TR201810585T4 - Bifenil-sübstitüe edilmiş spirosiklik ketoenoller. - Google Patents
Bifenil-sübstitüe edilmiş spirosiklik ketoenoller. Download PDFInfo
- Publication number
- TR201810585T4 TR201810585T4 TR2018/10585T TR201810585T TR201810585T4 TR 201810585 T4 TR201810585 T4 TR 201810585T4 TR 2018/10585 T TR2018/10585 T TR 2018/10585T TR 201810585 T TR201810585 T TR 201810585T TR 201810585 T4 TR201810585 T4 TR 201810585T4
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- TR
- Turkey
- Prior art keywords
- alkyl
- formula
- spp
- compounds
- phenyl
- Prior art date
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- 150000001875 compounds Chemical class 0.000 claims abstract description 160
- 238000000034 method Methods 0.000 claims abstract description 95
- 239000000203 mixture Substances 0.000 claims abstract description 60
- 238000002360 preparation method Methods 0.000 claims abstract description 50
- 239000004009 herbicide Substances 0.000 claims abstract description 44
- 244000038559 crop plants Species 0.000 claims abstract description 10
- 239000003961 penetration enhancing agent Substances 0.000 claims abstract description 6
- -1 cyano, nitro, methyl Chemical group 0.000 claims description 205
- 239000013543 active substance Substances 0.000 claims description 112
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 69
- 239000000460 chlorine Substances 0.000 claims description 58
- 239000001257 hydrogen Substances 0.000 claims description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims description 56
- 229910052801 chlorine Inorganic materials 0.000 claims description 54
- 230000000694 effects Effects 0.000 claims description 50
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 46
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 43
- 229910052794 bromium Inorganic materials 0.000 claims description 43
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 39
- 150000002431 hydrogen Chemical class 0.000 claims description 39
- 229910052731 fluorine Inorganic materials 0.000 claims description 36
- 229910052736 halogen Inorganic materials 0.000 claims description 36
- 150000002367 halogens Chemical class 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 34
- 239000011737 fluorine Substances 0.000 claims description 33
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 31
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 29
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 28
- 239000004480 active ingredient Substances 0.000 claims description 27
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 26
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 22
- 239000003085 diluting agent Substances 0.000 claims description 22
- 229910052796 boron Inorganic materials 0.000 claims description 21
- 239000007921 spray Substances 0.000 claims description 20
- 229910052721 tungsten Inorganic materials 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- 241001465754 Metazoa Species 0.000 claims description 18
- 241000607479 Yersinia pestis Species 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 17
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 235000010290 biphenyl Nutrition 0.000 claims description 16
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 16
- 230000001965 increasing effect Effects 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 14
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 14
- 239000004305 biphenyl Substances 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- OPGCOAPTHCZZIW-UHFFFAOYSA-N diethyl 1-(2,4-dichlorophenyl)-5-methyl-4h-pyrazole-3,5-dicarboxylate Chemical group CCOC(=O)C1(C)CC(C(=O)OCC)=NN1C1=CC=C(Cl)C=C1Cl OPGCOAPTHCZZIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 125000002541 furyl group Chemical group 0.000 claims description 9
- 150000002940 palladium Chemical class 0.000 claims description 9
- 230000008635 plant growth Effects 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 7
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 claims description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 7
- BWUPSGJXXPATLU-UHFFFAOYSA-N dimepiperate Chemical compound C=1C=CC=CC=1C(C)(C)SC(=O)N1CCCCC1 BWUPSGJXXPATLU-UHFFFAOYSA-N 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 7
- MWKVXOJATACCCH-UHFFFAOYSA-N isoxadifen-ethyl Chemical group C1C(C(=O)OCC)=NOC1(C=1C=CC=CC=1)C1=CC=CC=C1 MWKVXOJATACCCH-UHFFFAOYSA-N 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 6
- MCNOFYBITGAAGM-UHFFFAOYSA-N 2,2-dichloro-1-[5-(furan-2-yl)-2,2-dimethyl-1,3-oxazolidin-3-yl]ethanone Chemical compound C1N(C(=O)C(Cl)Cl)C(C)(C)OC1C1=CC=CO1 MCNOFYBITGAAGM-UHFFFAOYSA-N 0.000 claims description 6
- RFEBDZANCVHDLP-UHFFFAOYSA-N 3-[(4-cyanophenyl)methylamino]-6-(trifluoromethyl)quinoxaline-2-carboxylic acid Chemical compound OC(=O)C1=NC2=CC=C(C(F)(F)F)C=C2N=C1NCC1=CC=C(C#N)C=C1 RFEBDZANCVHDLP-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- NNYRZQHKCHEXSD-UHFFFAOYSA-N Daimuron Chemical compound C1=CC(C)=CC=C1NC(=O)NC(C)(C)C1=CC=CC=C1 NNYRZQHKCHEXSD-UHFFFAOYSA-N 0.000 claims description 6
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 6
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 6
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 6
- 125000003386 piperidinyl group Chemical group 0.000 claims description 6
- 125000000335 thiazolyl group Chemical group 0.000 claims description 6
- 125000001544 thienyl group Chemical group 0.000 claims description 6
- YIVXMZJTEQBPQO-UHFFFAOYSA-N 2,4-DB Chemical compound OC(=O)CCCOC1=CC=C(Cl)C=C1Cl YIVXMZJTEQBPQO-UHFFFAOYSA-N 0.000 claims description 5
- VYNOULHXXDFBLU-UHFFFAOYSA-N Cumyluron Chemical compound C=1C=CC=CC=1C(C)(C)NC(=O)NCC1=CC=CC=C1Cl VYNOULHXXDFBLU-UHFFFAOYSA-N 0.000 claims description 5
- 125000005620 boronic acid group Chemical class 0.000 claims description 5
- IWEDIXLBFLAXBO-UHFFFAOYSA-N dicamba Chemical compound COC1=C(Cl)C=CC(Cl)=C1C(O)=O IWEDIXLBFLAXBO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002794 2,4-DB Substances 0.000 claims description 4
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 claims description 4
- WNTGYJSOUMFZEP-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=C(Cl)C=C1C WNTGYJSOUMFZEP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 3
- 125000004008 6 membered carbocyclic group Chemical group 0.000 claims description 3
- 239000005504 Dicamba Substances 0.000 claims description 3
- 239000005574 MCPA Substances 0.000 claims description 3
- WHKUVVPPKQRRBV-UHFFFAOYSA-N Trasan Chemical compound CC1=CC(Cl)=CC=C1OCC(O)=O WHKUVVPPKQRRBV-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 229960003887 dichlorophen Drugs 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- ZAWPDPLWGKAAHU-UHFFFAOYSA-N 2,2-dichloro-n-[2-oxo-2-(prop-2-enylamino)ethyl]-n-prop-2-enylacetamide Chemical compound ClC(Cl)C(=O)N(CC=C)CC(=O)NCC=C ZAWPDPLWGKAAHU-UHFFFAOYSA-N 0.000 claims description 2
- AXHCGXRBOHBEQA-UHFFFAOYSA-N 2-(5-chloro-2-methylphenoxy)acetic acid Chemical compound CC1=CC=C(Cl)C=C1OCC(O)=O AXHCGXRBOHBEQA-UHFFFAOYSA-N 0.000 claims description 2
- BEWNYGSVADPYKQ-UHFFFAOYSA-N 3,6-dichloro-4-(1-ethoxy-1-oxopropan-2-yl)-2-methoxybenzoic acid Chemical compound CCOC(=O)C(C)C1=CC(Cl)=C(C(O)=O)C(OC)=C1Cl BEWNYGSVADPYKQ-UHFFFAOYSA-N 0.000 claims description 2
- PFJJMJDEVDLPNE-UHFFFAOYSA-N Benoxacor Chemical compound C1=CC=C2N(C(=O)C(Cl)Cl)C(C)COC2=C1 PFJJMJDEVDLPNE-UHFFFAOYSA-N 0.000 claims description 2
- UKSLKNUCVPZQCQ-UHFFFAOYSA-N Fluxofenim Chemical compound C=1C=C(Cl)C=CC=1C(C(F)(F)F)=NOCC1OCCO1 UKSLKNUCVPZQCQ-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001449 anionic compounds Chemical class 0.000 claims description 2
- MKQSWTQPLLCSOB-UHFFFAOYSA-N benzyl 2-chloro-4-(trifluoromethyl)-1,3-thiazole-5-carboxylate Chemical compound N1=C(Cl)SC(C(=O)OCC=2C=CC=CC=2)=C1C(F)(F)F MKQSWTQPLLCSOB-UHFFFAOYSA-N 0.000 claims description 2
- LDECUSDQMXVUMP-UHFFFAOYSA-N benzyl 3-[6-[[2-(butylamino)-1-[3-methoxycarbonyl-4-(2-methoxy-2-oxoethoxy)phenyl]-2-oxoethyl]-hexylamino]-6-oxohexyl]-4-methyl-2-oxo-6-(4-phenylphenyl)-1,6-dihydropyrimidine-5-carboxylate Chemical compound O=C1NC(C=2C=CC(=CC=2)C=2C=CC=CC=2)C(C(=O)OCC=2C=CC=CC=2)=C(C)N1CCCCCC(=O)N(CCCCCC)C(C(=O)NCCCC)C1=CC=C(OCC(=O)OC)C(C(=O)OC)=C1 LDECUSDQMXVUMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- JEMXUSHXYOXNFL-UHFFFAOYSA-N ethyl 2-(5-chloroquinolin-8-yl)oxyacetate Chemical compound C1=CN=C2C(OCC(=O)OCC)=CC=C(Cl)C2=C1 JEMXUSHXYOXNFL-UHFFFAOYSA-N 0.000 claims description 2
- YNZGZAJXHXGDBF-UHFFFAOYSA-N ethyl 5-phenyl-4,5-dihydro-1,2-oxazole-3-carboxylate Chemical compound C1C(C(=O)OCC)=NOC1C1=CC=CC=C1 YNZGZAJXHXGDBF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- JCHMGYRXQDASJE-UHFFFAOYSA-N metcamifen Chemical compound C1=CC(NC(=O)NC)=CC=C1S(=O)(=O)NC(=O)C1=CC=CC=C1OC JCHMGYRXQDASJE-UHFFFAOYSA-N 0.000 claims description 2
- DSLIOOISXCVKML-UHFFFAOYSA-N methyl 2-(8-chloroquinoxalin-5-yl)oxyacetate Chemical compound C1=CN=C2C(OCC(=O)OC)=CC=C(Cl)C2=N1 DSLIOOISXCVKML-UHFFFAOYSA-N 0.000 claims description 2
- 150000002891 organic anions Chemical class 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 13
- 230000001225 therapeutic effect Effects 0.000 claims 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 2
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 claims 1
- 125000006730 (C2-C5) alkynyl group Chemical group 0.000 claims 1
- VXJKYWLPNZBSMY-UHFFFAOYSA-N 1,1-dimethyl-3-[4-(naphthalen-1-ylsulfamoyl)phenyl]urea Chemical compound C1=CC(NC(=O)N(C)C)=CC=C1S(=O)(=O)NC1=CC=CC2=CC=CC=C12 VXJKYWLPNZBSMY-UHFFFAOYSA-N 0.000 claims 1
- AHXUVTKVCMOKIX-UHFFFAOYSA-N 1-bromo-4-(chloromethylsulfonyl)benzene Chemical compound ClCS(=O)(=O)C1=CC=C(Br)C=C1 AHXUVTKVCMOKIX-UHFFFAOYSA-N 0.000 claims 1
- XMPCGZCCOXWBKR-UHFFFAOYSA-N 2,2,5-trimethyl-1,3-oxazolidine Chemical compound CC1CNC(C)(C)O1 XMPCGZCCOXWBKR-UHFFFAOYSA-N 0.000 claims 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 claims 1
- JAXUXISKXAOIDD-UHFFFAOYSA-N 2-(5-chloroquinolin-8-yl)oxypropanedioic acid Chemical compound C1=CN=C2C(OC(C(=O)O)C(O)=O)=CC=C(Cl)C2=C1 JAXUXISKXAOIDD-UHFFFAOYSA-N 0.000 claims 1
- ULKOQNVFHBGETA-UHFFFAOYSA-N 5-(4-fluorophenyl)-5-phenyl-4h-1,2-oxazole Chemical compound C1=CC(F)=CC=C1C1(C=2C=CC=CC=2)ON=CC1 ULKOQNVFHBGETA-UHFFFAOYSA-N 0.000 claims 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims 1
- 229910014585 C2-Ce Inorganic materials 0.000 claims 1
- YRMLFORXOOIJDR-UHFFFAOYSA-N Dichlormid Chemical compound ClC(Cl)C(=O)N(CC=C)CC=C YRMLFORXOOIJDR-UHFFFAOYSA-N 0.000 claims 1
- NRFQZTCQAYEXEE-UHFFFAOYSA-N Fenclorim Chemical compound ClC1=CC(Cl)=NC(C=2C=CC=CC=2)=N1 NRFQZTCQAYEXEE-UHFFFAOYSA-N 0.000 claims 1
- 239000004606 Fillers/Extenders Substances 0.000 claims 1
- BWPYBAJTDILQPY-UHFFFAOYSA-N Methoxyphenone Chemical compound C1=C(C)C(OC)=CC=C1C(=O)C1=CC=CC(C)=C1 BWPYBAJTDILQPY-UHFFFAOYSA-N 0.000 claims 1
- VZZVOKHLRXJIEP-UHFFFAOYSA-N ethyl 2-benzhydryloxyacetate Chemical compound C=1C=CC=CC=1C(OCC(=O)OCC)C1=CC=CC=C1 VZZVOKHLRXJIEP-UHFFFAOYSA-N 0.000 claims 1
- ZKDUJUNNBWZZCO-UHFFFAOYSA-N ethyl 5-[(2,4-dichlorophenyl)methyl]-4,5-dihydro-1,2-oxazole-3-carboxylate Chemical compound C1C(C(=O)OCC)=NOC1CC1=CC=C(Cl)C=C1Cl ZKDUJUNNBWZZCO-UHFFFAOYSA-N 0.000 claims 1
- WWHBBYNEFXJGME-UHFFFAOYSA-N ethyl 5-tert-butyl-1-(2,4-dichlorophenyl)pyrazole-3-carboxylate Chemical compound N1=C(C(=O)OCC)C=C(C(C)(C)C)N1C1=CC=C(Cl)C=C1Cl WWHBBYNEFXJGME-UHFFFAOYSA-N 0.000 claims 1
- 125000002349 hydroxyamino group Chemical group [H]ON([H])[*] 0.000 claims 1
- DLCGDGOEOISSHF-UHFFFAOYSA-N methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate Chemical compound C=1C=CC=C(Cl)C=1N1N=C(C(=O)OC)C=C1C1=CC=CC=C1 DLCGDGOEOISSHF-UHFFFAOYSA-N 0.000 claims 1
- LQPRNRFJJUSONA-UHFFFAOYSA-N methyl 2-benzhydryloxyacetate Chemical compound C=1C=CC=CC=1C(OCC(=O)OC)C1=CC=CC=C1 LQPRNRFJJUSONA-UHFFFAOYSA-N 0.000 claims 1
- 150000004714 phosphonium salts Chemical class 0.000 abstract description 15
- 239000011814 protection agent Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 150000003863 ammonium salts Chemical class 0.000 abstract description 5
- 239000000543 intermediate Substances 0.000 abstract description 5
- 241000196324 Embryophyta Species 0.000 description 122
- 239000000126 substance Substances 0.000 description 51
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 41
- 239000003995 emulsifying agent Substances 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 33
- 238000009472 formulation Methods 0.000 description 32
- 230000002363 herbicidal effect Effects 0.000 description 29
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 26
- 230000035515 penetration Effects 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 238000002844 melting Methods 0.000 description 23
- 230000008018 melting Effects 0.000 description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 22
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000003623 enhancer Substances 0.000 description 20
- 240000008042 Zea mays Species 0.000 description 19
- 239000003112 inhibitor Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 17
- 239000002689 soil Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 239000008187 granular material Substances 0.000 description 15
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 125000002877 alkyl aryl group Chemical group 0.000 description 14
- 239000002585 base Substances 0.000 description 14
- 239000002917 insecticide Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 241000238631 Hexapoda Species 0.000 description 13
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 13
- 230000000895 acaricidal effect Effects 0.000 description 13
- 235000005822 corn Nutrition 0.000 description 13
- CPPKAGUPTKIMNP-UHFFFAOYSA-N cyanogen fluoride Chemical group FC#N CPPKAGUPTKIMNP-UHFFFAOYSA-N 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 13
- 229920000151 polyglycol Polymers 0.000 description 13
- 239000010695 polyglycol Substances 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 11
- 241000219146 Gossypium Species 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 150000002170 ethers Chemical class 0.000 description 11
- 108090000623 proteins and genes Proteins 0.000 description 11
- 239000007858 starting material Substances 0.000 description 11
- 229920000742 Cotton Polymers 0.000 description 10
- 235000010469 Glycine max Nutrition 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
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- 229940116861 trichinella britovi Drugs 0.000 description 1
- 229940096911 trichinella spiralis Drugs 0.000 description 1
- REEQLXCGVXDJSQ-UHFFFAOYSA-N trichlopyr Chemical compound OC(=O)COC1=NC(Cl)=C(Cl)C=C1Cl REEQLXCGVXDJSQ-UHFFFAOYSA-N 0.000 description 1
- NFACJZMKEDPNKN-UHFFFAOYSA-N trichlorfon Chemical compound COP(=O)(OC)C(O)C(Cl)(Cl)Cl NFACJZMKEDPNKN-UHFFFAOYSA-N 0.000 description 1
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 description 1
- ONCZDRURRATYFI-TVJDWZFNSA-N trifloxystrobin Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1CO\N=C(/C)C1=CC=CC(C(F)(F)F)=C1 ONCZDRURRATYFI-TVJDWZFNSA-N 0.000 description 1
- HSMVPDGQOIQYSR-KGENOOAVSA-N triflumizole Chemical compound C1=CN=CN1C(/COCCC)=N/C1=CC=C(Cl)C=C1C(F)(F)F HSMVPDGQOIQYSR-KGENOOAVSA-N 0.000 description 1
- XAIPTRIXGHTTNT-UHFFFAOYSA-N triflumuron Chemical compound C1=CC(OC(F)(F)F)=CC=C1NC(=O)NC(=O)C1=CC=CC=C1Cl XAIPTRIXGHTTNT-UHFFFAOYSA-N 0.000 description 1
- AKTQJCBOGPBERP-UHFFFAOYSA-N triflusulfuron Chemical compound FC(F)(F)COC1=NC(N(C)C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2C)C(O)=O)=N1 AKTQJCBOGPBERP-UHFFFAOYSA-N 0.000 description 1
- RROQIUMZODEXOR-UHFFFAOYSA-N triforine Chemical compound O=CNC(C(Cl)(Cl)Cl)N1CCN(C(NC=O)C(Cl)(Cl)Cl)CC1 RROQIUMZODEXOR-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- KVEQCVKVIFQSGC-UHFFFAOYSA-N tritosulfuron Chemical compound FC(F)(F)C1=NC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(F)(F)F)=N1 KVEQCVKVIFQSGC-UHFFFAOYSA-N 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- JARYYMUOCXVXNK-CSLFJTBJSA-N validamycin A Chemical compound N([C@H]1C[C@@H]([C@H]([C@H](O)[C@H]1O)O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)CO)[C@H]1C=C(CO)[C@@H](O)[C@H](O)[C@H]1O JARYYMUOCXVXNK-CSLFJTBJSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000002348 vinylic group Chemical group 0.000 description 1
- 229960004740 voriconazole Drugs 0.000 description 1
- BCEHBSKCWLPMDN-MGPLVRAMSA-N voriconazole Chemical compound C1([C@H](C)[C@](O)(CN2N=CN=C2)C=2C(=CC(F)=CC=2)F)=NC=NC=C1F BCEHBSKCWLPMDN-MGPLVRAMSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- WCJYTPVNMWIZCG-UHFFFAOYSA-N xylylcarb Chemical compound CNC(=O)OC1=CC=C(C)C(C)=C1 WCJYTPVNMWIZCG-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 1
- FJBGIXKIXPUXBY-UHFFFAOYSA-N {2-[3-(4-chlorophenyl)propyl]-2,4,4-trimethyl-1,3-oxazolidin-3-yl}(imidazol-1-yl)methanone Chemical compound C1=CN=CN1C(=O)N1C(C)(C)COC1(C)CCCC1=CC=C(Cl)C=C1 FJBGIXKIXPUXBY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
- A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P33/00—Antiparasitic agents
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P33/00—Antiparasitic agents
- A61P33/10—Anthelmintics
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P33/00—Antiparasitic agents
- A61P33/14—Ectoparasiticides, e.g. scabicides
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- C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
- C07C233/52—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a ring other than a six-membered aromatic ring
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- C07C255/46—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of non-condensed rings
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/65—Halogen-containing esters of unsaturated acids
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- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
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- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
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- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
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Abstract
Buluş, W, X, Y, Z ve CKE'nin yukarıda belirtilen anlamlara sahip olduğu formülün (I) yeni bileşikleri ile, hazırlanmalarına yönelik birçok proses ve ara ürün ile ve bitki koruma ajanı ve/veya herbisit olarak kullanımları ile ve aynı zamanda ilk olarak formülün (I) bileşiklerini ve ikinci olarak da en az bir kültür bitkilerinin toleransını iyileştirici bir bileşiği içeren selektif herbisit bileşimleri ile ilgilidir. Buluş ayrıca amonyum tuzları veya fosfonyum tuzları ve uygun olduğunda penetrasyon artırıcı eklenerek formülün (I) bileşiklerini içeren kültür bitkisi koruma bileşimlerinin güçlendirmesi ile ilgilidir.
