pipmidyl ether, sulfonamides, sulfonylureas, tpazines, tpazinones, tpazolinones, tpazol-carboxamides, uracils, phenylpyrazines and isoxazolines and their derivatives It may also be useful to apply the compounds alone or in combination with other herbicides or mixed with other agents for the protection of plants, for example with agents for combating phytopathogenic pests or fungi or else bacteria It is also interesting, the miscibility of solutions of mineral salt that are used to compensate for deficiencies of food and / or elements Also additives such as oils and non-phytotoxic oil concentrates can be added Part B Application examples The herbicidal action of the compounds of formula I could be tested by greenhouse tests. cultivation plastic pots were used with clay sand with approximately 3.0% humus as substrate The seeds of the test plants were seeded separated by species For the pre-emergence treatment the active principles suspended or emulsified in water were applied directly after of the planting, by means of nozzles of fine distribution The containers were slightly irrigated to encourage germination and growth and were then covered with transparent plastic covers, until the plants had grown. Due to the cover a uniform germination of the test plants was achieved , while this was not altered by the active ingredients
For the purposes of the post-emergence treatment, the test plants were grown according to the form of growth, first up to a growth height of 3 to 15 cm and then treated with the active principles suspended or emulsified in water. For this purpose, they are sown directly and raised in the same containers, or they were first reared as germinated plants and transplanted to the test vessels just a few days before the treatment.
The plants were maintained in a manner appropriate to each species, at temperatures of 10-25 ° C or 20-35 ° C. The trial period lasted from 2 to 4 weeks. During this time, the plants received care during that period and were evaluated. its reaction to the different treatments It was evaluated on a scale of 0 to 100 The value 100 means no plant outbreak or total destruction of at least the upper parts of the soil and 0 no damage or normal development of the growth An index of at least 70 corresponds to a good herbicidal activity and an index of at least 85 corresponds to a very good herbicidal activity The plants used in the greenhouse tests are composed of the following species
The compounds A 1, 10, A 1, 1 1, A 2,81, A 2,97, A 2,135, A 2,136, A2,222, A 2,223 A 2,224, A 2,226, and A 2,267 show a very good herbicidal action in the post-emergency procedure
In a post-emergency treatment and with an applied amount of 1 kg / ha, the compounds A 1, 10, A 1, 1 1, A 2,135, A2,222, A 2,223 and A 2,224 showed a very good herbicidal action against CHEAL In a post-emergency treatment and with an applied amount of 1 kg / ha, the compounds A 1, 10, A 1, 1 1, A 2,135, A2,222, A 2,223 A 2,224, A 2 226 and A 2 67 showed a very good herbicidal action against AMARE In a post-emergency treatment and with an applied amount of 1 kg / ha, the compounds A 1, 10, A 1, 11, A 2,97, A2,136, A 2,222, A 2 223 and A 2,226 showed a very good herbicidal action against SETVI In a post-emergency treatment and with an applied amount of 1 Kg / ha, compounds A 2.97, A2.136 and A 2.226 showed a very good herbicidal action against LOLMU In a post-emergence treatment and with an applied amount of 3 Kg / ha, compound A 2 81 showed a very good herbicidal action against ECHCG In a post-emergency treatment and with an applied amount of 1 Kg / ha, the compounds A 2,226 and A 2,287 showed a very good herbicidal action against ECHCG in a post-emergency treatment and with an applied amount of 3 Kg / ha , compound A 2 81 showed a very good herbicidal action against ALOMY and AVEFA. In a post-emergency treatment and with an applied amount of 3 kg / ha, the compounds A 2,64, A 2,65, A 2,133 A 2,135, A 2,251, A 2,255, A 2,265, A 2,267,
A 2,273 A 2,274 and A 2,275 showed a very good herbicidal action against SETFA
In a post-emergency treatment and with an applied amount of 1 Kg / ha, the compound
A 2 224 showed a very good herbicidal action against SETFA In a pre-emergency treatment and with an applied amount of 3 kg / ha the compounds A 2,64, A 2,105, A 2,133 A 2,135, A 2,265, A 2,267, A 2,273 A 2,274 and A 2,275 showed a good to very good herbicidal action with respect to ECHCG In a pre-emergency treatment and with an applied amount of 3 kg / ha the compounds A 1, 13 A 5,16, A 2,135, A 2,265, A 2,267, A 2,271, A 2,273 and A 2,276 showed a good to very good herbicidal action with respect to SETIT In a pre-emergency treatment and with an applied quantity of 1 kg / ha, the compounds A 2.97, A 2.136, A 2.224 and A 2,267 showed a very good herbicidal action with respect to APESV In a pre-emergency treatment and with an applied amount of 3kg / ha, the
compound A.2, 81 presented in preemergence a very good herbicidal action with respect to SETFA. In a pre-emergence treatment and with an applied amount of 0.5 kg / ha, compound A.6.17 presented in pre-emergence a very good herbicidal action with respect to AMARE.