Description
TARIFNAME
BIFENIL-SÜBSTITÜE EDILMIS SPIROSIKLIK KETOENOLLER
Mevcut bulus yeni bifenil sübstitüe edilmis spirosiklik ketoenoller ile, bunlarin
hazirlanmasi için birden çok yöntem ile ve bunlarin zararlilarla mücadele ajanlari
ve/veya herbisit olarak kullanilmasi ile ilgilidir. Bulusun konusu ayrica bir yandan bifenil
sübstitüe edilmis spirosiklik ketoenolleri ve diger yandan da kültür bitkilerinin toleransini
iyilestirici bir bilesigi içeren selektif herbisit ajanlar ile ilgilidir.
Mevcut bulus ayrica bilhassa bifenil sübstitüe edilmis ketoenolleri içeren bitki koruma
ajanlarinin etkisinin amonyum veya fosfin tuzlarinin ve gerektiginde penetrasyon
artiricilarin ilavesi ile artirilmasi ile, ilgili ajanlar ile, bunlarin hazirlanmasi için yöntemler
ile ve bunlarin insektisit ve/veya akarisit olarak bitki korumasinda ve/veya istenmeyen
bitkilerin büyümesini önlemek amaciyla kullanilmasi ile ilgilidir.
3-asiI-pirrolidin-2,4-di0nlarin farmasötik özellikleri tarif edilmistir (8. Suzuki et al. Chem.
bilesiklerin biyolojik etkileri tarif edilmemistir.
2,4-dionlar) bildirilmektedir, ancak bunlarin herbisit, insektisit veya akarisit etkisi
bilinmemektedir. Sübstitüe edilmemis, bisiklik 3-aril-pirr0lidin-2,4-dion türevleri (EP-A-
akarisit etkileriyle bilinmektedir.
bilinmektedir.
Ayrica fungusit etkili bifenil sübstitüe edilmis 1H-pirr0lidin-di0n türevleri bilinmektedir
Belirli sübstitüe edilmis A3-dihidrofuran-2-on türevlerinin herbisit özellikler tasidigi
bilinmektedir (bakiniz DE-A-4 014 420). Baslangiç bilesikleri olarak kullanilan tetronik
asitlerin (örnegin 3-(2-metiI-fenil)-4-hidroksi-5-(4-fl0rofeniI)-A3-dihidrofuranon-(2))
sentezi de DE-A-4 014 420'de tarif edilmektedir. Bir insektisit ve/veya akarisit etki
bulgusu olmayan benzer yapili bilesikler Publikation Campbell et al., J. Chem. Soc.,
türevleri bilinmektedir.
Bu bilesiklerin etkisi ve aktivite spektrumu ise özellikle düsük kullanim miktarlarinda ve
konsantrasyonlarda her zaman bütünüyle tatmin edici degildir. Ek olarak, kültür
bitkilerinin bu bilesiklere karsi toleransi da her zaman yeterli degildir. Ayrica, bu
bilesiklerin toksikolojik özellikleri ve/veya çevre açisindan özellikleri de her zaman tam
olarak tatmin edici degildir.
Simdi formül (I) ile gösterilen yeni bilesikler
bulunmustur,
W, hidrojen veya metil anlamina gelir,
X, klor veya metil anlamina gelir,
Y, hidrojen veya metil anlamina gelir,
Z radikali
anlamina gelir
V1, hidrojen, flor, klor, metil, metoksi veya triflorometil anlamina gelir,
V2, hidrojen veya flor anlamina gelir,
CKE grubu
H 0 anlamina gelir,
A, B ve bunlarin bagli oldugu karbon atomu doymus Cs-sikloalkil anlamina gelir,
burada bir halka üyesinin yerini oksijen almistir ve bu gerektiginde metil veya etil ile bir
defa sübstitüe edilmistir,
G, hidrojen (3) veya asagidaki gruplardan biri
JL R1 JJ`M/Rzioi
veya E (f) anlamina gelir,
L, oksijen anlamina gelir,
M, oksijen anlamina gelir ve
E, bir metal iyonu esdegeri veya bir amonyum iyonu anlamina gelir,
R1 her biri gerektiginde flor veya klor ile bir defa sübstitüe edilmis C1-C6-alkil, Cz-Cß-
alkenil, C1-C2-alk0ksi-C1-alkil, C1-Cz-alkiltiyo-C1-alkil veya her biri gerektiginde flor, klor,
metil veya metoksi ile bir defa sübstitüe edilmis siklopropil veya siklohekzil anlamina,
gerektiginde flor, klor, brom, siyano, nitro, metil, metoksi, triflorometil veya
triflorometoksi ile bir defa sübstitüe edilmis fenil anlamina gelir,
R2 her biri gerektiginde flor ile bir defa sübstitüe edilmis Ci-Cg-alkil, Cg-CG-alkenil veya
C1-C4-alkoksi-Cg-Cg-alkil, fenil veya benzil anlamina gelir.
Formül (I) ile gösterilen bilesikler, sübstitüentlerin türüne de bagli olarak, geometrik
ve/veya optik açidan aktif izomerler veya gerektiginde alisilageldik sekilde ayrilabilen
çesitli bilesimlerde izomer karisimlari seklinde mevcut olabilir. Herm saf izomerler hem
de izomer karisimlari, bunlarin hazirlanmasi ve kullanimi ve ayrica bunlari içeren
ajanlar mevcut bulusun konusudur. Kolaylik olmasi açisindan asagida her zaman
formül (I) ile gösterilen bilesikler zikredilecektir ancak hem saf bilesikler hem de
izomerik bilesikleri çesitli oranlarda içeren karisimlar kast edilmektedir.
CKE grubunun anlami (1) dikkate alindiginda asagidaki esas yapi (l-1) elde edilir:
A, B, G, W, X, Y ve Z yukarida belirtilen anlama sahiptir.
G grubunun farkli anlamlari (a), (b), (c) ve (f) dikkate alindiginda, CKE grup (1)
anlamina geldiginde asagidaki esas yapilar (I-1-a), (I-1-b), (I-1-c), (I-1-f) elde edilir,
A, B, E, L, M, w, x, Y, 2, R1, R2 yukarida belirtilen aniamiara sahiptir.
Ayrica, formül (I) ile gösterilen yeni bilesiklerin asagida tarif edilen yöntemlerden birine
göre elde edildigi bulunmustur:
(A) Formül (I-1-a) ile gösterilen sübstitüe edilmis 3-bifenilpirrolidin-2,4-dionlar veya
bunlarin enolleri elde edilir
A, B, W, X, Y ve Z yukarida belirtilen anlamlara sahiptir,
bu amaçla
formül (II) ile gösterilen N-asilamino asit esterleri
H (11)
A, B, W, X, Y ve Z yukarida belirtilen anlamlara sahiptir,
R8 alkil (tercihen C1-C6-alkil) anlamina gelir,
bir seyreltici varliginda ve bir baz varliginda intramoleküler olarak kondanse edilir.
(C) Ayrica, yukarida gösterilen formüller (I-1-a), (I-1-b), (l-1-c), (l-1-f) ile gösterilen
bilesiklerin, burada A, B, G, W, X, Y ve Z yukarida belirtilen anlama sahiptir, elde
edildigi bulunmustur, bu amaçla, formüller (I-1'-a), (I-1'-b), (I-1'-c), (I-1'-f), (l-1'-a), (I-1'
b), (I-1'-c), (I-1'-f) ile gösterilen bilesikler
A, B, G, W, X ve Z yukarida belirtilen anlama sahiptir ve
Z' klor, brom, iyot, tercihen brom anlamina gelir,
formül (IV) ile gösterilen boronik asitler veya boronik asit türevleri ile
Rg hidrojen, C1-C6-alkil veya Cg-Cs-alkandiil anlamina gelir
Z yukarida belirtilen anlama sahiptir,
bir solvent, bir baz ve bir katalizör varliginda reaksiyona sokulur, burada katalizör
olarak özellikle paladyum tuzlari veya paladyum kompleksleri degerlendirilir.
Ayrica,
(D) yukarida gösterilen formül (l-1-b) ile gösterilen bilesiklerin, burada A, B, R1, W, X, Y
ve Z yukarida belirtilen anlamlara sahiptir, elde edildigi bulunmustur, bu amaçla
yukarida gösterilen formül (I-1-a) ile gösterilen bilesikler, burada A, B, W, X, Y ve Z
yukarida belirtilen anlamlara sahiptir,
(0) formül (V) ile gösterilen asit halojenürler ile
R1 yukarida belirtilen anlama sahiptir ve
Hal halojen (özellikle klor veya brom) anlamina gelir
([3) formül (VI) ile gösterilen karboksilik asit anhidritler ile
R1-CO-O-CO-R1 (vi)
R1 yukarida belirtilen anlamlara sahiptir,
gerektiginde bir seyreltici varliginda ve gerektiginde bir asit baglayici madde varliginda
reaksiyona sokulur;
(E) yukarida gösterilen formül (I-1-o) ile gösterilen bilesiklerin, burada A, B, R2, M, W,
X, Y ve Z yukarida belirtilen anlamlara sahiptir ve L oksijen anlamina gelir, elde edildigi
bulunmustur, bu amaçla yukarida gösterilen formül (I-1-a) ile gösterilen bilesikler,
burada A, B, W, X, Y ve Z yukarida belirtilen anlamlara sahiptir,
formül (VII) ile gösterilen kloroformik asit esterleri ile
RZ-M-CO-CI (vii)
R2 ve M yukarida belirtilen anlamlara sahiptir,
gerektiginde bir seyreltici varliginda ve gerektiginde bir asit baglayici madde varliginda
reaksiyona sokulur;
(I) yukarida gösterilen formül (I-1-f) ile gösterilen bilesiklerin, burada A, B, E,
W, X, Y ve Z yukarida belirtilen anlamlara sahiptir, elde edildigi bulunmustur, bu
amaçla yukarida gösterilen formül (I-1-a) ile gösterilen bilesikler, burada A, B,
W, X, Y ve Z yukarida belirtilen anlamlara sahiptir,
formüller (XI) veya (Xll) ile gösterilen metal bilesikleri veya aminler ile
Me(OR1°)t (xi)
Me bir veya iki degerlikli bir metal (tercihen lityum, sodyum, potasyum,
magnezyum veya kalsiyum gibi bir alkali veya toprak alkali metal),
t 1 veya 2 sayisi ve
R”, R”, R12 birbirlerinden bagimsiz olarak hidrojen veya alkil (tercihen C1-Cg-
alkil) anlamina gelir,
gerektiginde bir seyreltici varliginda reaksiyona sokulur,
Ayrica, formül (I) ile gösterilen yeni bilesiklerin zararlilarla mücadele ajani olarak,
tercihen insektisit ve/veya akarisit ve/veya herbisit olarak iyi bir etkililige sahip oldugu,
ek olarak kültür bitkileri tarafindan çok iyi tolere edildigi ve/veya uygun toksikolojik
ve/veya çevreyle ilgili özellikler kazandirdigi bulunmustur.
Sasirtici bir sekilde, ayrica belirli bifenil sübstitüe edilmis, spirosiklik ketoenollerin,
asagida tarif edilen, kültür bitkilerinin toleransini iyilestiren bilesikler
(safenerler/antidotlar) ile birlikte kullanilmasi durumunda kültür bitkilerinin zarar
görmesini önlemekte belirgin derecede iyi oldugu ve özellikle avantajli genis
spektrumlu kombinasyon preparatlari olarak tarim bitkilerinde istenmeyen bitkiler ile
seçici mücadele için örnegin tahillarda ancak ayni zamanda misir, soya ve pirinçte
kullanilabilecegi bulunmustur.
Bulusun konusu ayrica asagidaki bilesenleri içeren bir etkin madde kombinasyonunun
etkili bir miktarini içeren selektif herbisit ajanlardir
(a') formül (I) ile gösterilen en az bir bifenil sübstitüe edilmis, spirosiklik
ketoenol, burada CKE, W, X, Y ve Z yukarida belirtilen anlamlara sahiptir
(b') kültür bitkilerinin toleransini iyilestiren asagidaki bilesik grubundan seçilen
en az bir bilesik:
4-Dikl0roasetiI-1-oksa-4-aza-spiro[, 1-
dikloroasetiI-hekza-hidr0-3,3,8a-trimetilpirrolo[1,2-a]-pirimidin-6(2H)-0n
benzoksazin (Benoxacor), 5-klor-kinolin-8-0ksi-asetik asit-(1-metiI-hekzil esteri)
üre (kumiluron), ci-(siyanometoksimin0)-fenilaset0nitriI (siyometrinil), 2,4-diklor-
fenoksiasetik asit (2,4-D), 4-(2,4-diklor-fenoksi)-bütirik asit (2,4-DB), 1-(1-metil-
1-feniI-etil)-3-(4-metiI-fenil) üre (Daimuron, Dimiron). 3,6-diklor-2-met0ksi-
benzoik asit (dikamba), piperidin-1-tiyokarboksilik asit-S-1-metiI-1-feniI-etil esteri
(dimepiperat), 2,2-diklor-N-(2-okso-2-(2-pr0penilamino)-etiI)-N-(2-pr0penil)-
asetamit (DKA-24), 2,2-dikl0r-N,N-di-2-pr0peniI-asetamit (diklormid), 4,6-diklor-
karboksilik asit etil esteri (fenklorazoI-etil - ayrica bakiniz EP-A-174562 ve EP-
A-346620'deki baglantili bilesikler), 2-klor-4-triflorometil-tiyazoI-ö-karboksilik asit
fenil metil esteri (flurazol), 4-klor-N-(1,3-dioksolan-2-iI-met0ksi)-a-triflor0-
asetofenonoksim (fluksofenim), 3-dikloroasetiI-ö-(Z-furaniI)-2,2-dimetil-
karboksilat (izoksadifen-etil - ayrica bakiniz WO-A-95/07897'deki baglantili
bilesikler), 1-(et0ksikarboniI)-etiI-3,6-diklor-2-met0ksibenzoat (laktidiklor), (4-
kIor-o-toIiI-oksi)-asetik asit (MCPA), 2-(4-kl0r-0-tolil0ksi)-pr0piy0nik asit
(mekoprop), dietiI-1-(2,4-diklor-fenil)-4,5-dihidro-5-metil-1H-pirazoI-3,5-
dikarboksilat (mefenpir-dietil - ayrica bakiniz WO-A-91/07874teki baglantili
dioksolan-2-iI-met0ksimin0)-fenilasetonitril (oksabetrinil), 2,2-diklor-N-(1.3-
metoksiasetik asit, difenil metoksiasetik asit metil esteri, difenil metoksiasetik
asit etil esteri, 1-(2-klor-feniI)-5-feniI-1H-pirazoI-S-karboksilik asit metil esteri, 1-
(2,4-diklor-feniI)-5-metiI-1H-pirazoI-3-karboksilik asit etil esteri, 1-(2,4-
diklorofeniI)-5-izopropiI-1H-pirazoI-3-karb0ksilik asit etil esteri. 1-(2.4-diklor-
feniI)-5-(1,1-dimetiI-etiI)-1H-pirazol-S-karboksilik asit etil esteri, 1-(2,4-diklor-
karboksilik asit etil esteri, 5-fenil-2-izoksazolin-3-karb0ksilik asit etil esteri, 5-(4-
flor-fenil)-5-fenil-2-izoksazolin-B-karboksilik asit etil esteri (ayrica bakiniz WO-A-
büt-1-il) esteri, 5-klor-kin0lin-8-0ksi-asetik asit-4-aliloksi-bütil esteri, 5-kl0r-
kinolin-8-oksi-asetik asit-1-aliloksi-prop-Z-il esteri, 5-kl0r-kinoksalin-8-oksi-asetik
asit-metil esteri, 5-kIor-kin0lin-8-oksi-asetik asit-etil esteri, 5-klor-kin0ksalin-8-
oksi-asetik asit-alil esteri, 5-klor-kinoIin-8-oksi-asetik asit-2-oksi-prop-1-il esteri,
asit-dialil esteri, 5-klor-kin0lin-8-0ksi-mal0nik asit-dietil esteri (ayrica bakiniz EP-
A-582198'deki baglantili bilesikler), 4-karboksi-kroman-4-II-asetik asit (AC-
metoksi-benzofenon, 1-brom-4-klor0metilsüIfoniI-benzen, 1-[4-(N-2-
metoksibenzoiI-süIfamoil)-feniI]-3-metil üre (diger adiyla N-(2-met0ksi-benzoil)-
4-[(metilamin0-karb0niI)-amino]-benzen sülfonamit), 1-[4-(N-2-
metoksibenzoilsülfamoil)-fenil] -3,3-dimetil üre, 1-[4-(N-4,5-
dimetilbenzoilsülfamoil)-fenil]-3-metil üre. 1-[4-(N-naftilsüIfamoiI)-feniI-3,3-dimetil
üre, N-(2-metoksi-5-metiI-benzoil)-4-(sikl0propil aminokarboniI)-benzen
sülfonamit,
ve/veya asagidaki genel formüller ile
genel formül (lla) ile gösterilen
veya genel formül (Ilb) ile gösterilen
veya genel formül (Ilc) ile gösterilen
R1 rii ilki
RH!