Claims (1)
- CLAIMS Use of piperazine compounds of formula I or of the salts acceptable for agricultural use of said piperazine compounds of formula I as herbicides, wherein in formula I the variables have the following meanings R and R 2 independently of each other meaning cyano, alkyl ACe, cycloalkyl C3-C6, alkenyl C3-C6 , C3-C6 cycloalkenyl, C3-C6 alkynyl, C3-C6 cycloalkynyl, phenyl, phenyl-alkyl (C ^ Ce), heterocyclyl, heterocyclyl-C6 alkyl, phenyl-falcoxycarbonyl-C ^ CeJ-alkyl (C? C6) or phenylheterocyclic (C6) alkyl, or COR21, where R21 means hydrogen, C ^ Ce alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C3-C6 cycloalkenyl, C2-C6 alkynyl, C3-C6 cycloalkynyl, hydroxy , C6-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkyloxy, amino, C6-alkylamino, [di-alkyl (C ^ Ce ^ amino, C3-C6 alkenylamino, C3-C6 alkylamino, alkylsulfonylamino CrC6, N- ( alkenyl C2-C6) - N- (alkyl? CrC6) -am? no, N- (alkyl? C2-C6) -N- (alkyl? -C6) -am? no, N- (C 1 -C 6 alkoxy) -N- (C 1 -C 6 alkyl) -amino, N- (C 2 -C 6 alkenyl) -N- (C 1 -C 6 alkoxy) - amn, N- (alkyl? C2-C6) -N- (alkox? -C? -C6) -amino, phenyl, phenylamino, phenoxy, naphthyl or heteroocichlo, or NR22R23, where R22 and R23 independently if they mean hydrogen, ACβ alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl, C3-C6 cycloalkenyl, C3-C6 alkynyl, C3-C6 cycloalkyl or C6 alkylcarbonyl, or OR24, where R24 signifies C-C alkyl, C3-C6 cycloalkyl , C3-C6 alkenyl, C3-C6 cycloalkenyl, C3-C6 alkyl, C3-C6 cycloalkynyl, phenyl or phenyl-alkyl (C, -C6), or S02R25, where R25 means C-? -C6 alkyl or phenyl, where the mentioned fatic, cyclic or aromatic parts of the substituents of R1 and R2 may be partially or totally halogenated and / or may carry one to three of the following cyano, hydroxy, alkyl groups C1-C4, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, C4 alkylthio, [di-alkylene- (C1-C4)] - ammonium, C, -C4 alkylcarbonyl, hydroxycarbonyl, alkoxycarbonyl C C4, aminocarbonyl, C4 alkylaminocarbonyl, [d? -alkyl- (C4-4)] aminocarbonyl or C5-4alkylalkylcarbonyl, and where R1 can also be hydrogen, R3 is a radical R26, OR27, SR28, NR29R30 or N (OR31) R32, wherein R26, R27, R28, R29 and R32 independently of each other mean hydrogen, C6 alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, formyl, alkylcarbonyl CrC6, cycloalkylcarbonyl C3-C6, alkenylcarbonyl C2-C6, alkynylcarbonyl C2-C6, alkoxy C6 alkoxycarbonyl, C2-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, alkylaminocarbonyl ACβ, C3-C6 alkenylaminocarbonyl, C3-C6 alkynylamocarbonyl, C5 alkylsulfonylaminocarbonyl, alkylaminocarbonyl N- (alken? Lo C3-C6) -N- (alkyl? -C? -C6) -am? Nocarbonyl, N- (alkyl? aminocarbonyl, N- (C 1 -C 6 alkoxy) -N- (C 1 -C 6 alkylamino) -aminocarbonyl, N- (C 3 -C 6 alkenyl) -N- (alkoxy C 1 -C 6) C6) -am? Nocarbon? Lo, N- (alkyl? C3-C6) -N- (alkox? -C? -C6) -am? Nocarbon? Lo, D? - (alkyl? C1-? C6) -am? Notcarbonyl, alkylcarbonyl C Ce-alkyl C Ce, alkoxnmino d-Cß-alkyl C C6, N- (alkylamino C? -C6) -? M? No-alkyl CrC6, N- (D? -alqu? Lam? Not CrC6) -? M? No- alkyl C? -C6 or [Tr? -alqu? L- (C1-C4)] only, where the isocyclic or aliphatic parts mentioned of the substituents may be partially or fully halogenated and / or may carry one to three of the following groups: cyano, hydroxy, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, Cr C 4 alkoxy, C 1 alkylthio ? -C, [d? -alkyl- (C? -C4)] -amino, C1-C-alkylcarbonyl, hydroxycarbonyl, C1-C4 alkoxycarbonyl, aminocarbonyl, C? -C4 alkylaminocarbonyl, [d? -alkyl? 1- (C1-C4)] aminocarbonyl or C1-C4 alkylcarbonyloxy, or phenyl, phenyl-d-C6 alkyl, phenylcarbonyl, phenylcarbonyl-C6-C6 alkyl, phenoxycarbonyl, phenylaminocarbonyl, phenylsulfonylammocarbonyl, N- (alkyl d-C6) -N- (phenol) -am? nocarbonyl, phenyl-alkylcarbonyl d-C6, heterocyclyl, heterocyclyl-C6alkyl, heterocyccarbonyl, heterocyccarbonyl-d6alkyl, heterocyc-loxycarbonyl, heterocyclylaminocarbonyl, heterocyclylsulphonylaminocarbonyl, N- (C1-C6alkyl) -N- (heterocyclic) -aminocarbonyl, or heterocyclic alkylcarbonyl d-C6, where the phenyl or heterocyclic portions of the substituents may be halogenated partially or totally and / or may carry one to three of the following nitro, cyano, d-C4 alkyl, C1-C4 haloalkyl, d-C4 alkoxy or d-C4 haloalkoxy groups, or S (0) nR33 where n means 1 or 2, and R33 means d-C6 alkyl, d-C6 haloalkyl or phenyl, and wherein the phenyl substituent may be partially or totally halogenated and / or may carry one to three of the following nitro, cyano, dd alkyl groups , haloalkyl d-C4, alkoxy d-C4 or haloalkoxy C1-C4, and R30 and R3 independently of each other mean hydrogen, C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl or C2-C6 alkynyl, where aliphatic or isocyclic portions of the substituents may be partially or fully halogenated and / or may carry one to three of the following cyan groups or, hydroxy, d-C4 alkyl, d-C4 haloalkyl, C3-C6 cycloalkyl, C4 alkoxy, C1-C4 alkylthio, [d? -alkyl- (d-C4)] - amine, alkylcarbonyl dC l hydroxycarbonyl, C 1 -C 4 alkoxycarbonyl, aminocarbonyl, d-C 4 alkylaminocarbonyl, [dα-alkyl- (C 1 -C 4)] aminocarbonyl or alkylcarbonyloxy d-C 4, phenyl, phenyl-C 6 alkyl, heterocyclyl or heterocyclic alkyl d-C6, wherein the phenyl or heterocyclic portions of the substituents may be partially or fully halogenated and / or may carry one to three of the following nitro, cyano, dd alkyl, haloalkyl d-C4 groups , C 4 alkoxy or C 4 haloalkoxy, R 4, R 5, R 6 independently of each other means hydrogen, C 1 -C 6 alkyl or d 6 alkoxy, where the mentioned aliphatic portions of the substituents R 4, R 5 or R 6 can be halogenated in partial or total form and / or they can carry one to three of the following groups: cyano, hydroxy, d-C4 alkyl, C halo-C4 haloalkyl, C3-C6 cycloalkyl, d-C4 alkoxy, alkylthio dd, [di-alk ?l- (C1-C4)] -amino, alkylcarbonyl dd, hydroxycarbonyl, alkoxycarbonyl dd, aminocarbonyl, alkylaminocarbonyl dd, [d? -alkyl- (dC4)] aminocarbonyl or alkylcarbonyloxy dd, R3 and R4 can also mean together keto group, R7, R8 independently of each other means hydrogen, hydroxy, dC6 alkyl, which may be partially or totally halogenated and / or may carry one to three of the following cyano, hydroxy, d-C4 alkyl, haloalkyl groups d- d, C3-C6 cycloalkyl, alkoxy dd, C, -C4 alkylthio, [d? -alkyl- (C1-C4)] -amino, alkylcarbonyl 0, -04, hydroxycarbonyl, C? -C4 alkoxycarbonyl , aminocarbonyl, C, -C4 alkylaminocarbonyl, [d? -alkyl- (d- d)] am? nocarbonyl or alkylcarbopyloxy C? -C4, A1, A2 independently of each other means aplo or heterolalk, with the exception of indohlo, where Ra is