m 0, 1, 2, 3, 4 veya 5 sayilari anlamina gelir,
tanimlanan bilesiklerden
A1 asagida kabaca çizimi gösterilen divalent heterosiklik gruplardan biri anlamina gelir,
n 0, 1, 2, 3, 4 veya 5 sayilari anlamina gelir,
A2 gerektiginde C1-C4-alkil ve/veya C1-C4-alkoksi-karb0nil ve/veya C1-C4-alkeniloksi-
karbonil ile sübstitüe edilmis, 1 veya 2 karbon atomuna sahip alkandiil anlamina gelir,
R14 hidroksi, merkapto, amino, Ci-Ce-alkoksi, Ci-CG-alkiltiyo, C1-CG-alkilamino veya di-
(Cq-C4-alkiI)-amino anlamina gelir,
R15 hidroksi, merkapto, amino, C1-C7-alkoksi, C1-Cs-alkeniloksi, C1-Cö-alkeniloksi-C1-
Cs-alkoksi, C1-Ce-alkiltiyo, C1-Cs-alkilamino veya di-(Ci-C4-alkiI)-amino anlamina gelir,
R16 gerektiginde flor, klor ve/veya brom ile sübstitüe edilmis C1-C4-alkil anlamina gelir,
R17 hidrojen, her biri gerektiginde flor, klor ve/veya brom ile sübstitüe edilmis 01-06-
alkil, Cg-Cö-alkenil veya Cg-Cö-alkinil, C1-C4-alkoksi-C1-C4-alkil, dioksolanil-C1-C4-alkil,
furil, furiI-C1-C4-alkil, tiyenil, tiyazolil, piperidinil veya gerektiginde flor, klor ve/veya brom
veya C1-C4-alkil ile sübstitüe edilmis fenil anlamina gelir,
R18 hidrojen, her biri gerektiginde flor, klor ve/veya brorn ile sübstitüe edilmis C1-Cs-
furil, furiI-C1-C4-alkil, tiyenil, tiyazolil, piperidinil veya gerektiginde flor, klor ve/veya brom
veya C1-C4-alkil ile sübstitüe edilmis fenil anlamina gelir, R17 ve R18 ayni zamanda
birlikte her biri gerektiginde C1-C4-alkil, fenil, furil, kaynasik bir benzen halkasi ile veya
bagli olduklari C atomu ile birlikte bir 5- veya 6-üyeli karbosiklus olusturan iki
sübstitüent ile sübstitüe edilmis Ca-Ce-alkandiil veya Cg-Cs-oksaalkandiil anlamina gelir,
R19 hidrojen, siyano, halojen veya istege bagli olarak her biri flor, klor ve/veya brom ile
sübstitüe edilmis C1-C4-alkil, Cg-Cs-sikloalkil veya fenil anlamina gelir,
R2° hidrojen, her biri gerektiginde hidroksi, siyano, halojen veya 01-04-alk0ksi ile
sübstitüe edilmis C1-Ce-alkil, Cg-Cs-sikloalkil veya tri-(C1-C4-alkiI)-silil anlamina gelir,
R21 hidrojen, siyano, halojen veya istege bagli olarak her biri flor, klor ve/veya brom ile
sübstitüe edilmis C1-C4-alkil, Cg-Cs-sikloalkil veya fenil anlamina gelir,
X1 nitro, siyano, halojen, 01-04-alkil, Ci-C4-halojen alkil, Ci-C4-alkoksi veya C1-C4-
halojen alkoksi anlamina gelir,
X2 hidrojen, siyano, nitro, halojen, Ci-C4-alkil, C1-C4-halojen alkil, C1-C4-alkoksi veya
C1-C4-halojen alkoksi anlamina gelir,
X3 hidrojen, siyano, nitro, halojen, C1-C4-alkil, C1-C4-halojen alkil, C1-C4-alkoksi veya
C1-C4-halojen alkoksi anlamina gelir,
ve/veya asagidaki genel formüller ile tanimlanan bilesikler
genel formül (lld) ile gösterilen
1Illill
tO, 1, 2, 3, 4 veya 5 sayilari anlamina gelir,
v 0, 1, 2, 3,4 veya 5 sayilari anlamina gelir,
R22 hidrojen veya C1-C4-alkil anlamina gelir,
R23 hidrojen veya C1-C4-alkil anlamina gelir,
R24 hidrojen, gerektiginde her biri siyano, halonen veya C1-C4-alkoksi ile sübstitüe
amino veya her biri gerektiginde siyano, halojen veya C1-C4-alkil ile sübstitüe edilmis
Cg-Cs-sikloalkil, Cg-Cß-sikloalkoksi, Cg-Ce-sikloalkiltiyo veya Cg-CG-sikloalkilamino
anlamina gelir,
R25 hidrojen, gerektiginde siyano, hidroksi, halojen veya C1-C4-alkoksi ile sübstitüe
edilmis C1-Cs-alkil, her biri gerektiginde siyano veya halojen ile sübstitüe edilmis Cg'Cs'
alkenil veya Ca-CG-alkinil veya gerektiginde siyano, halojen veya C1-C4-alkil ile
sübstitüe edilmis Cs-CG-sikloalkil anlamina gelir,
R26 hidrojen, gerektiginde siyano, hidroksi, halojen veya C1-C4-alk0ksi ile sübstitüe
edilmis C1-C6-alkil, her biri gerektiginde siyano veya halojen ile sübstitüe edilmis Cg-Cs-
alkenil veya C3-C6-alkinil, gerektiginde siyano, halojen veya C1-C4-alkil ile sübstitüe
edilmis Cg-Ce-sikloalkil veya gerektiginde nitro, siyano, halojen, C1-C4-alkil, C1-C4-
halojen alkil, C1-C4-alk0ksi veya C1-C4-halojen alkoksi ile sübstitüe edilmis fenil
anlamina gelir veya R25 ile birlikte her biri gerektiginde C1-C4-alkil ile sübstitüe edilmis
Cz-Cs-alkandiil veya Cg-C5-oksaalkandiil anlamina gelir,
X4 nitro, siyano, karboksi, karbamoil, formil, sülfamoil, hidroksi, amino, halojen, C1-C4-
alkil, C1-C4-halojen alkil, C1-C4-alkoksi veya C1-C4-halojen alkoksi anlamina gelir ve
X5 nitro, siyano, karboksi, karbamoil, formil, sülfamoil, hidroksi, amino, halojen, C1-C4-
alkil, C1-C4-halojen alkil, C1-C4-alk0ksi veya Ci-C4-halojen alkoksi anlamina gelir.
Yukarida listelenen genel veya tercih edilen araliklara göre listelenmis radikal tanimlari
veya açiklamalar kendi aralarinda. ilgili araliklara ve tercih araliklarina göre de istenen
sekilde kombine edilebilir. Bunlar hem son ürünler hem de ilgili öncül ve ara ürünler için
geçerlidir.
Bulusa göre, yukarida tercih edilen (tercihen) seklinde listelenen anlamlarin bir
kombinasyonunun bulundugu formül (I) ile gösterilen bilesikler tercih edilir.
Bulusa göre, yukarida özellikle tercih edilen seklinde listelenen anlamlarin bir
kombinasyonunun bulundugu formül (I) ile gösterilen bilesikler özellikle tercih edilir.
Bulusa göre, yukarida en özellikle tercih edilen seklinde listelenen anlamlarin bir
kombinasyonunun bulundugu formül (I) ile gösterilen bilesikler en özellikle tercih edilir.
Bulusa göre, yukarida bilhassa tercih edilen seklinde listelenen anlamlarin bir
kombinasyonunun bulundugu formül (I) ile gösterilen bilesikler bilhassa tercih edilir.
Alkil veya alkenil gibi doymus veya doymamis hidrokarbon radikalleri, örnegin
Asagidaki radikali içeren bilesikler özellikle öne çikar Z :
alkoksideki gibi heteroatomlar ile baglantili olarak da, mümkün oldugu ölçüde düz
Zincirli veya dallanmis olabilir.
Gerektiginde sübstitüe edilmis olan radikaller, aksi belirtilmedikçe, bir defa veya birden
fazla defa sübstitüe edilmis olabilir, burada birden fazla sübstitüsyon durumunda
sübstitüentler ayni veya farkli olabilir.
Örneklerde belirtilen bilesikler disinda, formül (I) ile gösterilen asagidaki bilesikler de
ayri ayri belirtilebilir:
4-CH3
4-OCH3
4-CH3
4-OCH3
3-CH3
3-OCH3
4-OCH3
4-CH3
4-OCH3
3-CH3
3-OCH3
4-CH3
4-OCH3
4-CH3
4-OCH3
3-CH3
3-OCH3
4-CH3
4-OCH3
4-CH3
4-OCH3
3-CH3
3-OCH3
CH3 CH3 CH3 2 4F &F
CH3 CH3 CH3 2 4r' &F
CH3 CH3 CH3 2 4ci &F
CH3 CH3 CH3 2 aci 4F
CH3 CH3 CH3 3 4F 5F
Bulusa göre etkin maddeler olarak tercihen W, X, Y, F, V1 ve V2 için Tablo 1'de
belirtilen radikal kombinasyonlarindan A ve B için Tablo 2'de belirtilen radikal
kombinasyonlarindan olusan bilesikler degerlendirilir.
40H9T84CH9T
-cHz-CHOCHa-(Cth-
-cm-CH-wHgspH-
CH2OCH3
CH2 ('3_(CH~2)3-
CH2OCH20Ha
CH2 (ll-(CH'Z)3
-(CH2›2 (is-(City
CHQOCHZCHS
('3_(CH'2)2-
(ciigizocHâcH3
Yukarida kültür bitkilerinin toleransini iyilestiren, formüller (Ila), (Ilb), (Ilc), (lld) ve (Ile)
ile gösterilen bilesikler ("herbisit safenerler) baglaminda listelenen gruplarin tercih
edilen anlamlari asagida tanimlanmistir.
m tercihen 0, 1, 2, 3 veya 4 sayilari anlamina gelir.
A1 tercihen asagida kabaca çizimi gösterilen divalent heterosiklik gruplardan biri
anlamina gelir
(1: RH R'ü
n tercihen O, 1, 2, 3 veya 4 sayilari anlamina gelir.
A2 tercihen her biri gerektiginde metil, etil, metoksikarbonil, etoksikarbonil veya
alkiloksikarbonil ile sübstitüe edilmis olan metilen veya etilen anlamina gelir.
R14 tercihen hidroksi, merkapto, amino, metoksi, etoksi, n- veya i-propoksi, n-, i-, 3-
veya t-bütoksi, metiltiyo, etiltiyo, n- veya i-propiltiyo, n-, i-, 3- veya t-bütiltiyo,
metilamino, etilamino, n- veya i-propilamino, n-, i-, 5- veya t-bütilaminoi dimetilamino
veya dietilamino anlamina gelir.
R15 tercihen hidroksi, merkapto, amino, metoksi, etoksi, n- veya i-propoksi, n-, i-, 5-
veya t-bütoksi, 1-metiI-hekziloksi, aliloksi, 1-aliloksimetiI-etoksi, metiltiyo, etiltiyo, n-
veya i-propiltiyo, n-, i-, 5- veya t-bütiltiyo, metilamino. etilamino, n- veya i-propilamino,
n-, i-, 5- veya t-bütilamino. dimetilamino veya dietilamino anlamina gelir.
R16 tercihen her biri gerektiginde flor, klor ve/veya brom ile sübstitüe edilmis metil, etil,
n- veya i-propil anlamina gelir.
R" tercihen hidrojen, her biri gerektiginde flor ve/veya klor ile sübstitüe edilmis metil,
etil, n- veya i-propil, n-, i-, 3- veya t-bütil, propenil, bütenil, propinil veya bütinil,
metoksimetil, etoksimetil, metoksietil, etoksietil, dioksolanilmetil, furili furilmetil, tiyenil,
tiyazolil, piperidinil veya gerektiginde flor, klor, metil, etil, n- veya i-propil, n-, i-, 3- veya
t-bütil ile sübstitüe edilmis fenil anlamina gelir.
R18 tercihen hidrojen, her biri gerektiginde flor ve/veya klor ile sübstitüe edilmis metil,
etil, n- veya i-propil, n-, i-, 3- veya t-bütil, propenil, bütenil, propinil veya bütinil,
metoksimetil, etoksimetil, metoksietil, etoksietil, dioksolanilmetil, furil, furilmetil, tiyenil,
tiyazolil, piperidinil veya gerektiginde flor, klor, metil, etil, n- veya i-propil, n-, i-, 3- veya
t-bütil ile sübstitüe edilmis fenil anlamina veya R17 ile birlikte, gerektiginde metil, etil,
furil, fenil, kaynasik bir benzen halkasi ile veya bagli olduklari C atomu ile birlikte 5-
veya 6-üyeli bir karbosiklus olusturan iki sübstitüent ile sübstitüe edilmis olan -CHg-O-
CHz-CHz' ve -CHz-CHz-O-CHz-CHz- radikallerinden biri anlamina gelir.
R19 tercihen hidrojen, siyano, flor, klor, brom veya her biri gerektiginde flor, klor ve/veya
brom ile sübstitüe edilmis metil, etil, n- veya i-propil, siklopropil, siklobütil, siklopentil,
siklohekzil veya fenil anlamina gelir.
R20 tercihen hidrojen, her biri gerektiginde hidroksi, siyano, flor, klor, metoksi, etoksi, n-
veya i-propoksi ile sübstitüe edilmis metil, etil, n- veya i-propil, n-, i-, 3- veya t-bütil
anlamina gelir.
R21 tercihen hidrojen, siyano, flor, klor, brom veya her biri gerektiginde flor, klor ve/veya
brorn ile sübstitüe edilmis metil, etil, ri- veya i-propil, n-, i-. 5- veya t-bütil, siklopropil,
siklobütil, siklopentil, siklohekzil veya fenil anlamina gelir.
X1 tercihen nitro, siyano, flor, klor, brom, metil, etil, n- veya i-propil, n-, i-, 3- veya t-bütil,
diflorometil, diklorometil, triflorometil, trikloroetil, klordiflorometil, flordiklorometil,
metoksi, etoksi, n- veya i-propoksi, diflorometoksi veya triflorometoksi anlamina gelir.
X2 tercihen hidrojen, nitro, siyano, flor, klor, brom, metil, etili n- veya i-propil, n-, i-, 8-
veya t-bütil, diflorometil, diklorometil, triflorometil, trikloroetil, klordiflorometil,
flordiklorometil, metoksi, etoksi, n- veya i-propoksi, diflorometoksi veya triflorometoksi
anlamina gelir.
X3 tercihen hidrojen, nitro, siyano, flor, klor, brom, metil, etil, n- veya i-propil, n-, i-, 3-
veya t-bütil, diflorometil, diklorometil, triflorometil, trikloroetil, klordiflorometil,
flordiklorometil, metoksi, etoksi, n- veya i-propoksi, diflorometoksi veya triflorometoksi
anlamina gelir.
ttercihen 0, 1, 2, 3 veya 4 sayilari anlamina gelir.
v tercihen O, 1, 2, 3 veya 4 sayilari anlamina gelir.
R22 tercihen hidrojen, metil, etil, n- veya i-propil anlamina gelir.
R23 tercihen hidrojen, metil, etil, n- veya i-propil anlamina gelir.
R24 tercihen hidrojen, her biri gerektiginde siyano, fluor, klor, metoksi, etoksi, n- veya i-
propoksi ile sübstitüe edilmis metil, etil, n- veya i-propil, n-, i-, 3- veya t-bütil, metoksi,
etoksi, n- veya i-propoksi, n-, i-, 3- veya t-bütoksi, metiltiyo, etiltiyo, n- veya i-propiltiyo,
n-, i-, 8- veya t-bütiltiyo, , metilamino, etilamino, n- veya i-propilamino, n-, i-, 3- veya t-
bütilamino, dimetilamino veya dietilamino veya her biri gerektiginde siyano, fluor, klor,
brom, metil, etil, n- veya i-propil ile sübstitüe edilmis siklopropil, siklobütil, siklopentil,
siklohekzil, siklopropiloksi, siklobütiloksi, siklopentiloksi, siklohekziloksi, siklopropiltiyo,
siklobütiltiyo, siklopentiltiyo, siklohekziltiyo, siklo-propilamino, siklobütilamino,
siklopentilamino veya siklohekzilamino anlamina gelir.
R25 tercihen hidrojen, her biri gerektiginde siyano, hidroksi, flor, klor, metoksi, etoksi, n-
veya i-propoksi ile sübstitüe edilmis metil, etil, n- veya i-propil, n-, i- veya s-bütil, her biri
gerektiginde siyano, flor, klor veya brom ile sübstitüe edilmis propenil, bütenil, propinil
veya bütinil veya her biri gerektiginde siyano, flor, klor, brom, metil, etil, n- veya i-propil
ile sübstitüe edilmis siklopropil, siklobütil, siklopentil veya siklohekzil anlamina gelir.
R26 tercihen hidrojen, her biri gerektiginde siyano, hidroksi, flor, klor, metoksi, etoksi, n-
veya i-propoksi ile sübstitüe edilmis metil, etil, n- veya i-propil, n-, i- veya s-bütil, her biri
gerektiginde siyano, flor, klor veya brom ile sübstitüe edilmis propenil, bütenil, propinil
veya bütinil, her biri gerektiginde siyano, flor, klor, brom, metil, etil, n- veya i-propil ile
sübstitüe edilmis siklopropil, siklobütil, siklopentil veya siklohekzil veya gerektiginde
nitro, siyano, flor, klor, brom, metil, etil, n- veya i-propil, n-, i-, 5- veya t-bütil,
triflorometil, metoksi, etoksi, n- veya i-propoksi, diflorometoksi veya triflorometoksi ile
sübstitüe edilmis fenil veya R25 ile birlikte her biri gerektiginde metil veya etil ile
sübstitüe edilmis bütan-1,4-diil (trimetilen), pentan-1,5-diil, 1-0ksa-bütan-1,4-diil veya 3-
0ksa-pentan-1,5-diil anlamina gelir.
X4 tercihen nitro, siyano, karboksi, karbamoil, formil, sülfamoil, hidroksi, aminoi flor,
klor, brom, metil, etil, n- veya i-propil, n-, i-, 5- veya t-bütil, triflorometil, metoksi, etoksi,
n- veya i-propoksi, diflorometoksi veya triflorometoksi anlamina gelir.
X5 tercihen nitro, siyano, karboksi, karbamoil, formil, sülfamoil, hidroksi, amino, flor,
klor, brom, metil, etil, n- veya i-propil, n-, i-, 8- veya t-bütil, triflorometil, metoksi, etoksi,
n- veya i-propoksi, diflorometoksi veya triflorometoksi anlamina gelir.
Bulusa göre herbisit safener olarak en özellikle tercih edilen formül (lla) ile gösterilen
bilesiklerin örnekleri asagidaki tabloda Iistelenmistir.
Tablo: Formül (Ila) ile gösterilen bilesiklere örnekler
m 11'-
A1JkR14 < `U
Örnek Numarasi (Pozisyonlar) (X1)m A1 R14
lIa-3 (2) ci, (4) ci OCzH5
(2) ci, (4) ci
(2) Cl, (4) Cl
(2) ci, (4) ci
OC2H5
(2) Cl, (4) CF3
(2) ci, (4) ci
(2) ci, (4) ci
(2) ci, (4) ci
(2) ci, (4) ci
(2) ci, (4) ci
OC2H5
OC2H5
OC2H5
OC2H5
Bulusa göre herbisit safener olarak en özellikle tercih edilen formül (llb) ile gösterilen
bilesiklerin örnekleri asagidaki tabloda Iistelenmistir.
Tablo: Formül (Ilb) ile gösterilen bilesiklere örnekler
Örnek Numarasi (Pozisyon) X2 (Pozisyon) X3 A2 R15
lIb-2 (5) ci - CH2 OCH3
H2(|3
H2(l3
Örnek Numarasi (Pozisyon) x2 (Pozisyon) x3 A2 R15
llb-13 (5) Cl - OCHgCH=CH2
lIb-14 (5) ci - 00sz
lIb-15 (5) ci - OCH3
Bulusa göre herbisit safener olarak en özellikle tercih edilen formül (llc) ile gösterilen
bilesiklerin örnekleri asagidaki tabloda listelenmistir.
ORTGJLN/R
([10)
Tablo: Formül (Ilc) ile gösterilen bilesiklere örnekler
Örnek Numarasi R16 N(R"R'8)
Örnek Numarasi R16 N(R"R'8)
Bulusa göre herbisit safener olarak en özellikle tercih edilen formül (Ild) ile gösterilen
bilesiklerin örnekleri asagidaki tabloda Iistelenmistir.
Tablo: Formül (Ild) ile gösterilen bilesiklere örnekler
Örnek Numarasi
R22 R23 R24
(Pozisyonlar) (X4):
(2) OCH3
(2) OCH3
(2) OCH3
(2) OCH3
(2) OCH3
(2) OCH3
(5) CHa
(2) OCHs
(5) CHs
(2) 00H3
(5) CH3
(2) OCH3
(5) CH3
(2) OCH3
(5) CHs
(2) OCH3
(5) CHei
(2) OCH3
(5) CH3
(2) OCH3
(5) CH3
(Pozisyonlar) (X5)v
Örnek Numarasi
Bulusa göre herbisit safener olarak en özellikle tercih edilen formül (Ile) ile
R22 R23 R24
(Pozisyonlar) (X4)t
(2) OCH3
(5) CHs
(2) OCH3
(5) CH?,
(2) OCH3
(5) CHs
(2) OCH3
(5) CHs
(2) OCH3
(5) CHs
(2) OCH3
(5) CH3
(2) OCH3
(5) CH3
(2) OCH3
(2) OCHg
(2) OCH3
(3) CHa
(4) CHs
(2) OCHs
bilesiklerin örnekleri asagidaki tabloda Iistelenmistir.