united in po ortho to the binding site of A1 to a C atom or an N atom of A1 and where Ra has one of the meanings indicated below Ra is halogen, cyano, nitro, d-C6 alkyl, C3-C6 cycloalkyl, C2 alkenyl -C6, C3-C6 cycloalkenyl, C-C10 alkanedienyl, C2-C6 alkynyl, [Tr? -alkyl- (C1-C6) -s? I?] -alkyl (C-C6), C3-C6 cycloalkynyl, alkylthio d-C6, alkylsulfinyl Cr C6, aplo, phenyl-alkyl (d-C6), phenol-alkenyl- (C2-C6), phenylsulfonyl-alkyl (d-C6), heterocyclyl, heterocyclic (C6) alkyl or phenol - [C 1 -C 6 alkoxycarbon] - C 1 -C 6 alkyl, Z 1 P (0) (OR 9) 2, Z 2 B (OR 10) 2, where R 9 and R 10, where appropriate, mean hydrogen or alkyl dC 6 and R 10 in Z2B (OR 0) 2 can together form a C2-d, or Z3COR11 alkylene chain, where R11 is hydrogen, d-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C3-C6 cycloalkenyl, C2-C6 alkynyl, cycloalkynyl C3-C6, hydroxy, d-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, amino, alkylamino C ^ Ce, [di-alkyl (d-C6)] amine, alkoxyamino d-C6, [d? - (d-C6) - alkoxy?] ammonium, alkylsulfonylamino C Ce alkylamino C C6sulfon? Lam? No, [di-alkylamino (CrC6)] sulfon? Lam? No, C3-C6 alkenylamino, C3-C6 alkynylamino, N- (C2-C6 alkenyl) -N- (alkyl? CrC6) - amino, N- (alkyl? C2-C6) -N- (alkyl? CrC6) -am? no, N- (alkox? d-C6) - N- (alkyl? CrC6) - amn, N- (alkenyl C2-C6) -N- (alkox? -C? -C6) -am? no, N- (alkyl? C2-C6) -N- (alkoxy? CrC6) -amino, phenyl, phenoxy, phenylamino, naphthyl or heterocyclic, or Z4NR12R13, where Ri- and pi3? Ncjepenc]? Between each other means hydrogen, d-C6 alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl , C3-C6 cycloalkenyl, C3-C6 alkynyl, C3-C6 cycloalkynyl, CrC6 alkylcarbonyl, C3-C6 cycloalkylcarbonyl, [di-alkylamino (CrC6)] carbonyl, alkoxycarbonyl CrC6, alkoxyl carbon ld-C6-alkyl (d-C6), alkylsulfonyl CrC6, alkylaminosulfonyl CrC6, [di-alkylamino (C6)] sulfonyl, phenylcarbonyl, phenylaminocarbonyl, phenylsulfonyl, phenylsulfonylaminocarbonyl or heterocyclylcarbonyl, or Z5CH = N-0-R14, where R4 means hydrogen or alkyl d-C6, or Z6OR15, where R15 is hydrogen, alkyl d-C6 , C3-C6 cycloalkyl, C3-C6 alkenyl, C3-C6 cycloalkenyl, C3-C6 alkyl, C3-C6 cycloalkynyl, CrC6 alkylcarbonyl, C6-alkyl alkoxycarbonyl (d-C6), [di-alkoxy] carbon? I- (CrC6)] - alkyl (CrC6), phenyl or phenyl-alkyl (CrC6), or Z7S02R16, where R16 is alkyl d-Ce or phenyl, and where Z Z2, Z3, Z4, Z5, Z6, Z7 independently of each other means a bond, - CH2-, -CH2-CH2-, -0-CH (R17) -, -S-CH (R18) -, -S (0) -CH (R19) - or -S02CH (R20) -, and where R7, R18, R19 and R20 independently of each other mean hydrogen or alkyl dd, and where the mentioned aliphatic, cyclic or aromatic portions of the Ra substituent may be partially or totally halogenated and / or they can carry one to three of the following groups cyano, hydroxy, d-C4 alkyl, d-C4 haloalkyl, C3-C6 cycloalkyl, d-alkoxy, alkylthio dd, [di-alk- (CrC4)] - amine, alkylcarbonyl CrC4, hydroxycarbonyl, C4 alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl dd, [d? -alkyl- (dC4)] ammoncarbon or alkylcarbon niloxy d-d, and Rb, Rc, Rd, Re and Rf in each case independently of each other are hydrogen or have a meaning indicated for Ra, and where two radicals Ra, Rb or Rc bound to adjacent cyclic atoms of A1 or two residues Rd, Re or Rf bonded to adjacent cyclic atoms of A2 are also