(Pozisyonlar) (X5)v
gösterilen
Tablo: Formül (Ile) ile gösterilen bilesiklere örnekler
Örnek Numarasi
C3H7-n
C3H7-i
C3H7-n
C3H7-i
(Pozisyonlar) (X4)t
(2) OCH3
(2) OCH3
(2) OCH3
(2) OCH3
(2) OCH3
(2) OCH3
(2) OCH3
(5) CH3
(2) OCH3
(5) CHs
(2) OCHs
(5) CH3
(2) OCH3
(5) CH3
(2) OCH3
(5) CHs
(2) OCH3
(Pozisyonlar) (X5)v
Örnek Numarasi R22 R25 R2'î (Pozisyonlar) (X4)t (Pozisyonlar) (X5)v
(5) CHs
Kültür bitkilerinin toleransini iyilestiren bilesik [bilesen (b')] olarak klokuintoset-meksil,
fenklorazoI-etil, izoksadifen-etil, mefenpir-dietil, furilazol, fenklorim, kumiluron, dimiron,
dimepiperatlar ve lie-5 ve Ile-11 bilesikleri en çok tercih edilir. burada klokuintoset-
meksil ile mefenpir-dietil ayni zamanda izoksadifen-etil özellikle öne çikabilir.
Safener olarak bulusa göre kullanilacak olan, genel formül (Ila) ile gösterilen bilesikler
bilinmektedir ve/veya bilinen yöntemlerle hazirlanabilmektedir (bakiniz WO-A-
Safener olarak bulusa göre kullanilacak olan, genel formül (Ilb) ile gösterilen bilesikler
bilinmektedir ve/veya bilinen yöntemlerle hazirlanabilmektedir (bakiniz 191736).
Safener olarak bulusa göre kullanilacak olan, genel formül (llc) ile gösterilen bilesikler
bilinmektedir ve/veya bilinen yöntemlerle hazirlanabilmektedir (bakiniz DE-A-2218097,
Safener olarak bulusa göre kullanilacak olan, genel formül (Ild) ile gösterilen bilesikler
bilinmektedir ve/veya bilinen yöntemlerle hazirlanabilmektedir (bakiniz DE-A-
Safener olarak bulusa göre kullanilacak olan, genel formül (Ile) ile gösterilen bilesikler
bilinmektedir ve bilinen yöntemlerle hazirlanabilmektedir (bakiniz WO-A-99/66795/US-
A-6251827).
Formül (I) ile gösterilen bir etkin madde ile yukarida tanimlanan bir safenerden olusan
bulusa göre selektif herbisit kombinasyonlarin örnekleri asagidaki tabloda listelenmistir.
Tablo: Bulusa göre kombinasyonlara örnekler
Formül (I) ile gösterilen etkin maddeler Safener
l-1 -a KIokuintoset-meksil
Formül (I) ile gösterilen etkin maddeler
Safener
FenklorazoI-etil
Izoksadifen-etil
Mefenpir-dietil
Furilazol
Fenklorim
Ku miluron
Daimuron /Dimiron
Dimepiperat
KIokuintoset-meksil
FenklorazoI-etil
Izoksadifen-etil
Mefenpir-dietil
Furilazol
Fenklorim
Ku miluron
Daimuron /Dimiron
Dimepiperat
KIokuintoset-meksil
FenklorazoI-etil
Izoksadifen-etil
Mefenpir-dietil
Formül (I) ile gösterilen etkin maddeler Safener
l-1-c Furilazol
l-1-c Ile-5
Formül (I) ile gösterilen etkin maddeler Safener
l-1 -f Izoksadifen-etil
l-1 -f Mefenpir-dietil
l-1-f Ile-11
Simdi sasirtici bir sekilde, yukarida tanimlanan, genel formül (I) ile gösterilen bifenil
sübstitüe edilmis spirosiklik ketoenollerden ve yukarida listelenen grup (b') içerisinden
safenerlerden (antidotlar) olusan etkin madde kombinasyonlarinin çok iyi bir tarim
bitkisi toleransi ile birlikte özellikle yüksek bir herbisit etkililige sahip oldugu ve farkli
kültürlerde, özellikle tahillarda (öncelikle bugday), ancak ayni zamanda soya, patates,
misir ve pirinçte de selektif yabani ot mücadelesi için kullanilabilecegi bulunmustur.
Burada, bir herbisitin kültür bitkileri üzerindeki zarar verici etkisini antagonize edebilen
çok sayida bilinen safener veya antidot içerisinden özellikle yukarida listelenen grup
(b') bilesiklerinin, yabani otlara karsi herbisit etkiyi önemli ölçüde bozmaksizin bifenil
sübstitüe edilmis spirosiklik ketoenollerin kültür bitkileri üzerindeki zarar verici etkisini
neredeyse tamamen kaldirmak için uygun olmasi sasirticidir.
Burada grup (b')'den özellikle ve en çok tercih edilen kombinasyon ortaginin özellikle
kültür bitkileri olarak örnegin bugday, arpa ve çavdar gibi tahil bitkilerinin ancak ayni
zamanda misir ve pirincin korunmasindaki avantajli etkisi vurgulanabilir.
Literatürde çesitli etkin maddelerin etkisinin amonyum tuzlarinin ilave edilmesiyle
artirilabildigi tarif edilmistir. Burada deterjan etkili tuzlar (örnegin WO 95/017817) veya
uzun alkil ve/veya aril sübstitüentlere sahip tuzlar, permeabilize edici etki gösteren veya
etkin maddenin çözünürlügünü yükselten tuzlardir (örnegin EP-A 0 453 086, EP-A 0
belirli etkin maddeler ve/veya ilgili ajanlarin belirli uygulamalari için etkiyi açiklar. Yine
diger durumlarda, asitlerin kendisinin insektler üzerinde paralize edici etki gösterdigi
sülfonik asit tuzlari söz konusudur (US 2 842 476). Etkinin örnegin amonyum sülfat ile
artirilmasi örnegin glifosat, fosfinotrisin ve belirli siklik ketoenoller için tarif edilmistir (US
için benzer bir etki WO 07/068428'de tarif edilmistir.
Ayrica belirli etkin maddeler ve uygulamalari için formülasyon yardimci maddesi olarak
amonyum sülfatin kullanimi da tarif edilmistir (WO 92/16108), ancak buralarda etkinin
artirilmasi için degil formülasyonun stabilize edilmesi için kullanilmistir.
Simdi tamamen sasirtici bir sekilde, formül (I) ile gösterilen bifenil sübstitüe edilmis
spirosiklik ketoenoller sinifindan insektisitlerin ve/veya akarisitlerin ve/veya herbisitlerin
etkisinin, uygulama solüsyonuna amonyum veya fosfonyum tuzlari ilave edilerek veya
bu tuzlar formül (I) ile gösterilen bifenil sübstitüe edilmis spirosiklik ketoenolleri içeren
bir formülasyona dahil edilerek belirgin ölçüde artirilabilecegi bulunmustur. Mevcut
bulusun konusu ayrica amonyum veya fosfonyum tuzlarinin, etkin madde olarak
insektisit ve/veya akarisit etkili, formül (I) ile gösterilen bifenil sübstitüe edilmis
spirosiklik ketoenolleri içeren bitki koruma ajanlarinin etkisinin artirilmasi amaciyla
kullanilmasidir. Mevcut bulusun konusu ayrica, herbisit ve/veya akarisit ve/veya
insektisit etkili, formül (I) ile gösterilen bifenil sübstitüe edilmis spirosiklik ketoenolleri ve
etkiyi artiran amonyum veya fosfonyum tuzlarini içeren ajanlardir ve hatta hem formüle
edilmis etkin maddelerdir hem de kullanima hazir ajanlardir (püskürtme sivilari).
Bulusun konusu son olarak ayrica bu ajanlarin zararli insektler ve/veya örümcek
akarlari ve/veya istenmeyen bitkilerin büyümesi ile mücadele amaciyla kullanilmasidir.
Formül (I) ile gösterilen bilesikler genis bir insektisit ve/veya akarisit ve/veya herbisit
etki spektrumuna sahiptir, bununla birlikte, bagimsiz olarak etki ve/veya bitkinin
toleransi yetersizdir. Bununla birlikte, bu özellikler amonyum veya fosfonyum tuzlarinin
ilavesiyle bütünüyle veya kismen iyilestirilebilir.
Etkin maddeler bulusa göre bilesimlerde genis bir konsantrasyon araliginda
kullanilabilir. Burada etkin maddelerin formülasyondaki konsantrasyonu genellikle
agirlikça %0,1-50'dir.
Bulusa göre, formül (1) ile gösterilen, bifenil sübstitüe edilmis spirosiklik ketoenoller
sinifindan etkin maddeleri içeren bitki koruma ajanlarinin etkisini yükselten amonyum
veya fosfonyum tuzlari formül (III') ile tanimlanir
R29_ li): R27 RSO ("11)
D azot veya fosfor anlamina gelir,
D tercihen azot anlamina gelir,
R26, R27, R28 ve R29 birbirlerinden bagimsiz olarak hidrojen veya her biri
gerektiginde sübstitüe edilmis Ci-Ca-alkil veya bir veya birden fazla defa
doymamis, gerektiginde sübstitüe edilmis C1-Cg-alkilen anlamina gelir, burada
sübstitüentler halojen, nitro ve siyano içerisinden seçilebilir,
R26, R”, R2& ve R29 birbirlerinden bagimsiz olarak hidrojen veya her biri
gerektiginde sübstitüe edilmis C1-C4-alkil anlamina gelir, burada sübstitüentler
halojen, nitro ve siyano içerisinden seçilebilir,
RZG', R27, R28 ve R29 özellikle tercihen birbirlerinden bagimsiz olarak hidrojen,
metil, etil, n-propil, i-propil, n-bütil, i-bütil, s-bütil veya t-bütil anlamina gelir,
R26', R27, R28 ve R29 en özellikle tercihen hidrojen anlamina gelir,
n 1, 2, 3 veya 4 anlamina gelir,
n tercihen 1 veya 2 anlamina gelir,
R3° bir inorganik veya organik anyon anlamina gelir,
R30 tercihen hidrojen karbonat, tetraborat, florür, bromür, iyodür, klorür,
monohidrojen fosfat, dihidrojen fosfat, hidrojen sülfat, tartrat, sülfat, nitrat,
tiyosülfat, tiyosiyanat, formiyat, Iaktat, asetat, propiyonat, bütirat, pentanoat
veya oksalat anlamina gelir,
R3° tercihen Iaktat, sülfat, nitrat, tiyosülfat, tiyosiyanat, oksalat veya formiyat
anlamina gelir.
R30 en özellikle tercihen sülfat anlamina gelir.
Bulusa göre öne çikan etkin madde, tuz ve penetrasyon artirici kombinasyonlari
asagidaki tabloda Iistelenmistir. Burada, "teste göre penetrasyon artirici" kütikula
artirici olarak etki eden herhangi bir bilesigin uygun oldugu anlamina gelir.
Formül (III') ile gösterilen amonyum ve fosfonyum tuzlari, formül (I) ile gösterilen, bifenil
sübstitüe edilmis siklik ketoenolleri içeren bitki koruma ajanlarinin etkisini yükseltmek
amaciyla genis bir konsantrasyon araliginda kullanilabilirler. Genellikle, kullanima hazir
bitki koruma ajanlarinda amonyum veya fosfonyum tuzlari 0,5 ila 80 mmoI/I, tercihen
Formüle edilmis bir üründe, amonyum ve/veya fosfonyum tuzu konsantrasyonu
formülasyonun istenen etkin madde konsantrasyonuna seyreltilmesinin ardindan
burada belirtilen genel, tercih edilen veya özellikle tercih edilen araliklar içerisinde
kalacak sekilde seçilir. Burada tuzun formülasyondaki konsantrasyonu genellikle
agirlikça %1-50'dir.
Bulusun tercih edilen bir düzenlemesinde, etkiyi artirmak amaciyla bitki koruma
ajanlarina yalnizca bir amonyum ve/veya fosfonyum tuzu degil, ayni zamanda ek
olarak bir penetrasyon artirici da ilave edilir. Ancak, bu durumlarda bile etkide daha da
büyük bir artisin gözlenmesi çok sasirticidir. Mevcut bulusun konusu ayrica
penetrasyon artiricilar ile amonyum ve/veya fosfonyum tuzlarinin bir
kombinasyonunun, etkin madde olarak insektisit etkili, formül (I) ile gösterilen bifenil
sübstitüe edilmis siklik ketoenolleri içeren bitki koruma ajanlarinin etkisinin artirilmasi
amaciyla kullanilmasidir. Mevcut bulusun konusu ayrica, herbisit ve/veya akarisit
ve/veya insektisit etkili, formül (I) ile gösterilen bifenil sübstitüe edilmis siklik
ketoenolleri, penetrasyon artiricilari ve amonyum ve/veya fosfonyum tuzlarini içeren
ajanlardir ve hatta hem formüle edilmis etkin maddelerdir hem de kullanima hazir
ajanlardir (püskürtme sivilari). Bulusun konusu son olarak ayrica bu ajanlarin zararli
insektler ve/veya örümcek akarlari ile mücadele için kullanilmasidir.
Mevcut baglamda, penetrasyon artiricilar olarak agrokimyasal etkin maddelerin
bitkilere nüfuzunu iyilestirmek amaciyla genellikle kullanilan tüm maddeler
degerlendirilir. Penetrasyon artiricilar bu baglamda, aköz püskürtme sivilarindan
ve/veya püskürtme kalintisindan bitkinin kütikulasina penetre olmalari ve bu sekilde,
etkin maddelerin kutikuladaki hareketliligini (mobilite) artirabilmeleri ile tanimlanirlar.
özelligin tayin edilmesi amaciyla kullanilabilir.
Penetrasyon artiricilar olarak örnegin alkanoI-alkoksilatlar degerlendirilir. Bulusa göre
penetrasyon artiricilar formül (IV') ile gösterilen alkanoI-alkoksilatlardir
R-O-(-AO)V-R' (iv')
R 4 ila 20 karbon atomuna sahip düz Zincirli veya dallanmis alkil anlamina gelir,
R' hidrojen, metil, etil, n-propil, i-propil, n-bütil, I-bütil, t-bütil, n-pentil veya n-hekzil
anlamina gelir,
AO bir etilen oksit radikali, bir propilen oksit radikali, bir bütilen oksit radikali veya etilen
oksit ile propilen oksit veya bütilen oksit radikallerinin karisimlari anlamina gelir ve
v 2 ila 30 arasindaki sayilar anlamina gelir.
Tercih edilen bir penetrasyon artirici grubu, asagidaki formül ile gösterilen
alkanoilalkoksilatlardir
R-O-(-EO-)n-R' (IV'-a)
R yukarida belirtilen anlamlara sahiptir,
R' yukarida belirtilen anlamlara sahiptir,
EO -CHz-CHz-O- anlamina gelir ve
n 2 ila 20 arasindaki sayilar anlamina gelir.
Diger bir tercih edilen bir penetrasyon artirici grubu, asagidaki formül ile gösterilen
alkanoI-alkoksilatlardir
R yukarida belirtilen anlamlara sahiptir,
R' yukarida belirtilen anlamlara sahiptir,
PO grubu CH,, anlamina gelir,
p 1 ila 10 arasindaki sayilar anlamina gelir ve
q 1 ila 10 arasindaki sayilar anlamina gelir.
Diger bir tercih edilen bir penetrasyon artirici grubu, asagidaki formül ile gösterilen
alkanoI-alkoksilatlardir
R-O-(-PO-),-(EO-)s-R' (lV'-c)
R yukarida belirtilen anlamlara sahiptir,
R' yukarida belirtilen anlamlara sahiptir,
PO CHs grubu anlamina gelir,
r 1 ila 10 arasindaki sayilar anlamina gelir ve
s 1 ila 10 arasindaki sayilar anlamina gelir.
Diger bir tercih edilen bir penetrasyon artirici grubu, asagidaki formül ile gösterilen
alkanol-alkoksilatlardir
R-O-(-EO-)p-(-BO-)q-R'
R ve R' yukarida belirtilen anlamlara sahiptir,
EO CHg-CHg-O- anlamina gelir,
BO CHa grubu anlamina gelir,
p 1 ila 10 arasindaki sayilar anlamina gelir ve
q 1 ila 10 arasindaki sayilar anlamina gelir.
Diger bir tercih edilen bir penetrasyon artirici grubu, asagidaki formül ile gösterilen
alkanol-alkoksilatlardir
R ve R' yukarida belirtilen anlamlara sahiptir,
BO CHs grubu anlamina gelir,
EO CH2-CH2-O- anlamina gelir,
r 1 ila 10 arasindaki sayilar anlamina gelir ve
s 1 ila 10 arasindaki sayilar anlamina gelir.
Diger bir tercih edilen bir penetrasyon artirici grubu, asagidaki formül ile gösterilen
alkanoI-alkoksilatlardir
R' yukarida belirtilen anlamlara sahiptir,
t 8 ila 13 arasindaki sayilar anlamina gelir
u 6 ila 17 arasindaki sayilar anlamina gelir.
Yukarida verilen formüllerde
R tercihen bütil, i-bütil, n-pentil, i-pentil, neopentil, n-hekzil, i-hekzil, n-oktil, i-oktil, 2-etil-
hekzil, nonil, i-nonil, desil, n-dodesil, i-dodesil, Iauril, miristil, i-tridesil, trimetiI-nonil,
palmitil, stearil veya eikosil anlamina gelir.
Formül (IV-c) ile gösterilen alkanoI-alkoksilatlara örnek olarak asagidaki formül ile
gösterilen 2-etiI-hekzil-alkoksilat
PO CH3 radikali anlamina gelir ve
8 ve 6 sayilari ortalama degerleri gösterirler, verilebilir.
iEOlß-I
Formül (IV-d) ile gösterilen alkanoI-alkoksilatlara örnek olarak asagidaki formül
EO CHz-CHz-O- anlamina gelir,
BO CHa radikali anlamina gelir ve
, 6 ve 2 sayilari ortalama degerleri gösterirler, verilebilir.
Formül (IV'-f) ile gösterilen özellikle tercih edilen alkanol-alkoksilatlar, bu formül ile
gösterilen bilesiklerdir, burada
t 9 ila 12 arasindaki sayilar ve
u 7 ila 9 arasindaki sayilar
grubu anlamina gelir.
Formül (IV'-f-1) ile gösterilen alkanoI-alkoksilatlar en özellikle tercihen belirtilir,
t 10,5 ortalama deger anlamina gelmektedir ve
u 8,4 ortalama deger anlamina gelmektedir.
Alkanol alkoksilatlar yukaridaki formüller ile genel olarak tanimlanir. Bu maddeler, farkli
zincir uzunluklarina sahip belirtilen tipte maddelerin karisimlaridir. Bu nedenle, indisler
için tam sayilardan sapabilecek olan ortalama degerleri hesaplayin.
Verilen formüller ile gösterilen alkanol-alkoksilatlar bilinmektedir ve kismen piyasadan
satin alinabilirler veya bilinen yöntemlerle hazirlanabilirler (bakiniz WO 98/35 553, WO
Penetrasyon artirici olarak örnegin formül (I) ile gösterilen bilesiklerin püskürtme
kalintisindaki yararlanimini artiran maddeler de degerlendirilir. Bunlar arasinda örnegin
mineral veya bitkisel yaglar bulunur. Yaglar olarak genellikle agrokimyasal ajanlarda
kullanilabilen mineral veya bitkisel, gerektiginde modifiye edilmis tüm yaglar
degerlendirilebilir. Ömek olarak ayçiçek yagi, kolza yagi, zeytinyagi. bezir yagi,
misirözü yagi, pamuk çekirdegi yagi ve soya fasülyesi yagi veya belirtilen yaglarin
esterleri belirtilebilir. Kolza yagi, ayçiçek yagi ve bunlarin metil veya etil esterleri tercih
Bulusa göre ajanlarda penetrasyOn artiricilarin konsantrasyonu genis bir aralikta
degistirilebilir. Bunlar formüle edilmis bir bitki koruma ajaninda genellikle agirlikça %1
ila 95 oraninda, tercihen agirlikça %1 ila 55 oraninda. özellikle tercihen agirlikça %15 -
40 oraninda bulunurlar. Kullanima hazir ajanlarda (püskürtme sivilari) konsantrasyon
genellikle 0,1 ile 10 9/1 arasinda, tercihen 0,5 ile 5 g/I arasinda yer alir.
Bulusa göre bitki koruma ajanlari örnegin tensidler veya dispersan yardimci maddeler
veya emülgatörler gibi baska bilesenler de içerebilir.
Iyonik olmayan tensidler veya dispersan yardimci maddeler olarak genellikle
agrokimyasal ajanlarda kullanilabilen bu tür bütün maddeler degerlendirilebilir.
Tercihen polietilen oksit-polipropilen oksit blok kopolimerleri, linear alkollerin polietilen
glikol eterleri, yag asitlerinin etilen oksit ve/veya propilen oksit ile reaksiyon ürünleri,
ayrica polivinil alkol, polivinil pirrolidon, polivinil alkol ve polivinil pirrolidonun karisik
polimerleri ve ayrica (met)akrilik asit ve (met)akrilik asit esterlerinin kopolimerleri,
ayrica gerektiginde fosfatlanmis ve gerektiginde bazlar ile nötralize edilmis olabilecek
alkil etoksilat ve alkilaril etoksilat, bunlara örnek olarak sorbitol etoksilat belirtilebilir ve
ayrica polioksialkilen amin türevleri.
Anyonik tensidler olarak genellikle agrokimyasal ajanlarda kullanilabilen bu tür bütün
maddeler degerlendirilebilir. Alkilsülfonik asitlerin veya aralkilsülfonik asitlerin alkali
metal ve toprak alkali metal tuzlari tercih edilir.
Diger bir tercih edilen anyonik tensid veya dispersan yardimci madde grubu, bitkisel
yaglarda az çözünen polistiren sülfonik asit tuzlari, polivinil sülfonik asit tuzlari, naftalen
sülfonik asit-formaldehit kondenzasyon ürünlerinin tuzlari, naftalen sülfonik asit. fenol
sülfonik asit ve formaldehit kondenzasyon ürünlerinin tuzlari ve ayrica Iignin sülfonik
asit tuzlaridir.
Bulusa göre formülasyonlarin içerebilecegi katki maddeleri olarak emülgatörler, köpük
önleyici ajanlar, koruyucu ajanlar, antioksidanlar, boyar maddeler ve inert dolgu
materyalleri degerlendirilir.
Tercih edilen emülgatörler etoksillenmis nonilfenoller, alkil fenollerin etilen oksit ve/veya
propilen oksit ile reaksiyon ürünleri, etoksillenmis aril alkil fenoller, ayrica etoksillenmis
ve propoksilenmis aril alkil fenoller ve ayrica sülfatlanmis veya fosfatlanmis aril alkil
etoksilatlar veya etoksi-propoksilatlardir, burada polietilen oksit-sorbitan yag asidi
esterleri ve sorbitan yag asidi esterleri gibi sorbitan türevleri örnek olarak verilebilir.
Yöntem (A)'ya göre baslangiç maddesi olarak N-[6-metiI-3(4-flor-feniI)-fenilasetiI]-1-
amino-siklohekzan-karboksilik asit etil esteri kullanilirsa, bulusa göre yöntemin akisi
asagidaki reaksiyon semasiyla gösterilebilir;
Yöntem (C)'ye göre baslangiç ürünleri olarak 3-[(2,6-dimetiI-3-br0m)-feniI]-4,4-
(pentametilen)-pirrolidin-2,4-dion ve 4-florofenil boronik asit kullanilirsa, reaksiyonun
akisi asagidaki semayla gösterilebilir:
Fîalalizi'ir
Yöntem (Dd)'ya göre baslangiç maddeleri olarak 9-[(2-kl0r-5-(4-flor-fenil))-fenil]-4-0ksa-
7-aza-bisiklo[5.4.0]dekan-8,10-dion ve pivaloil hidroklorür kullanilirsa, bulusa göre
yöntemin akisi asagidaki reaksiyon semasiyla gösterilebilir:
Yöntem (D)'ye (vaiyant ß) göre baslangiç bilesikleri olarak 3-[(6-metil-3-(4-fl0r-fenil))-
feniI]-4-hidroksi-5,5-pentametilen-A3-dihidrofuran-2-on ve asetik hidrit kullanilirsa,
bulusa göre yöntemin akisi asagidaki reaksiyon semasiyla gösterilebilir:
/\ (1_ O P CC_\ i HICJLÜ
Yöntem (E)'ye göre baslangiç bilesikleri olarak 9-[2,6-dimetil-3-(4-fl0rofenil)-feniI]-4-
oksa-7-aza-bisikIo-[5.4.0]-dekan-8,10-dion ve kloroformik asit etil esteri kullanilirsa,
bulusa göre yöntemin akisi asagidaki reaksiyon semasiyla gösterilebilir:
Yöntem (I)'ya göre baslangiç maddesi olarak 9-[2-metiI-5-(3,4-difl0r-fenil)-fenil]-4-oksa-
7-aza-bisiklo[5.4.0]-dekan-8,10-dion ve NaOH kullanilirsa, bulusa göre yöntemin akisi
asagidaki reaksiyon semasiyla gösterilebilir:
Bulusa göre yöntem (A)'da baslangiç maddeleri olarak kullanilan, formül (Il) ile
gösterilen bilesikler
A, B, W, X, Y, 2 ve R8 yukarida belirtilen anlamlara sahiptir,
yenidir.
Formül (II) ile gösterilen asilamino asitler, örnegin formül (XV) ile gösterilen amino asit
türevleri
A COZRS
A, B ve R8 yukarida belirtilen anlamlara sahiptir,
formül (XVI) ile gösterilen sübstitüe edilmis fenilasetik asit türevleri ile
W, X, Y ve Z yukarida belirtilen anlamlara sahiptir ve
U örnegin karbonil diimidazol, karbonil diimitler (örnegin disiklohekzil karbodiimit) gibi
karboksilik asit aktivasyon reaktifleri, fosforilasyon reaktifleri (örnegin POCIg, BOP-Cl),
halojenasyon ajanlari, örnegin tiyonil klorür, oksalil klorür, fosgen veya kloroformik asit
esterleri ile katilan bir ayrilan grup anlamina gelir,
,1968)
veya formül (XVII) ile gösterilen asilamino asitleri
A, B, W, X, Y ve Z yukarida belirtilen anlamlara sahiptir,
esterlestirerek elde edebilir (Chem. Ind. (London) 1568 (1968)).
Formül (XVII) ile gösterilen bilesikler
A, B, W, X, Y ve Z yukarida belirtilen anlamlara sahiptir,
yenidir.
Formül (XVII) ile gösterilen bilesikler, formül (XVIII) ile gösterilen amino asitler
AXCOZH
B NH (xviii)
A ve B yukarida belirtilen anlamlara sahiptir,
formül (XVI) ile gösterilen sübstitüe edilmis fenilasetik asit halojenürleri ile
U, W, X, Y ve Z yukarida belirtilen anlamlara sahiptir
örnegin Schotten-Baumann'a göre asillenerek elde edilir (Organikum, VEB Deutscher
Verlag der Wissenschaften, Berlin 1977, S. 505).
Formül (XVI) ile gösterilen bilesikler yenidir. Prensipte bilinen yöntemlerle
hazirlanabilirler (bakiniz örnegin H. Henecka, Houben-Weyl, Methoden der
basvurulari).
Formül (XVI) ile gösterilen bilesikler, örnegin formül (XIX) ile gösterilen sübstitüe
edilmis fenilasetik asitler
W, X, Y ve Z yukarida belirtilen anlama sahiptir,
halojenasyon ajanlari ile (örnegin tiyonil klorür, tiyonil bromür, oksalil klorür, fosgen,
fosfor triklorür, fosfor tribromür veya fosfor pentaklorür) veya fosforilasyon reaktifleri ile
(örnegin POCI3, BOP-CI), gerektiginde bir seyreltici (Örnegin tolüen veya metilen klorür
gibi gerektiginde klorlu alifatik veya aromatik hidrokarbonlar) varliginda, -20°C ila
150°C araligindaki, tercihen -10°C ile 100°C arasindaki sicakliklarda reaksiyona
sokularak elde edilebilir.
Formül (XV) ve (XVIII) ile gösterilen bilesikler kismen giriste atifta bulunulan patent
basvurularindan bilinmektedir ve/veya bilinen yöntemlerle hazirlanabilirler (bakiniz
Formül (XVIIIa) ile gösterilen, A ve B'nin bir halka olusturdugu sübstitüe edilmis siklik
aminokarboksilik asitler genellikle Bucherer-Bergs sentezi ile veya Strecker sentezi ile
elde edilebilirler ve farkli izomerik formlarda bulunurlar. Böylece, Bucherer-Bergs
sentezi kosullarinda agirlikli olarak R radikallerinin ve karboksil gruplarinin ekvatoryal
konfigürasyonda oldugu izomerler (kolaylik saglamasi amaciyla asagida [3 olarak ifade
edilmektedir) elde edilirlen, Strecker sentezi kosullarina göre agirlikli olarak amino
grubunun ve R radikallerinin ekvatoryal konfigürasyonda oldugu izomerler (kolaylik
saglamasi amaciyla asagida 0 olarak ifade edilmektedir) olusur.
R H NH? R H COZH
Buchcrcr-Scrgs scntczi Strecker scntczi
3339 (1975).
Ayrica, yukaridaki yöntem (A)'da kullanilan formül (II) ile gösterilen baslangiç maddeleri
A, B, W, X, Y, Z ve R8 yukarida belirtilen anlamlara sahiptir,
formül (XX) ile gösterilen aminonitriller
H_'î' CEN (XX)
A ve B yukarida belirtilen anlamlara sahiptir,
formül (XVI) ile gösterilen sübstitüe edilmis fenilasetik asit halojenürleri ile
COU (XVI)
W, X, Y ve Z yukarida belirtilen anlamlara sahiptir,
formül (XXI) ile gösterilen bilesikleri verecek sekilde
A, B, W, X, Y ve Z yukarida belirtilen anlamlara sahiptir,
reaksiyona sokularak,
ve bunlar akabinde bir asidik alkolize tabi tutularak hazirlanabilir. (EP-A-595130).
Formül (XXI) ile gösterilen bilesikler de yenidir.
burada tarif edilen yöntemlerle hazirlanabilmektedir.
Örnegin formül (XlX) ile gösterilen bilesikler,
W, X, Y ve Z yukarida belirtilen anlamlara sahiptir,
a) formül (XIX-a) ile gösterilen bilesikler
Y CH2-002H (XlX-u)
X ve Y yukarida belirtilen anlama sahiptir,
2' klor, brom veya iyot, tercihen brom anlamina gelir,
formül (IV) ile gösterilen boronik asitler veya boronik asit türevleri ile
2 ve R9 yukarida belirtilen anlama sahiptir,
bir solvent, bir baz ve bir katalizör (tercihen bir paladyum tuzu veya paladyum
kompleksi, örnegin paladyum tetrakis(trifenilfosfin)) varliginda reaksiyona sokularak
CO'R” {\..\`Illi
W, X, Y, Z ve R8 yukarida belirtilen anlama sahiptir,
asitlerin veya bazlarin varliginda, bir solvent varliginda, genel olarak bilinen standart
kosullar altinda saponifiye edilerek veya
y) formül (XIX-b) ile gösterilen fenilasetik asitler
v CHQ-COQH (XIX-b)
W, X ve Z yukarida belirtilen anlama sahiptir,
formül (XXIV) ile gösterilen halojen bilesikleri ile,
Z-Hal (XXIV)
2 yukarida belirtilen anlama sahiptir ve
Hal klor, brom veya iyot, tercihen brom ve iyot anlamina gelir,
bir solvent, bir baz ve bir katalizör (tercihen bir paladyum tuzu veya yukarida belirilen
paladyum komplekslerinden biri) varliginda reaksiyona sokularak elde edilir.
Formüller (N) ve (XXlV) ile gösterilen bilesikler kismen bilinmektedir. kismen satin
alinabilmektedir veya burada prensipte bilinen yöntemlerle hazirlanabilmektedir.
ve WO 98/05 6538'den bilinmektedir veya buralarda tarif edilen yöntemlerle
hazirlanabilmektedir. Formül (XIX-b) ile gösterilen bilesikler kismen WO 05/016873'ten
bilinmektedir veya burada tarif edilen yöntemlerle hazirlanabilmektedir.
burada tarif edilen yöntemlerle hazirlanabilmektedir.
Formül (XXIII) ile gösterilen bilesikler
CO R” iXXIlI!
W, X, Y, 2 ve R8 yukarida belirtilen anlama sahiptir,
örnegin,
formül (XXIII-a) ile gösterilen fenilasetik asit esterleri
Y CO.__R“-' i:\\iii-J.»
R8, W, X, Y ve Z' yukarida belirtilen anlama sahiptir,
formül (IV) ile gösterilen boronik asitler ve boronik asit türevleri ile
2 ve R9 yukarida belirtilen anlama sahiptir,
bir solvent, bir baz ve bir katalizör (tercihen bir paladyum tuzu veya yukarida belirilen
paladyum komplekslerinden biri) varliginda reaksiyona sokularak elde edilir.
ve WO 98/0563 basvurularindan bilinmektedir veya buralarda tarif edilen yöntemlerle
hazirlanabilmektedir.
Yukaridaki yöntem (C)'de baslangiç maddeleri olarak kullanilan formül (I-1'-a), (I-1'-b),
(l-1'-c), (I-1'-f) ile gösterilen bilesikler, burada A, B, W, X ve Y yukarida belirtilen
anlamlara sahiptir ve Z' klor, brom veya iyot anlamina, tercihen brom anlamina gelir,
tarif edilen yöntemlerle hazirlanabilmektedir.
Formül (IV) ile gösterilen boronik asitler veya boronik asit türevleri
Z ve R9 yukarida belirtilen anlamlara sahiptir,
kismen satin alinabilir veya genel olarak bilinen yöntemlerle kolay bir sekilde
hazirlanabilir.
Bulusa göre yöntemler (D), (E), (I)'nin yürütülmesinde ayrica baslangiç maddeleri
olarak kullanilan formül (V) ile gösterilen asit halojenürler, formül (VI) ile gösterilen
karboksilik asit anhidritler, formül (VII) ile gösterilen kloroformik asit esterleri ve formül
(Xl) ve (XII) ile gösterilen metal hidroksitleri, metal alkoksitleri veya aminler organik
veya inorganik kimyada genel olarak bilinen bilesiklerdir.
Yöntem (A)'nin özelligi, formül (H) ile gösterilen bilesiklerin, burada A, B, W, X, Y, Z ve
R8 yukarida belirtilen anlamlara sahiptir, bir baz varliginda bir intramoleküler
kondenzasyona sokulmasi ile karakterize edilmesidir.
Seyreltici maddeler olarak bulusa göre yöntem (A)'da tüm inert organik solventler
kullanilabilir. Tercihen hidrokarbonlar, örnegin tolüen ve ksilen, ayrica eterler, örnegin
dibütil eter, tetrahidrofuran, dioksan, glikol dimetil eter ve diglikol dimetil eter, ayrica
polar solventler, örnegin dimetil sülfoksit, sülfolan, dimetil formamit ve N-metiI-pirrolidon
ve ayrica örnegin metanol, etanol, propanol, izo-propanol, bütanol, izo-bütanol ve tert.-
bütanol gibi alkoller kullanilabilir.
Baz (deprotonasyon ajani) olarak, bulusa göre yöntem (A) yürütülürken alisildik bütün
proton akseptörleri kullanilabilir. Tercihen, ayni zamanda örnegin trietil benzil amonyum
klorür, tetrabütil amonyum bromür, Adogen 464 (= metil trialkiI(C3-C10)amonyum klorür)
veya TDA 1 (= tris-(metoksietoksietil)-amin) gibi faz transfer katalizörlerinin varliginda
da kullanilabilen alkali metal ve toprak alkali metal oksitleri, hidroksitleri ve karbonatlari,
örnegin sodyum oksit, potasyum oksit, magnezyum oksit, kalsiyum oksit, sodyum
karbonat, potasyum karbonat ve kalsiyum karbonat kullanilir. Ayrica sodyum veya
potasyum gibi alkali metaller kullanilabilir. Ayrica alkali metal ve toprak alkali metal
amitleri ve hidrürleri, örnegin sodyum amit, sodyum hidrür ve kalsiyum hidrür ve ayrica
ayni zamanda sodyum metilat, sodyum etilat ve potasyum tert.bütilat gibi alkali metal
Reaksiyon sicakliklari bulusa göre yöntem (A) yürütülürken genis bir aralikta
degistirilebilir. Genellikle 0°C ile 250°C arasindaki, tercihen 50°C ile 150°C arasindaki
sicakliklarda çalisilir.
Bulusa göre yöntem (A) genellikle normal basinç altinda yürütülür.
Bulusa göre yöntem (A) yürütülürken formül (II) ile gösterilen reaksiyon bilesenleri ve
deprotonize olmus bazlar genellikle yaklasik olarak iki kat es molar miktarlarda
kullanilir. Ancak bilesenlerden birinin veya digerinin daha yüksek bir fazlalikla (3 mol'e
kadar) kullanilmasi da mümkündür.
Bulusa göre yöntem (C)'nin gerçeklestirilmesi için katalizör olarak paladyum(0)
kompleksleri uygundur. Örnegin tetrakis-(trifeniIfosfin)paladyum tercih edilir.
Gerektiginde paladyum(ll) tuzlari da, örnegin PdCIz, Pd(N03)2 kullanilabilir.
Bulusa göre yöntem (C) yürütülürken asit akseptörleri olarak inorganik veya organik
bazlar degerlendirilir. Bunlar tercihen toprak alkali metal veya alkali metal hidroksitleri,
asetatlari, karbonatlari veya hidrojen karbonatlari, örnegin sodyum, potasyum, baryum
veya amonyum hidroksiti, sodyum, potasyum, kalsiyum veya amonyum asetati,
sodyum, potasyum veya amonyum karbonati, sodyum hidrojen veya potasyum hidrojen
karbonati, alkali florürleri, örnegin sezyum florürü ve ayrica örnegin trimetilamin,
trietilamin, tribütilamin, N,N-dimetilanilin, N,N-dimetilbenzilamin, piridin, N-
metilpiperidin, N-metilmorfolin, N,N-dimetilaminopiridin, diazabisiklooktan (DABCO),
diazabisiklononen (DBN) veya diazabisikloundeken (DBU) gibi tersiyer aminleri içerir.
Bulusa göre yöntem (C) yürütülürken seyreltici olarak su, organik solventler ve bunlarin
istenen karisimlari degerlendirilir. Örnek olarak asagidakiler belirtilebilir: alifatik, alisiklik
veya aromatik hidrokarbonlar, örnegin petrol eteri, hekzan, heptan, siklohekzan, metil
siklohekzan, benzen, tolüen, ksilen veya dekalin; halojenli hidrokarbonlar, örnegin
klorobenzen, diklorobenzen, metilen klorür, kloroform, tetraklorometan, dikloro-,
trikloroetan veya tetrakloroetilen; eterler, örnegin dietiI-, diizopropiI-, metil-t-bütiI-, metil-
t-amil eter, dioksan, tetrahidrofuran, 1,2-dimetoksietan, 1,2-dietoksietan, dietilenglikol
dimetil eter veya anisol; alkoller, örnegin metanol, etanol, n- veya i-propanol, n-, izo-,
sek.- veya tert.-bütanol, etandiol, propan-1,2-di0l, etoksietanol, metoksietanol,
dietilenglikol monometil eter, dietilenglikol monometil eter; su.
Reaksiyon sicakligi bulusa göre yöntem (C)'de genis bir aralikta degistirilebilir.
Genellikle O°C ile +140°C arasindaki, tercihen 50°C ile +100°C arasindaki sicakliklarda
çalisilir.
Bulusa göre yöntem (C) yürütülürken formül (IV) ile gösterilen boronik asit türevleri,
burada Z yukarida belirtilen anlama sahiptir ve formül (l-1'-a) ile gösterilen bilesikler,
burada A, 8, W, X, Y ve Z' yukarida belirtilen anlama sahiptir, 1:1 ila 321, tercihen 1:1
ila 211 molar oranda kullanilir. Katalizörden genellikle formüller (I-1-a) ile (l-8-a)
kullanilir. Baz genellikle fazlalik miktarda kullanilir.
Yöntem (D-d)'nin özelligi, formül (l-1-a) ile gösterilen bilesiklerin formül (V) ile
gösterilen karboksilik asit halojenürler ile gerektiginde bir seyreltici varliginda ve
gerektiginde bir asit baglayici madde varliginda reaksiyona sokulmasi ile karakterize
olmasidir.