equivalents of linear C3-C6 alkylene, which may be fully or partially halogenated and which may carry one to three of the following cyano, hydroxy, dd alkyl, d-C4 haloalkyl, C3- cycloalkyl groups C6, CrC4 alkoxy, alkylthio CrC4, [d? -alkyl- (d-C4)] -amino, alkylcarbonyl CrC4, hydroxycarbonyl, alkoxycarbonyl dd, aminocarbonyl, alkylaminocarbonyl CrC4, [d? -alkyl- (dC4)] am? nocarbonyl or alkylcarbonyloxy CrC4, where a CH2 group in C3-C6 alkylene can be substituted with a carbonyl group, thiocarbonyl group or sulfonyl group and where one or two non-adjacent CH2 groups in C3-C6 alkylene can they are substituted in each case with oxygen, sulfur or a group NR34, where R34 has a meaning indicated for R12 2 Use of piperazine compounds of formula I according to claim 1, characterized in that A1 and A2 independently of each other were selected from the group phenyl, naphthyl, fuplo, thienyl, pyrrolyl, pyrazolyl, thiazole, isothiazolyl, oxazolyl, isoxazolyl, lopalo, tetrazolyl, pipdmilo, pipdazinyl, pipmidinyl, pyrazinyl, tpazinyl and tetrazinyl Use of piperazine compounds of formula I according to one of the preceding claims, characterized in that A1 and A2 independently of each other were selected from the group phenyl, fupol, thienyl, tpazolyl, tetrazolyl and pipdinyl. 4 Use of piperazine compounds of formula I according to one of the preceding claims, characterized in that A1 is equivalent to phenyl or pipdinyl. Use of piperazine compounds of formula I according to one of claims 1 to 4, characterized in that A2 is equivalent to phenyl or thienyl. piperazine of formula I according to one of the preceding claims, characterized in that Ra was selected from halogen, cyano, nitro, C2-C6 alkenyl, C2-C6 alkyl, ZP (0) (0R9) 2, Z3COR11, Z4NR12R13, Z5CH = N-0-R14, Z6OR15, Z7S02R16, alkylthio dC6, alkylsulfinyl CrC6, aplo and heterocyclyl, where Z1 signifies a bond or CH2 and R9 and R10 signify hydrogen or dC6 alkyl, where Z3 means a A union and R is hydrogen, alkyl d-C6, hydroxy, alkoxy CrC6, C3-C6 alkenyloxy, C3-C6 alkynyloxy, amino, alkylamine CrC6, [di-alkyl (d-C6)] amine, alkoxyamino CrC6, N-alkoxy dC6-N-alkylamine d-C6, alkylsulfonylamino CrC6, alkylammo CrC6sulfon? lam? no, [di-alkylamino (C C6)] sulfon? lam? no, phenyl, phenoxy, phenylamino, naphthyl or heterocyclic, or Z4 means a bond or CH2 and R2 and R13 independently between if they mean hydrogen, d-C6 alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, d-C6 alkylcarbonyl, [di-alkylamino (d-C6)] -carbonyl, alkoxycarbonyl CrC6, alkylsulfonyl CrC6, phenylcarbonyl, phenylsulfonyl, or heterocyccarbonyl, or Z5 means a bond or CH and R14 is hydrogen or alkyl dd, or Z6 means a bond or CH2 and R15 is hydrogen, d-C6 alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, C6 alkylcarbonyl, alkoxycarbonyl-CrC6-alkyl (CrC6), phenyl or phenyl-alkyl (CrC6), or Z7 means a bond and R16 is d-C6 alkyl or phenyl, and where Rb, Rc, Rd, Re and Rf regardless of each other e quivalen to hydrogen, have a meaning indicated for Ra as well as can be equivalent to d-C6 alkyl, C3-C6 cycloalkyl, [Tr? -alk? l- (d-C6) -s? l?] -alk? No. (C2-C6), and wherein the mentioned aliphatic, cyclic or aromatic portions of the substituents Ra, Rb, Rc, Rd, Re and Rf may be partially or fully halogenated. Use of piperazine