Seyreltici maddeler olarak bulusa göre yöntem (D-oi)'da asit halojenürlere karsi inert
olan tüm solventler kullanilabilir. Tercihen benzin, benzen, tolüen, ksilen ve tetralin gibi
hidrokarbonlar, ayrica metilen klorür, kloroform, tetraklorokarbon, klorbenzen ve o-
diklorobenzen gibi klorohalojenli hidrokarbonlar, ayrica aseton ve metil izopropil keton
gibi ketonlar, ek olarak dietil eter, tetrahidrofuran ve dioksan gibi eterler, ayrica etil
asetat gibi karboksilik asit esterleri ve ayni zamanda dimetil sülfoksit ve sülfolan gibi
kuvvetli polar solventler kullanilir. Asit halojenürlerin hidroliz stabilitesi izin verdiginde,
reaksiyon su varliginda da gerçeklestirilebilir.
Bulusa göre yöntem (D-oi)'ya göre reaksiyonda asit baglayici ajanlar olarak tüm
alisilageldik asit akseptörleri degerlendirilebilir. Tercihen tersiyer aminler, örnegin
trietilamin, piridin, diazabisiklooktan (DABCO), diazabisikloundeken (DBU),
diazabisiklononen (DBN), Hünig bazi ve N,N-dimetil anilin, ayrica toprak alkali metoal
oksitler, örnegin magnezyum ve kalsiyum oksit, ayrica alkali ve toprak alkali metal
karbonatlar, örnegin sodyum karbonat, potasyum karbonat ve kalsiyum karbonat ve
ayrica örnegin sodyum hidroksit ve potasyum hidroksit gibi alkali hidroksitler
kullanilabilir.
Reaksiyon sicakliklari bulusa göre yöntem (D-oi)'da genis bir aralikta degistirilebilir.
Genellikle 20°C ile +150°C arasindaki, tercihen O°C ile 100°C arasindaki sicakliklarda
çalisilir.
Bulusa göre yöntem (D-d) yürütülürken formül (I-1-a) ile gösterilen baslangiç maddeleri
ve formül (V) ile gösterilen karboksilik asit halojenür genellikle birbirine yakin esdeger
miktarlarda kullanilirlar. Ancak karboksilik asit halojenürün daha yüksek bir fazlalikla (5
mol'e kadar) kullanilmasi da mümkündür. Takip eden islemler alisilageldik yöntemlere
göre gerçeklestirilir.
Yöntem (D-ß)'nin özelligi, formül (I-1-a) ile gösterilen bilesiklerin formül (VI) ile
gösterilen karboksilik asit anhidritler ile gerektiginde bir seyreltici varliginda ve
gerektiginde bir asit baglayici madde varliginda reaksiyona sokulmasi ile karakterize
olmasidir.
Bulusa göre yöntem (D-ß)'da seyreltici olarak tercihen asit halojenürlerin kullaniminda
da tercihen degerlendirilen seyrelticiler kullanilabilir. Ayrica fazlalaik miktarda kullanilan
karboksilik asit anhidrit de seyreltici madde islevi görebilir.
Yöntem (D-ß)'da gerektiginde ilave edilen asit baglayici ajanlar olarak tercihen asit
halojenürlerin kullaniminda da tercihen degerlendirilen asit baglayici ajanlar
kullanilabilir.
Reaksiyon sicakliklari bulusa göre yöntem (D-ß)'da genis bir aralikta degistirilebilir.
Genellikle 20°C ile +150°C arasindaki, tercihen 0°C ile 100°C arasindaki sicakliklarda
çalisilir.
Bulusa göre yöntem (D-ß) yürütülürken formül (l-1-a) ile gösterilen baslangiç
materyalleri ve formül (VI) ile gösterilen karboksilik asit anhidritler genellikle birbirine
yakin esdeger miktarlarda kullanilirlar. Ancak karboksilik asit anhidritin daha yüksek bir
fazlalikla (5 mol'e kadar) kullanilmasi da mümkündür. Takip eden islemler alisilageldik
yöntemlere göre gerçeklestirilir.
Prosedür genel olarak seyrelticinin ve fazlalik miktarda bulunan karboksilik asit
anhidritin ve ayrica olusan karboksilik asitin distilasyonla veya bir organik solvent veya
su ile yikayarak uzaklastirilmasini içerir.
Yöntem (E)'nin özelligi, formül (I-1-a) ile gösterilen bilesiklerin formül (VII) ile gösterilen
kloroformik asit esterleri ile gerektiginde bir seyreltici varliginda ve gerektiginde bir asit
baglayici madde varliginda reaksiyona sokulmasi ile karakterize olmasidir.
Bulusa göre yöntem (E)'ye göre reaksiyonda asit baglayici ajanlar olarak tüm
alisilageldik asit akseptörleri degerlendirilebilir. Tercihen tersiyer aminler, örnegin
trietilamin, piridin, DABCO, DBU, DBA, Hünig bazi ve N,N-dimetil anilin, ayrica toprak
alkali metoal oksitler, örnegin magnezyum ve kalsiyum oksit, ayrica alkali ve toprak
alkali metal karbonatlar, örnegin sodyum karbonat, potasyum karbonat ve kalsiyum
karbonat ve ayrica örnegin sodyum hidroksit ve potasyum hidroksit gibi alkali
hidroksitler kullanilabilir.
Seyreltici maddeler olarak bulusa göre yöntem (E)'de kloroformik asit esterlerine veya
kloroformik asit tiyolesterlerine karsi inert olan tüm solventler kullanilabilir. Tercihen
benzin, benzen, tolüen, ksilen ve tetralin gibi hidrokarbonlar. ayrica metilen klorür,
kloroform, tetraklorokarbon. klorbenzen ve o-diklorobenzen gibi klorohalojenli
hidrokarbonlar, ayrica aseton ve metil izopropil keton gibi ketonlar, ek olarak dietil eter,
tetrahidrofuran ve dioksan gibi eterler, ayrica etil asetat gibi karboksilik asit esterleri ve
ayni zamanda dimetil sülfoksit ve sülfolan gibi kuvvetli polar solventler kullanilir.
Reaksiyon sicakliklari bulusa göre yöntem (E) yürütülürken genis bir aralikta
degistirilebilir. Bir seyreltici madde ve asit baglayan madde varliginda çalisilirken,
reaksiyon sicakliklari genellikle -20°C ile +100°C arasinda, tercihen 0°C ile 50°C
arasinda yer alir.
Bulusa göre yöntem (E) genellikle normal basinç altinda yürütülür.
Bulusa göre yöntem (E) yürütülürken formül (I-1-a) ile gösterilen baslangiç materyalleri
ve formül (VII) ile gösterilen ilgili kloroformik asit esterleri genellikle birbirine yakin
esdeger miktarlarda kullanilirlar. Ancak bilesenlerden birinin veya digerinin daha
yüksek bir fazlalikla (2 mol'e kadar) kullanilmasi da mümkündür. Takip eden islemler
alisilageldik yöntemlere göre gerçeklestirilir. Prosedür genellikle çöken tuzun
uzaklastirilmasini ve kalan reaksiyon karisiminin seyrelticinin uzaklastirilmasi yoluyla
konsantre edilmesini içerir.
Yöntem (l)'nin özelligi, formül (I-1-a) ile gösterilen bilesiklerin formül (XI) ile gösterilen
metal hidroksitleri veya metal alkoksitleri veya formül (XII) ile gösterilen aminler ile,
gerektiginde bir seyreltici varliginda reaksiyona sokulmasi ile karakterize olmasidir.
Bulusa göre yöntem (l)'da seyreltici maddeler olarak tercihen tetrahidrofuran, dioksan,
dietil eter gibi eterler ancak ayni zamanda metanol, etanol, izopropanol gibi alkoller
veya ayni zamanda su kullanilabilir.
Bulusa göre yöntem (I) genellikle normal basinç altinda yürütülür.
Reaksiyon sicakliklari genellikle -20°C ile 100°C. tercihen 0°C ile 50°C arasinda yer
Bulusa göre etkin maddeler bitkiler tarafindan iyi tolere edilebilme, sicakkanlilar
açisindan uygun bir toksisite ve çevre ile iyi uyumluluk özellikleri ile, bitki ve bitki
organlarinin korunmasi için, hasat verimlerinin artirilmasi için, hasat kalitesinin
iyilestirilmesi için ve tarimda, bahçecilikte, hayvan besiciliginde, ormanlarda,
bahçelerde ve rekreasyon amaçli ortamlarda, stok ve malzemelerin korunmasinda ve
hijyen sektöründe hayvani zararlilar ile, bilhassa insektler, örümcegimsiler, helmintler,
nematodlar ve yumusakçalar ile mücadele için kullanilmak üzere uygundur. Tercihen,
bitki koruma ajanlari olarak kullanilabilirler. Normal duyarliliga sahip ve dirençli türlere
karsi ve ayrica bütün veya tek tek gelisim evrelerinde etkilidirler. Yukarida belirtilen
zararlilar sunlari içerir:
Anoplura (Phthiraptera) takimindan örnegin Damalinia spp., Haematopinus spp.,
Linognathus spp., Pediculus spp., Trichodectes spp.
Arachnida sinifindan örnegin Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp.,
Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa,
Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri,
Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes
spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros
spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus Iatus,
Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp.i Sarcoptes spp., Scorpio
maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates
Bivalva sinifindan örnegin Dreissena spp.
Chilopoda takimindan örnegin Geophilus spp., Scutigera spp.
Coleoptera takimindan örnegin Acanthoscelides obtectus, Adoretus spp., Agelastica
alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp.,
Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria spp., Attagenus spp.,
Bruchidius obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus,
Conoderus spp., Cosmopolites spp., Costelytra zealandica, Curculio spp.,
Cryptorhynchus Iapathi, Dermestes spp.. Diabrotica spp.. Epilachna spp., Faustinus
cubae, Gibbium psylloides, Heteronychus arator, Hylamorpha elegans, Hylotrupes
bajulus, Hypera postica, Hypothenemus spp., Lachnosterna consanguinea,
Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp.,
Meligethes aeneus, Melolontha melolontha, Migdolus spp.. Monochamus spp.,
Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus
surinamensis, Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon cochleariae,
Phyllophaga spp., Popillia japonica, Premnotrypes spp., Psylliodes Chrysocephala,
Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus
spp., Sternechus spp., Symphyletes spp., Tenebrio molitor, Tribolium spp.,
Trogoderma Spp., Tychius spp., Xylotrechus spp., Zabrus spp.
Collembola takimindan örnegin Onychiurus armatus.
Dermaptera takimindan örnegin Forficula auricularia.
Diplopoda takimindan örnegin Blaniulus guttulatus.
Diptera takimindan örnegin Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora
erythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia
anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia hominis,
Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp.,
Hypoderma spp., Liriomyza spp.. Lucilia spp.i Musca spp., Nezara spp.i Oestrus spp.,
Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanus spp.,
Tannia spp., Tipula paludosa, Wohlfahrtia spp.
Gastropoda sinifindan örnegin Arion spp., Biomphalaria spp., Bulinus spp., Derooeras
spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
Helmintler sinifindan örnegin Ancylostoma duodenale, Ancylostoma ceylanicum,
Acylostoma braziliensis, Ancylostoma spp., Ascaris Iubricoides, Ascaris spp., Brugia
malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia
spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium Iatum, Dracunculus
medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius
vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana,
Hyostrongulus spp., Loa Loa, Nematodirus spp.. Oesophagostomum spp.,
Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp.,
Schistosomen spp, Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides
spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella
britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris
trichuria, Wuchereria bancrofti.
Ayrica, Eimeria gibi protozoalar ile mücadele edilebilir.
Heteroptera takimindan örnegin Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris
spp., Campylomma Iivida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus
piperis, Dichelops furcatus, Dioonoooris hewetti, Dysdercus spp., Euschistus spp.,
Eurygaster spp., Heliopeltis spp., Horcias nobilellus. Leptocorisa spp., Leptoglossus
phyllopus, Lygus spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp.,
Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seriatus, Pseudacysta persea,
Rhodnius spp., Sahlbergella singularis, Scotinophora spp., Stephanitis nashi, Tibraca
spp., Triatoma spp.
Homoptera takimindan örnegin Acyrthosipon spp., Aeneolamia spp., Agonoscena spp.,
Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis
cardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Aspidiella
spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp.i Brachycaudus
helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata,
Carneocephala fulgida, Ceratovacuna Ianigera, Cercopidae, Ceroplastes spp.,
Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis
juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp.,
Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp.,
Doralis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp.,
Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Geococcus coffeae,
Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., ldiocerus spp., Idioscopus
spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi,
Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfiella spp.,
Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp.,
Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia
praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp.,
Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli,
Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis,
Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla
spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp.,
Saissetia spp., Scaphoides titanus, Schizaphis graminum. Selenaspidus articulatus,
Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina. Tenalaphara
malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes
vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii.
Hymenoptera takimindan örnegin Diprion spp., Hoplocampa spp., Lasius spp.,
Monomorium pharaonis, VeSpa spp.
Lepidoptera takimindan örnegin Acronicta major, Aedia Ieucomelas, Agrotis spp.,
Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella,
Bupalus piniarius, Cacoecia podana, Capua reticulana, Carpocapsa pomonella,
Cheimatobia brumata, Chilo spp., Choristoneura fumiferana, Clysia ambiguella,
Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea,
Euxoa spp., Feltia spp., Galleria mellonella, Helicoverpa spp., Heliothis spp.,
Hofmannophila pseudospretella, Homona magnanima, Hyponomeuta padella,
Laphygma spp., Lithocolletis blancardella, Lithophane antennata, Loxagrotis albicosta,
Lymantria spp., Malacosoma neustria, Mamestra brassicae, Mocis repanda, Mythimna
separata, Oria spp., Oulema oryzae, Panolis flammea, Pectinophora gossypiella,
Phyllocnistis citrella, Pieris spp., Plutella xylostella, Prodenia spp., Pseudaletia spp.,
Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp.. Thermesia gemmatalis,
Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp.
Orthoptera takimindan örnegin Acheta domesticus, Blatta orientalis, Blattella
germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp.,
Periplaneta americana, Schistocerca gregaria.
Siphonaptera takimindan örnegin Ceratophyllus spp., Xenopsylla cheopis.
Symphyla takimindan örnegin Scutigerella immaculata.
Thysanoptera takimindan örnegin Baliothrips biformis, Enneothrips flavens,
Frankliniella Spp-, Heliothrips spp., Hercinothrips femoralis, Kakothrips spp.,
Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
Thysanura takimindan örnegin Lepisma saccharina.
Bitki paraziti nematodlar arasinda örnegin Anguina spp., Aphelenchoides spp.,
Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp.,
Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp.,
Pratylenchus spp., Radopholus similis, Rotylenchus spp., Trichodorus spp.,
Tylenchorhynchus spp., Tylenchulus spp., Tylenchulus semipenetrans, Xiphinema spp.
Bulusa göre bilesikler, gerektiginde, belirli konsantrasyonlarda veya kullanim
miktarlarinda ayni zamanda herbisit, safener, büyüme düzenleyici veya bitki
özelliklerini iyilestirici maddeler olarak veya mikrobisitler olarak, örnegin fungusit,
antimikotik, bakterisit, virisit (viroidlere karsi maddeler dahil) olarak veya MLO'ya
(mikoplazma benzeri organizma) ve RLO'ya (riketsia benzeri organizma) karsi
maddeler olarak kullanilabilir. Bunlar, ayni zamanda, baska etkin maddelerin
sentezinde ara ürün veya öncül ürün olarak da kullanilabilir.
Bulusa göre, bütün bitkiler ve bitki kisimlari muamele edilebilir. Bitkilerden, istenen ve
istenmeyen yabani bitkiler veya kültür bitkileri (dogal olarak bulunan kültür bitkileri
dahil) gibi bütün bitkiler ve bitki popülasyonlari anlasilmaktadir. Kültür bitkileri,
geleneksel islah ve optimizasyon yöntemleri ile veya transgenik bitkiler dahil ve çesit
koruma kanunlari ile korunabilen veya korunamayan bitki çesitleri dahil, biyoteknolojik
yöntemler ve gen teknolojisi yöntemleri veya bu yöntemlerin kombinasyonlari ile elde
edilebilen bitkiler olabilir. Bitki kisimlarindan bitkilerin filiz, yaprak, çiçek ve kök gibi
bütün toprak üstü ve toprak alti kisimlari ve organlari, örnegin yapraklar, igneler,
saplar, gövdeler, çiçekler, sporokarplar, meyveler ve tohumlar ve ayrica kökler,
yumrular ve rizomlar anlasilacaktir. Ekinler ve ayrica vejetatif ve jeneratif üreme
materyalleri, örnegin çelikler, yumrular, rizomlar, sürgünler ve tohumlar da bitki
kisimlarina dahildir.
Bitkilerin ve bitki kisimlarinin etkin maddeler ile bulusa göre muamele edilmesi
dogrudan gerçeklesebilir veya çevreleri, habitatlari veya saklama alanlari üzerine,
örnegin daldirma, püskürtme, buharlastirma, sisleme, serpme, sürme, enjekte etme
yoluyla ve üreme materyalleri, bilhassa tohumlar söz konusu oldugunda ayrica tek
veya çok katmanli kaplama gibi alisilageldik muamele yöntemleri ile etki etmek
suretiyle gerçeklestirilebilir.
Etkin maddeler solüsyonlar, emülsiyonlar, sprey tozlari, su ve yag bazli süspansiyonlar,
tozlar, serpme tozlari, macunlar, çözünür tozlar, çözünür granüller, serpme granülleri,
süspansiyon-emülsiyon konsantreleri, etkin madde emdirilmis dogal maddeler, etkin
madde emdirilmis sentetik maddeler, gübreler gibi alisilageldik formülasyonlara ve
ayrica polimerik maddeler içerisinde mikroenkapsülasyonlara dönüstürülebilir.
Bu formülasyonlar bilinen sekilde örnegin etkin maddelerin çogalticilar ile, yani sivi
solventler ve/veya kati tasiyici maddeler ile karistirilmasi yoluyla, gerektiginde yüzey
aktif maddeler, ayrica emülgatörler ve/veya dispersanlar ve/veya köpük meydana
getirici maddeler kullanilarak hazirlanabilir. Formülasyonlar uygun sistemlerde veya
ayni zamanda, uygulamadan önce veya uygulama sirasinda hazirlanabilir.
Yardimci maddeler olarak, maddenin kendisine ve/veya ondan elde edilen preparatlara
(örnegin püskürtme sivilari, tohum ilaçlama sivilari) belirli özellikler, örnegin belirli
teknik özellikler ve/veya özel biyolojik özellikler kazandirmaya uygun maddeler
kullanilabilir. Tipik yardimci maddeler olarak asagidakiler degerlendirilir: Çogalticilar,
solventler ve tasiyici maddeler.
Çogalticilar olarak, örnegin su, ayrica örnegin aromatik ve aromatik olmayan
hidrokarbonlar (örnegin parafinler, alkil benzenler, alkil naftalinler, klorobenzenler),
alkoller ve polioller (gerektiginde sübstitüe edilmis. eterlestirilmis ve/veya
esterlestirilmis olabilirler), basit ve sübstite edilmis aminlerin, amitlerin, Iaktamlarin
(örnegin N-alkilpirrolidon) ve Iaktonlarin ketonlar (örnegin aseton, siklohekzanon),
esterler (kati ve sivi yaglar dahil) ve (poli-)eterleri, sülfonlar ve sülfoksitler (örnegin
dimetilsülfoksit) sinifindan polar ve polar olmayan organik kimyasal sivilar uygundur.
Çogaltici olarak su kullanilan durumlarda, örnegin organik solventler de yardimci
solvent olarak kullanilabilir. Sivi solventler olarak esasen asagidakiler degerlendirilir:
Ksilen, tolüen veya alkil naftalinler gibi aromatik bilesikler, örnegin klorobenzenler,
kloroetilenler veya metilen klorür gibi klorlu aromatik bilesikler ve klorlu alifatik
hidrokarbonlar, örnegin siklohekzan veya parafin gibi alifatik hidrokarbonlar, örnegin
petrol fraksiyonlari, mineral ve bitkisel yaglar. örnegin bütanol veya glikol gibi alkoller
ve ayrica bunlarin eterleri ve esterleri, örnegin aseton, metil etil keton, metil izobütil
keton veya siklohekzanon gibi ketonlar, örnegin dimetilsülfoksit gibi kuvvetli polar
solventler ve ayrica su.