compounds of formula I according to one of the preceding claims, characterized in that R1 signifies hydrogen or d-C6 alkyl, and R2 signifies d-C6 alkyl, where d-C6 alkyl may be partially or totally halogenated in R and R2 8 Use of piperazine compounds of Formula I according to one of the preceding claims, characterized in that R3 is equivalent to R26 or OR27, where R26 and R27 independently of each other mean hydrogen, alkyl dC6 alkylcarbonyl dd, phenyl-alkyl dd or phenylcarbonyl, where the mentioned aliphatic or aromatic portions of the substituents may be partially halogenated or total, or they mean a group S02R31, where R31 means alkyl dd or phenyl and where the phenyl substituent can be partially or totally halogenated and / or can carry one to three groups alkyl dd 9 Use of piperazine compounds of formula I according to one of the preceding claims, characterized in that R4, R5, R6, R7 and R8 are hydrogen equivalent. Use of piperazine compounds of formula I according to one of the claims above, characterized in that both chiral centers in the piperazine ring have the configuration (S, S). Means characterized in that they contain an herbicidally effective amount of at least one piperazine compound of formula I or of an acceptable salt for agricultural use of I according to one of claims 1 to 10 and the usual adjuvants for the formulation of herbicides 12 Process for the preparation of media according to claim 11, characterized in that an effective amount is mixed as a herbicide of at least one piperazine compound of formula I or an acceptable salt for agricultural use von I according to one of claims 1 to 10 and the adjuvants Uses for the formulation of herbicides 13 Process for combating unwanted growth of plants, characterized in that an effective amount is allowed to act as a herbicide of at least one piperazine compound of formula I or of an acceptable salt for agricultural use of I according to with one of claims 1 to 10 about plants, their seeds and / or their habitat 14 Piperazine compounds characterized in that they have the general formula I according to one of the preceding claims, excluding the compounds of the formula I, wherein A1 and A2 are phenyl, R1 is methyl, R2 is hydrogen or methyl, R3, R4, R5, R6, R7, R8 mean hydrogen, the substituents Ra and Rb in each case are equivalent to hydroxy, which are arranged in the two ortho positions of the phenyl ring A1 and Rc, Rd, Re and Rf signify hydrogen, further excluding the compound of formula I wherein A1 is equivalent to phenyl and A2 means 4-? m? dazol? or A1 is equivalent to 4-? m? dazol? lo and A2 means phenyl, furthermore excluding the compound of formula I, where A1 is phenyl, Ra means chlorine, R and Rc are hydrogen, the group A2 (RdReRf) is equivalent to o-chlorophenyl, R and R 2 are methylcarbonyl, and R 3 to R 8, where appropriate, are hydrogen. Process for the preparation of piperazine compounds of formula I according to claim 14, characterized in that a dipeptide of formula II is converted at an elevated temperature. where the variables A1, A2, R1 - R8, Ra, Rb, Rc, Rd, Re and Rf have the meaning indicated for formula I and where ORx is equivalent to a leaving group bound through an oxygen atom, in the presence of a Acid or a base 16 Process for the preparation of piperazine compounds of formula I according to claim 14 with R1? hydrogen, characterized in that a piperazine compound of formula I, wherein R1 is hydrogen, is transformed with an alkylation or an acylating agent, which contains the R1 moiety other than hydrogen Process for the preparation of piperazine compounds of formula I according to claim 14 with R2? Hydrogen, characterized in that a piperazine compound of formula I is transformed, where R2 is hydrogen, with an alkylating agent or an acylation, which contains the R2 residue different from hydrogen. Process for the preparation of piperazine compounds of formula I according to claim 14, characterized in that a piperazine compound of the formula la is transformed, where L means halogen or S (0) nR, with n = 0, 1, 2 and Rk in the meaning of d-C6 alkyl, haloalkyl (d-C6) optionally halogenated or aplo substituted with C4 alkyl, and where the other variables A1, A2, R-R8, Rb, Rc, Rd, Re and Rf have the meaning indicated for formula I, in the presence of a catalyst and a base and a coupling partner containing Ra 19 Process for the preparation of piperazine compounds of formula I according to claim 14, characterized in that Rd is equivalent to COOH, characterized in that a piperazine compound of formula I is transformed, where Ra is equivalent to COOCH3, is transformed with Me3SnOH. Process for the preparation of piperazine compounds of formula I according to claim 14, characterized because Ra is equivalent to a residue CONRuRv or COORw, where Ru and Rv independently of each other mean hydrogen, alkyl dd, C2-C6 alkenyl, C2-C2 alkynyl, alkoxy dd, alkylsulfonyl CrC6, alkylaminosulfomide C C6, [di-alkylamino (CrC6) ] sulphonyl or phenyl, and Rw is d-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl, characterized in that a piperazine compound of formula I is transformed, where Ra is equivalent to COOH, with a chlorination reagent in the acid chloride of formula III where the variables A1, A2, R1-R8, Rb, Rc, Rd, Re and Rf have the indicated meaning for formula I, and then formula III is transformed with an amine HNRURV or an alcohol HORw 21 Procedure for the preparation of compounds of piperazm of formula I according to claim 14, characterized in that a piperazine compound of formula IV is transformed where A2, R1, R2, R5, R6, R7, R8, Rd, Re and Rf have the meanings previously indicated in the presence of a base with a compound of formula V, where A1, R3, R4, Ra, R and Rc have the meanings previously indicated and where L is a leaving group 22 Dipeptides characterized because they have the formula II, where the variables A1, A2, R1 - R8, Ra, Rb, Rc, Rd, Re and Rf have the meanings indicated for formula I and where ORx equals a leaving group bound through an oxygen atom 23 Dipeptides characterized because they have the formula VI, where the variables A1, A2, R1 - R8, Ra, Rb, Rc, Rd, R ° and Rf have the meanings indicated for formula I and SG means a protection group and where ORx is equivalent to a leaving group linked through a oxygen atom
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06000013.0 | 2006-01-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MX2008007819A true MX2008007819A (en) | 2008-09-02 |
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