Kati tasiyici maddeler olarak asagidakiler degerlendilir:
örnegin kaolinler, killer, talk, tebesir, kuvars, attapulgit, montmorillonit veya diatome
topraklar gibi amonyum tuzlari, dogal kaya unlari ve yüksek dispers silisik asit,
alüminyum oksit ve silikatlar gibi sentetik kaya unlari, granüller için kati tasiyici
maddeler olarak asagidakiler degerlendirilir: örnegin kalsit, mermer, bims, sepiolit,
dolomit gibi çatlakli ve parçalanmis kayalar ve ayrica, inorganik ve organik unlardan
elde edilen sentetik granülatlar ile kagit, testere tozu, hindistan cevizi kabuklari, misir
koçanlari ve tütün saplari gibi organik granülatlardan elde edilen sentetik granülatlar;
emülgatör ve/veya köpük meydana getirici maddeler olarak asagidakiler degerlendirilir:
örnegin polioksietilen yag asidi esterleri gibi noniyonik ve anyonik emülgatörler, örnegin
alkilaril poliglikol eterler gibi polioksietilen yag alkolü eterleri, alkilsülfonatlar,
alkilsülfatlar, arilsülfonatlar ve protein hidrolizatlari; dispersanlar olarak noniyonik
ve/veya iyonik maddeler, örnegin asagidaki siniflardan maddeler degerlendirilir: alkol-
POE- ve/veya POP eterleri, asit- ve/veya POP-POE esterleri, alkil-aril- ve/veya POP-
POE eterleri, yag- ve/veya POP-POE katilma ürünleri, POE- ve/veya POP-poliol
türevleri, POE- ve/veya POP-sorbitan- veya seker katilma ürünleri, alkil veya aril
sülfatlar, sülfonatlar ve fosfatlar veya ilgili PO-eter katilma ürünleri. Ayrica, örnegin
vinilik monomerlerin, akrilik asitlerin, tek basina veya örnegin (poIi-) alkoller veya (poIi-)
aminler ile birlikte EO ve/veya PO'nun diger uygun oligo- veya polimerleri. Ayrica, lignin
ve sülfonik asit türevleri, basit ve modifiye edilmis selülozlar, aromatik ve/veya alifatik
sülfonik asitler ve ayrica bunlarin formaldehit ile katilma ürünleri kullanilabilir.
Formülasyonlarda, ayrica, örnegin karboksimetil selüloz, örnegin arap zamki, polivinil
alkol, polivinil asetat gibi dogal ve sentetik, toz halinde, parçacikli veya lateks formunda
polimerler ve ayrica kefalin ve Iesitin gibi dogal fosfolipitler ve sentetik fosfolipitler gibi
yapistirici maddeler de kullanilabilir.
Inorganik pigmentler, örnegin demir oksit, titanyum oksit, ferrosiyanür mavisi ve organik
boyalar, örnegin alizarin, azo ve metalftalosiyanin boyar maddeler gibi boyar maddeler
ve demir, manganez, bor, bakir, kobalt, molibden ve çinko tuzlari gibi mikrobesinler
kullanilabilir.
Ilave katki maddeleri koku maddeleri, mineral veya bitkisel, gerektiginde modifiye
edilmis siviyaglar, vakslar ve demir, manganez, bor, bakir, kobalt, molibden ve çinko
tuzlari gibi besinler (mikrobesinler) olabilir.
Ayrica soguk stabilizörleri, koruyucu maddeler, oksidasyona karsi koyuyan maddeler,
isiga karsi koruyan maddeler veya kimyasal ve/veya fiziksel stabiliteyi iyilestiren
maddeler gibi stabilizörler de mevcut olabilir.
Formülasyonlar, genellikle, agirlikça %0,01 ila 98 oraninda, tercihen %05 ila 90
oraninda etkin madde içerir.
Bulusa göre etkin madde, ticari formülasyonlarinda ve bu formülasyonlardan
hazirlanan uygulama formlarinda insektisitler, feromonlar, sterillestiriciler, bakterisitler,
akarisitler, nematisitler, fungusitler, büyümeyi regüle eden maddeler, herbisitler,
safenerler, gübreler veya semiyokimyasal gibi baska etkin maddeler ile karisim halinde
bulunabilir.
Özellikle uygun karisim ortaklari, örnegin asagidakilerdir:
Fu ngusitler:
Nükleik asit sentezi inhibitörleri
Benalaksil, benalaksil-M, bupirimat, kiralaksil, klozilakon, dimetirimol, etirimol,
furalaksil, himeksazol, metalaksil, metalaksil-M, ofuras, oksadiksil, oksolik asit
Mitoz ve hücre bölünmesi inhibitörleri
Benomil, karbendazim, dietofenkarb, fuberidazol, pensikuron, tiyabendazol,
tiyofanat metil, zoksamit
Solunum zinciri kompleks l inhibitörleri
Diflumetorim
Solunum zinciri kompleks II inhibitörleri
Boskalid, karboksin, fenfuram, flutolanil, furametpir, mepronil, oksikarboksin,
pentiyopirad, tifluzamit
Solunum zinciri kompleks III inhibitörleri
Azoksistrobin, siazofamit, dimoksistrobin. enestrobin, famoksadon, fenamidon,
fluoksastrobin, kresoksimmetil, metominostrobin, orisastrobin, piraklostrobin,
pikoksistrobin, trifloksistrobin
Ayiricilar
Dinokap, fluazinam
ATP üretimi inhibitörleri
Fentin asetat, fentin klorür, fentin hidroksit, siltiyofam
Amino asit ve protein biyosentezi inhibitörleri
Andoprim, blastisidin-S, siprodinil, kasugamisin, kasugamisin hidroklorür hidrat,
mepanipirim, pirimetanil
Sinyal iletimi inhibitörleri
Fenpiklonil, fludioksonil, kuinoksifen
Yag ve membran sentezi inhibitörleri
Klozolinat, iprodion, prosimidon, vinklozolin
Ampropilfos, potasyum ampropilfos, edifenfos, iprobenfos (IBP), izoprotiyolan,
pirazofos
Tolklofos-metil, bifenil
Iyodokarb, propamokarb, propamokarb hidroklorür
Ergosterol biyosentezi inhibitörleri
Fenhekzamit,
Azakonazol, bitertanol, bromukonazol, siprokonazol, diklobütrazol,
difenokonazol, dinikonazol, dinikonazoI-M, epoksikonazol, etakonazol,
fenbükonazol, flukuinkonazol, flusilazol, flutriafol, furkonazol. furkonazoI-cis,
hekzakonazol, imibenkonazol, ipkonazol, metkonazol, miklobütanil,
paklobütrazol, penkonazol, propikonazol, protiyokonazol, simekonazol,
tebükonazol, tetrakonazol, triadimefon, triadimenol, tritikonazol, ünikonazol,
vorikonazol, imazalil, imazalil sülfat, okspokonazol, fenarimol, flurprimidol,
nuarimol, pirifenoks, triforin, pefurazoat, prokloraz, triflumizol, vinikonazol,
Aldimorf, dodemorf, dodemorf asetat, fenpropimorf, tridemorf, fenpropidin,
spiroksamin,
Naftifin, piribütikarb, terbinafin
Hücre duvari sentezi inhibitörleri
Bentiyavalikarb, bialafos, dimetomorf, flumorf, iprovalikarb, polioksinler,
polioksorim, validamisin A
Melanin biyosentezi inhibitörleri
Kapropamit, diklosimet, fenoksanil, ftalit, pirokuilon, trisiklazol
Direnç indüksiyonu
Asibenzolar-S-metil, probenazol, tiadinil
Birden çok noktada aktif:
Kaptafol, kaptan, klorotalonil, bunlar gibi bakir tuzlari: Bakir hidroksit, bakir
naftenat, bakir oksiklorür, bakir sülfat, bakir oksit, bakir oksin ve bordo
bulamaci, diklorofluanid, ditiyanon, dodin, dodin serbest bazi, ferbam, folpet,
florofolpet, guazatin, guazatin asetat, iminoktadin, iminoktadin albesilat,
iminoktadin triasetat, mankupfer, mankozeb, maneb, metiram, çinko metiram,
propamidin, propineb, kükürt ve kalsiyum polisülfit, tiram, tolilfluanid, zineb,
Bilinmeyen mekanizma
Amibromdol, bentiyazol, betoksazin, kapsimisin, karvon, kinometiyonat,
kloropikrin, kufraneb, siflufenamit, simoksanil, dazomet, debakarb, diklomezin,
diklorofen, dikloran, difenzokuat, difenzokuat metil sülfat, difenilamin,
etaboksam, ferimzon, flumetover, flusülfamit, fluopikolid, floroimit,
hekzaklorobenzen, 8-hidr0ksikin0lin sülfat, irumamisin, metasülfokarb,
metrafenon, metil izotiyosianat, mildiomisin, natamisin, nikel dimetilditiyo
karbamat, nitrotaI-izopropil, oktilinon, oksamokarb, oksifentiin, pentaklorofenol
ve tuzlari, 2-fenilfenol ve tuzlari, piperalin, propanosin sodyum, prokuinazid,
pirrolnitrin, kuintozen, tekloftalam, teknazen, triazoksit, triklamit, zarilamit ve
2,3,5,6-tetraklor-4-(metilsülfoniI)-piridin, N-(4-kl0r-2-nitrofenil)-N-etiI-4-metil-
benzen sülfonamit, 2-amin0-4-metil-N-feniI-5-tiyazol karboksamit, 2-klor-N-(2,3-
sikloheptanol, 2,4-dihidro-5-metoksi-2-metiI-4-[[[[1-[3-(trifl0rometiI)-fenil]-
2,6-piridindikarbonitril, metil 2-[[[siklopropil[(4-metoksifenil)
imin0]metil]tiyo]metil]-.alfa.-(metoksimetilen)-benzasetat, 4-klor-alfa-pr0piniloksi-
klorofenil)-2-propinil]0ksi] -3-metoksifenil]etiI]-3-metiI-2-[(metilsülf0nil)amin0]-
piridin-2-il)etiI]-2,4-dikloronikotinamit, N-(5-br0m-3-klorpiridin-2-il)metiI-2,4-
dikloronikotinamit, 2-büt0ksi-6-iy0do-3-propiI-benzopiranon-4-on, N-{(Z)-
benzasetamit, N-(3-etil-3,5,5-trimetil-sikl0hekzil)-3-f0rmiIamino-Z-hidroksi-
benzamit, 2-[[[[1-[3(1flor-2-feniletil)oksi] fenil] etiliden]amin0]oksi]metin-alfa-
(metoksiimino)-n-metiI-alfaE-benzasetamit, N-{2-[3-kl0r-5-(triflormetil)piridin-2-
il]etiI}-2-(triflor0metil)-benzamit, N-(3',4'-diklor-5-florbifenil-2-il)-3-(difl0rmetiI)-1-
metiI-1H-pirazoI-4-karboksamit, N-(6-metoksi-3-piridiniI)-sikl0propan
karboksamit, 1-[(4-met0ksifen0ksi)-metiI]-2,2-dimetilpr0piI-1H-imidazoI-1-
karboksilik asit, O-[1-[(4-met0ksifen0ksi)-metiI]-2,2-dimetilpr0piI]-1H-imidazol- 1-
(metoksiimino)-N-metil asetamit
Bakterisitler:
Bronopol, diklorofen, nitrapirin, nikel dimetilditiyokarbamat, kasugamisin, oktilinon,
furankarboksilik asit, oksitetrasiklin, probenazol, streptomisin, tekloftalam, bakir sülfat
ve diger bakir preparatlari.
Insektisitler I Akarisitlerl Nematisitler:
Asetilkolinesteraz (AChE) inhibitörleri
Karbamatlar,
örnegin alanikarb, aldikarb, aldoksikarb, aliksikarb, aminokarb, bendiokarb,
benfurakarb, büfenkarb, bütakarb, bütokarboksim, bütoksikarboksim, karbaril,
karbofuran, karbosülfan, kloetokarb, dimetilan, etiyofenkarb, fenobükarb,
fenotiyokarb, formetanat, furatiyokarb, izoprokarb, metam sodyum, metiyokarb,
metomil, metolkarb, oksamil, pirimikarb, promekarb, propoksur, tiyodikarb,
tiyofanoks, trimetakarb, XMC, ksililkarb, triazamat
Organofosfatlar,
örnegin asefat, azametifos, azinfos (-metil, -etil), bromofos-etil, bromfenvinfos (-
metil), bütatiyofos, kadusafos, karbofenotiyon, kloretoksifos, klorfenvinfos,
klormefos, klorpirifos (-metil/-etil), kumafos, siyanofenfos, siyanofos,
klorfenvinfos, demeton-S-metil, demeton-S-metilsülfon, dialifos, diazinon,
diklofentiyon, diklorovos/DDVP. dikrotofos, dimetoat, dimetilvinfos,
dioksabenzofos, disülfoton, EPN, etiyon, etoprofos, etrimfos, famfur, fenamifos,
fenitrotiyon, fensülfotiyon, fentiyon, flupirazofos, fonofos, formotiyon, fosmetilan,
fostiyazat, heptenofos, iyodofenfos, iprobenfos, izazofos, izofenfos, izopropil O-
salisilat, izoksatiyon, malatiyon, mekarbam, metakrifos, metamidofos,
metidatiyon, mevinfos, monokrotofos, naled, ometoat, oksidemeton-metil,
paratiyon (-metiI/-etil), fentoat, forat, fosalon, fosmet, fosfamidon, fosfokarb,
foksim, pirimifos (-metil/-etil), profenofos, propafos. propetamfos, protiyofos,
protoat, piraklofos, piridafentiyon, piridatiyon, kuinalfos, sebufos, sülfotep,
sülprofos, tebupirimfos, temefos, terbufos, tetraklorovinfos, tiyometon, triazofos,
triklorofon, vamidotiyon
Sodyum kanali modülatörleri / voltaj bagimli sodyum kanali blokerleri
Piretroidler,
örnegin akrinatrin, alletrin (d-cis-trans, d-trans), beta-siflutrin, bifentrin,
biyoalletrin, biyoaIIetrin-S-siklopentil izomeri, biyoetanometrin, biyopermetrin,
biyoresmetrin, klovaportrin, cis-sipermetrin, cis-resmetrin, cis-permetrin,
klositrin, sikloprotrin, siflutrin, sihalotrin, sipermetrin (alfa-. beta-, teta-. zeta-),
sifenotrin, deltametrin, empentrin (1R izomeri), esfenvalerat, etofenproks,
fenflutrin, fenpropatrin, fenpiritrin, fenvalerat, flubrositrinat, flusitrinat,
flufenproks, flumetrin, fluvalinat, fubfenproks, gama-sihalotrin, Imiprotrin,
kadetrin, lambda-sihalotrin, metoflutrin, permetrin (cis-, trans-), fenotrin (1 R-
trans izomeri), pralletrin, proflutrin, protrifenbut, piresmetrin, resmetrin, RU
15525, silafluofen, tau-fluvalinat, teflutrin, teralletrin, tetrametrin (-1R izomeri),
tralometrin, transflutrin, ZXI 8901. piretrinler (piretrum)
Oksadiazinler,
örnegin indoksakarb
Semikarbazonlar,
örnegin metaflumizon (BAS 3201)
Asetilkolin reseptör agonistleri/antagonistleri
Kloronikotiniller,
örnegin asetamiprid, klotiyanidin, dinotefuran, imidakloprid, nitenpiram,
nitiyazin, tiyakloprid, tiyametoksam
Nikotin, bensültap. kartap
Asetilkolin reseptörü modülatörleri
Spinosinler,
örnegin spinosad
GABA kapili klorür kanali antagonistleri
Organoklorlar,
örnegin kamfeklor, klordan, endosülfan, gama-HCH, HCH, heptaklor, Iindan,
metoksiklor
Fiproller,
örnegin asetoprol, etiprol, fipronil, pirafluprol, piriprol, vaniliprol
Klorür kanali aktivatörleri
Mektinler,
örnegin avermektin, emamektin, emamektin benzoat, ivermektin, milbemisin
Jüvenil hormon mimetikleri,
örnegin diofenolan, epofenonan, fenoksikarb, hidropren, kinopren, metopren,
piriproksifen, tripren
Ekdizon agonistleri/bozucular
Diasilhidrazinler,
örnegin kromafenozit, halofenozit, metoksifenozit, tebufenozit
Kitin biyosentezi inhibitörleri
Benzoil üreler,
örnegin bistrifluron, klorofluazuron, diflubenzuron, fluazuron, flusikloksuron,
flufenoksuron, hekzaflumuron, quenuron, novaluron, noviflumuron, penfluron,
teflubenzuron, triflumuron
Büprofezin
Siromazin
Oksidatif fosforilasyon inhibitörleri, ATP bozucular
Diafentiuron
Organokalay bilesikleri,
örnegin azosiklotin, sihekzatin, fenbütatin oksit
H-proton gradyanini kesintiye ugratan oksidatif fosforilasyon ayiricilar
Pirroller,
örnegin klorofenapir
Dinitrofenoller,
örnegin binapakril, dinobüton, dinokap, DNOC
Kompleks I elektron transport inhibitörleri
METI'Ier,
örnegin fenazakuin, fenpiroksimat, pirimidifen,
tolfenpirad
Hidrametilnon
Dikofol
Kompleks Il elektron transport inhibitörleri
Kompleks III elektron transport inhibitörleri
Asekuinosil, fluakripirim
Mikrobiyal insekt bagirsak membrani bozucular
Bacillus thuringiensis suslari
Yag sentezi inhibitörleri
Tetronik asitler,
örnegin spirodiklofen, spiromesifen
Tetramik asitler,
örnegin spirotetramat
Karboksamitler
örnegin flonikamit
Oktopaminerjik agonistler,
örnegin amitraz
Magnezyum tarafindan stimüle edilen ATPaz inhibitörleri,
Propargit
Riyanodin reseptörü efektörleri
a) Benzoik asit dikarboksamitler,
örnegin flubenamit
b) Antranilamitler, örnegin
piridaben,
tebufenpirad,
Rinaksapir (3-bromo-N-{4-kl0r0-2-metiI-6-[(metilamino)karb0nil]fenil}-1-(3-
kloropiridin-2-il)-1H-pirazoI-5-karboksamit)
Nereistoksin analoglari,
örnegin tiyosiklam hidrojen oksalat, tiyosültap sodyum
Biyolojikler, hormonlar veya feromonlar
Azadiraktin, Bacillus spec., Beauveria spec., kodlemon, Metarrhizium spec.,
Paecilomyces spec., turingiensin, Verticillium spec.
Bilinmeyen veya spesifik olmayan etki mekanizmalarina sahip etkin maddeler
Fumigantlar,
örnegin alüminyum fosfür, metil bromür, sülfüril florür
beslenme inhibitörleri,
örnegin kriyolit, flonikamit, pimetrozin
Akar büyüme inhibitörleri,
örnegin klofentezin, etoksazol, hekzitiyazoks
Amidoflumet, benklotiaz, benzoksimat, bifenazat, bromopropilat, buprofezin,
kinometiyonat, klordimeform, klorobenzilat. kloropikrin, klotiazoben, siklopren,
siflumetofen, disiklanil, fenoksakrim, fentrifanil, flubenzimin, flufenerim, flutenzin,
gossyplure, hidrametilnon, japonilur, metoksadiazon, petrol, piperonil bütoksit,
potasyum oleat, piridalil, sülfluramit, tetradifon, tetrasul, triaraten,verbutin.
Herbisitler, gübreler, büyüme regülatörleri, safenerler, semiyokimyasallar gibi diger
bilinen etkin maddeler ile veya bitki özelliklerinin gelistirilmesi için ajanlarla karisimlar
da mümkündür.
Bulusa göre etkin maddeler ayrica insektisit olarak kullanimda ticari formülasyonlarinda
ve bu formülasyonlardan hazirlanan uygulama formlarinda, sinerjistler ile karisim
halinde bulunabilir. Sinerjistler etkin maddelerin etkisini, ilave edilen sinerjistin
kendisinin aktif sekilde etkili olmasini gerektirmeksizin artiran bilesiklerdir.
Bulusa göre etkin maddeler ayrica insektisit olarak kullanimda ticari formülasyonlarinda
ve bu formülasyonlardan hazirlanan uygulama formlarinda, bitki çevresine, bitki
kisimlarinin yüzeyine veya bitki dokulari içerisine uygulanmasinin ardindan etkin
maddenin bozunmasini azaltan inhibitörler ile karisim halinde de bulunabilir.
Ticari formülasyonlardan hazirlanan uygulama formlarinin etkin madde içerigi genis bir
aralikta degisebilir. Uygulama formunun etkin madde konsantrasyonu agirlikça
araliginda yer alabilir.
Uygulama, uygulama formlari için uygun olan alisilageldik bir yolla gerçeklestirilir.
Yukarida belirtildigi üzere, bulusa göre, bütün bitkiler ve bunlarin kisimlari muamele
edilebilir. Tercih edilen bir düzenlemede, yabani olarak bulunan veya çaprazlama veya
protoplast füzyonu gibi geleneksel biyolojik islah yöntemleri ile elde edilmis olan bitki
türleri ve bitki çesitleri ve ayrica bunlarin kisimlari muamele edilir. Diger bir tercih edilen
uygulamada, gerektiginde geleneksel yöntemler ile kombine edilen gen teknolojisi
yöntemleri ile elde edilen transgenik bitkiler ve bitki çesitleri (Genetically Modified
Organisms, Genetigi Degistirilmis Organizmalar) ile bunlarin kisimlari muamele edilir.
açiklanmistir.
Bulusa göre tercihen bilhassa ticari veya kullanimda olan bitki çesitleri muamele edilir.
Bitki çesitlerinden, hem geleneksel islah hem de mutajenez veya rekombinant DNA
teknikleri ile kültive edilmis olan, yeni özelliklere ("traits") sahip bitkiler anlasilir. Bunlar
varyete, biyo- ve genotip olabilir.
Bitki türüne veya bitki çesidine, bunlarin konumuna ve büyüme kosullarina (zemin,
iklim, vejetasyon periyotlari, beslenme) bagli olarak, bulusa göre muamele ile aditifin
üzerinde ("sinerjik") etkiler de ortaya çikabilir. Bu sekilde, örnegin, gerçekte beklenen
etkileri asan asagidaki etkiler mümkündür: bulusa göre kullanilabilecek etkin
maddelerin ve bilesimlerin uygulama miktarinin azalmasi ve/veya etki spektrumunun
genislemesi ve/veya etkililiginin yükselmesi, daha iyi bitki büyümesi, yüksek veya
düsük sicakliklara karsi toleransin yükselmesi, kurakliga veya su veya zemin tuz
içerigine karsi toleransin yükselmesi, çiçeklenme performansinin artmasi, hasat
etmenin kolaylasmasi, olgunlasmanin hizlanmasi, daha yüksek verimler, daha büyük
meyveler, daha fazla bitki yüksekligi, yapraklarin yesil renginin daha koyu olmasi, daha
erken çiçeklenme, hasat edilen ürünün kalitesinin yükselmesi ve/veya besin degerinin
yükselmesi, meyvelerde daha yüksek seker orani, hasat edilen ürünlerin
depolanabilirliginde ve/veya islenebilirliginde iyilesme.
Bulusa göre muamele edilecek olan tercih edilen transgenik (gen teknolojisi ile elde
edilmis olan) bitkiler veya bitki çesitleri, genetik materyalin, gen teknolojisi kullanilarak
bu bitkilere özellikle avantajli degerli özellikler ("traits") kazandiracak sekilde
degistirildigi tüm bitkileri içerir. Bu tür özelliklerin örnekleri arasinda daha iyi bitki
büyümesi, yüksek veya düsük sicakliklara karsi toleransin yükselmesi, kurakliga veya
su veya zemin tuz içerigine karsi toleransin yükselmesi, çiçeklenme performansinin
artmasi, hasat etmenin kolaylasmasi, olgunlasmanin hizlanmasi, daha yüksek
verimler, hasat edilen ürünün kalitesinin yükselmesi ve/veya besin degerinin
yükselmesi, hasat edilen ürünlerin depolanabilirliginde ve/veya islenebilirliginde
iyilesme bulunur. Bu tür özelliklerin diger ve özellikle önem verilen örnekleri bitkilerin
insektler, akarlar, fitopatojenik mantarlar, bakteriler ve/veya virüsler gibi hayvani ve
mikrobiyal zararlilara savunmasinin artmasini ve ayrica bitkilerin belirli herbisit etkin
maddelere karsi toleransinin artmasini içerir. Transgenik bitkiler örnek olarak, önemli
kültür bitkileri, Örnegin tahillar (bugday, pirinç), misir, soya, patates, seker pancari,
domates, bezelye ve diger sebze çesitleri, pamuk, tütün, kolza ve ayrica meyve bitkileri
(elma, armut, narenciye meyveleri ve üzüm asmalari dahil) belirtilebilir; bunlar
içerisinden misir, soya, patates, pamuk, tütün ve kolza özellikle öne çikar. Özellikler
("Traits") olarak, bilhassa, bitkilerin insektler, örümcegimsiler, nematodlar ve
salyangozlara karsi savunmasinin bitki bünyesinde olusan, bilhassa, Bacillus
Thuringiensis (örnegin CrylA(a), CrylA(b), CrylA(C), CryIIA, CryIIIA, CryIIIBZ, Cry9c
Cry2Ab, Cry38b ve CryIF genleri ve bunlarin kombinasyonari ile) genetik
materyalinden (metnin devaminda "Bt bitkiler" olarak anilacaktir) elde edilen toksinler
yoluyla kuvvetlendirilmesi öne çikmaktadir. Özellikler ("Traits") olarak, ayrica, bitkilerin,
mantarlara, bakterilere ve virüslere karsi savunmasinin Sistemik Edinilmis Direnç
(SAR), sistemin, fitoaleksinler, elisitörler ve ayrica direnç genleri ve ilgili sekilde ifade
edilen proteinler ve toksinler yoluyla kuvvetlendirilmesi de öne çikar. Özellikler ("traits")
olarak ayrica bitkilerin belirli herbisit etkin maddelere, örnegin imidazolinonlara,
sülfonilürelere, glifosata veya fosfinotrisine (örnegin "PAT" geni) karsi toleransindaki
yükselme özellikle öne çikar. Arzu edilen özellikleri (“traits") kazandiran genler ayrica
transgenik bitkilerde birbirleri ile kombine sekilde de bulunabilir. "Bt bitkilere" örnek
olarak, YIELD GARD® (örnegin misir, pamuk, soya), KnockOut® (örnegin misir),
StarLink® (örnegin misir), Bollgard® (pamuk), Nucotn® (pamuk) ve NewLeaf®
(patates) ticari adlari altinda satilan misir çesitleri, pamuk çesitleri, soya çesitleri ve
patates çesitleri belirtilebilir. Herbisit toleransi olan bitkilere örnek olarak Roundup
Ready® (glifosata toleransli, örnegin misir, pamuk, soya), Liberty Link® (fosfinotrisine
toleransli, örnegin kolza), IMI® (imidazolinona toleransli) ve STS® (sülfonilürelere
toleransli, örnegin misir) ticari adlari altinda satilan misir çesitleri, pamuk çesitleri ve
soya çesitleri belirtilebilir. Herbisit dirençli (geleneksel olarak herbisit toleransi için islah
edilmis olan) bitkiler ayni zamanda Clearfield® adi altinda satilan çesitler (örnegin
misir) olarak da belirtilmektedir. Tabii ki, bu önermeler ayni zamanda, gelecekte
gelistirilecek veya gelecekte piyasaya sürülecek olan bu veya gelecekte gelistirilecek
olan genetik özellikleri ("traits") tasiyan bitki çesitleri için de geçerlidir.
Listelenen bitkiler, genel formül l ile gösterilen bilesikler veya bulusa göre etkin madde
karisimlari ile bulusa göre özellikle avantajli sekilde muamele edilebilir. Yukarida etkin
maddeler veya karisimlari için belirtilen tercih edilen araliklar, bu bitkilerin muamele
edilmesi için de geçerlidir. Bitkilerin mevcut metinde özel olarak listelenen bilesikler
veya karisimlar ile muamele edilmesine özel önem verilir.
Bulusa göre etkin maddeler yalnizca bitki, hijyen ve depo zararlilarina karsi degil, ayni
zamanda veteriner tibbi alaninda, örnegin sert keneler, yumusak keneler, uyuz akari,
kadife akari, sinekler (sokucu ve yalayici), parazitik sinek larvalari, bitler, saç bitleri,
kanatli bitleri ve pireler gibi hayvan parazitlerine (ekto- ve endoparazitler) karsi da
etkilidir. Bu parazitler asagidakileri içerir:
Anoplurida takimindan örnegin Haematopinus spp., Linognathus spp., Pediculus spp.,
Mallophagida takimindan ve Amblycerina ve Ischnocerina alt takimlarindan örnegin
Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp.,
Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
Diptera takimindan ve Nematocerina ve Brachycerina alt takimlarindan örnegin Aedes
spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp.,
Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp.,
Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,
Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina
spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga
spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena
spp., Melophagus spp.
Siphonapterida takimindan örnegin Pulex spp., Ctenocephalides spp., Xenopsylla spp.,
Ceratophyllus spp.
Heteropterida takimindan örnegin Cimex spp., Triatoma Spp-. Rhodnius spp.,
Panstrongylus spp.
Blattarida takimindan örnegin Blatta orientalis, Periplaneta americana, Blattela
germanica, Supella spp.
Acari (Acarina) alt sinifindan ve Meta- ve Mesostigmata takimlarindan örnegin Argas
spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp.,
Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp.,
Dermanyssus spp., Raillietia spp., Pneumonyssus Spil, Sternostoma spp., Varroa spp.
Actinedida (Prostigmata) ve Acaridida (Astigmata) takimlarindan örnegin Acarapis
spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex
spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus
spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes
spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp.,
Laminosioptes spp.
Formül (I) ile gösterilen bulusa göre etkin maddeler ayni zamanda örnegin sigir, koyun,
keçi, at, domuz, esek, deve, manda, tavsan, tavuk, hindi, ördek, kaz, ari gibi tarim
hayvanlarini, örnegin köpek, kedi, kafes kuslari, akvaryum baliklari gibi çesitli ev
hayvanlarini ve ayrica, örnegin hamster, kobay, siçan ve fare gibi deney hayvanlarini
istila eden eklembacaklilar ile mücadele amaciyla da uygundur. Bu eklembacaklilar ile
mücadele yoluyla, ölüm olaylari ve verim düsüsleri (et, süt, yün, deri, yumurta, bal, vb.)
azaltilabilir, böylece bulusa göre etkin maddelerin kullanimi ile daha ekonomik ve kolay
bir hayvan besiciligi mümkün hale gelir.
Bulusa göre etkin maddelerin kullanimi veterinerlik ve hayvancilik alanlarinda, bilinen
sekilde, örnegin tablet, kapsül, içirme, islatma, granül, macun, bolus, kesintisiz
besleme yöntemi, süpozituvar formunda enteral uygulama ile, örnegin enjeksiyon
(intramüsküler, subkütan, intravenöz, intraperitoneal vd.), implant yoluyla parenteral
uygulama ile, nazal uygulama ile, örnegin daldirma veya banyo (batirma), püskürtme
(sprey), üzerine akitma (dökme ve damlatma), yikama, pudralama, formunda ve ayrica
tasma, kulak markasi, kuyruk markasi, ekstremite markasi, yular, isaretleme
düzenekleri vb. gibi etkin madde içeren objeler yoluyla dermal uygulama ile
gerçeklestirilebilir.
Büyükbas hayvanlar, kümes hayvanlari, ev hayvanlari vb. için kullanimda formül (I) ile
gösterilen etkin maddeler, etkin maddeleri agirlikça %1 ila 80 oraninda içeren
formülasyonlar seklinde (örnegin toz, emülsiyon, akiskan madde) dogrudan veya 100
ile 10000 defa seyreltme sonrasinda uygulanabilir veya kimyasal banyo olarak
kullanilabilir.
Ayrica, bulusa göre bilesiklerin, teknik malzemelere zarar veren insektlere karsi yüksek
insektisit etki gösterdigi bulunmustur.
Örnek olarak ve tercihen, bunlarla sinirli kalmaksizin, asagidaki insektler belirtilmistir:
Kinkanatlilar, örnegin Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,
Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Emobius mollis,
Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus Iinearis,
Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec.
Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus
brunneus, Sinoxylon spec. Dinoderus minutus;
Zarkanatlilar, örnegin Sirex juvencus, Urocerus gigas, Urocerus gigas taignus,
U rocerus aug U r;
Termitler, örnegin Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,
Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes Iucifugus,
Mastotermes darvviniensis, Zootermopsis nevadensis, Coptotermes formosanus;
Kilkuyruklar, örnegin Lepisma saccharina.
Teknik materyallerden, mevcut baglamda, tercihen plastikler, adezivler, tutkallar,
kagitlar ve kartonlar, deri, ahsap, agaç isleme ürünleri ve boyalar gibi, canli olmayan
materyaller anlasilacaktir.
Uygulama için hazir maddeler gerektiginde ayrica baska insektisitler ve gerekli
oldugunda ayrica bir veya daha fazla fungusit içerebilir.
Olasi ilave karisim ortaklari olarak, yukarida belirtilen insektisitlere ve fungusitlere atif
yapilir.
Bulusa göre bilesikler ayrica bilhassa gemi gövdeleri, elekler, aglar, binalar, rihtimlar ve
denize veya tuzlu suya temas eden sinyalizasyon tesislerinin yosun olusumuna karsi
korunmasi amaciyla da kullanilabilirler.
Ayrica, bulusa göre bilesikler, tek basina veya baska etkin maddeler ile birlikte, çürüme
önleyici maddeler olarak da kullanilabilir.
Etkin maddeler ayrica ev içi, hijyenik ve depolanmis ürün koruma amaciyla, digerlerinin
yani sira, örnegin konutlar, fabrika binalari, bürolar, araç kabinleri gibi kapali alanlarda
bulunabilen hayvani zararlilar ile, bilhassa insektler, örümcegimsiler ve akarlar ile
mücadele için uygundur. Bunlar, bu zararlilar ile mücadele için, evde kullanima yönelik
insektisit ürünler içerisinde tek basina veya diger etkin ve yardimci maddeler ile birlikte
kullanilabilirler. Duyarli ve dirençli türlere karsi ve ayrica bütün gelisim evrelerinde
etkilidirler. Bu zararlilar asagidakileri içerir:
Scorpionidea takimindan örnegin Buthus occitanus.
Acarina takimindan örnegin Argas persicus, Argas reflexus, Bryobia ssp.,
Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus
sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides
pteronissimus, Dermatophagoides forinae.
Araneae takimindan örnegin Aviculariidae, Araneidae.
Opiliones takimindan örnegin Pseudoscorpiones chelifer, Pseudoscorpiones
cheiridium, Opiliones phalangium.
lsopoda takimindan örnegin Oniscus asellus, Porcellio scaber.
Diplopoda takimindan örnegin Blaniulus guttulatus, Polydesmus spp.
Chilopoda takimindan örnegin Geophilus spp.
Zygentoma takimindan örnegin. Ctenolepisma spp., Lepisma saccharina, Lepismodes
inquilinus.
Blattaria takimindan örnegin Blatta orientalies, Blattella germanica, Blattella asahinai,
Leucophaea maderae, Panchlora spp., Parcoblatta Spil. Periplaneta australasiae,
Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella
Saltatoria takimindan örnegin Acheta domesticus.
Dermaptera takimindan örnegin Forficula auricularia.
Psocoptera takimindan örnegin Lepinatus spp., Liposcelis spp.
Coleoptera takimindan örnegin Anthrenus spp., Attagenus spp., Dermestes spp.,
Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus
granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.
Diptera takimindan örnegin Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus,
Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex
quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis,
Musca domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp., Stomoxys
calcitrans, Tipula paludosa.
Lepidoptera takimindan örnegin Achroia grisella, Galleria mellonella, Plodia
interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
Siphonaptera takimindan örnegin Ctenocephalides canis, Ctenocephalides felis, Pulex
irritans, Tunga penetrans, Xenopsylla cheopis.
Hymenoptera takimindan örnegin Camponotus herculeanus, Lasius fuliginosus, Lasius
niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium
caespitum.
Anoplura takimindan örnegin Pediculus humanus capitis, Pediculus humanus corporis,
Pemphigus spp., Phylloera vastatrix, Phthirus pubis.
Heteroptera takimindan örnegin Cimex hemipterus, Cimex Iectularius, Rhodinus
prolixus, Triatoma infestans.
Ev ortaminda kullanim amaçli insektisitler seklindeki kullanim tek basina veya fosforik
asit esterleri, karbamatlar, piretiroitler, neonikotinoidler, büyüme regülatörleri veya diger
bilinen insektisit siniflarindan etkin maddeler gibi baska uygun etkin maddeler ile
kombine sekilde gerçeklestirilebilir.
Uygulama aerosoller, basinçsiz spreyler, örnegin pompali ve atomizör spreyler, sis ve
duman makineleri, köpükler, jeller, selüloz veya plastikten buharlasma çipli buharlasma
ürünleri, sivi buharlastiricilar, jel ve membran buharlastiricilar, itici ile çalistirilan
buharlastirioilar, güç tüketmeyen veya pasif buharlastirici sistemler, güve kagitlari,
güve toplari ve güve jelleri içerisinde, granüller veya tozlar seklinde, yem kutusu veya
istasyonlari içerisinde gerçeklesir.
Bulusa göre etkin maddeler/etkin madde kombinasyonlari ayrica yaprak döktürücü,
kurutucu, sap kurutucu ajan olarak ve bilhassa yabani bitki öldürücü ajan olarak da
kullanilabilirler. Yabani bitki ifadesinden, en genis anlamiyla, istenmedikleri yerlerde
çikan tüm bitkiler anlasilacaktir. Bulusa göre maddelerin total veya selektif herbisit etki
gösterip göstermemesi esasen kullanilan miktara baglidir.
Bulusa göre etkin maddeler/etkin madde kombinasyonlari örnegin asagidaki bitkilerde
kullanilabilir:
Asagidaki cinslerden çift çenekli yabani otlar: Abutilon, Amaranthus, Ambrosia, Anoda,
Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea,
Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum,
Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium,
Lepidium, Lindemia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver,
Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala,
Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea,
Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
Asagidaki cinslerden çift Çenekli kültürler: Arachis, Beta, Brassica, Cucumis, Cucurbita,
Helianthus, Daucus, Glycine, Gossypium, lpomoea, Lactuca, Linum, Lycopersicon,
Nicotiana, Phaseolus, Pisum, Solanum, Vicia.
Asagidaki cinslerden tek çenekli yabani otlar: Aegilops, Agropyron, Agrostis,
Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon,
Cyperus, Dactyloctenium, Digitaria, Echinoohloa, Eleocharis, Eleusine, Eragrostis,
Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, lschaemum, Leptochloa,
Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia,
Sagittaria, Scirpus, Setaria, Sorghum.
Asagidaki cinslerden tek Çenekli kültürler: Allium, Ananas, Asparagus, Avena,
Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea.
Ancak bulusa göre etkin maddelerin/etkin madde kombinasyonlarinin kullanimi hiçbir
sekilde bu cinslerle sinirli degildir, ayni sekilde diger bitkilere de uzanir.
Bulusa göre etkin maddeler/etkin madde kombinasyonlari, konsantrasyona bagli olarak
örnegin sanayi ve demiryolu hatlarinda, agaçli ve agaçsiz yol ve meydanlarda total
yabani bitki mücadelesi için uygundur. Bulusa göre etkin maddeler ayrica çok yillik
bitkilerde, örnegin orman, süs, meyve, asma, narenciye, findik, muz, kahve, çay, sakiz,
palm yagi, kakao, dutsu meyveler ve serbetçi otu alanlarinda, süs ve spor amaçli çim
alanlarda ve meralarda yabani bitki mücadelesi için ve ayrica tek yillik kültürlerde
yabani bitki mücadelesi için kullanilabilirler.
Bulusa göre formül (I) ile gösterilen bilesikler/etkin madde kombinasyonlari topraga ve
bitkilerin toprak üstü kisimlarina uygulandiginda kuvvetli herbisit etkililige ve genis bir
etki spektrumuna sahiptir. Belirli bir ölçüde ayni zamanda hem çikis öncesi hem de
çikis sonrasi yöntemlerde tek çenekli ve çift çenekli kültürlerdeki tek çenekli ve çift
çenekli yabani bitkilerle selektif mücadele için uygundurlar.
Bulusa göre etkin maddeler/etkin madde kombinasyonlari belirli konsantrasyonlarda
veya uygulama miktarlarinda ayni zamanda hayvani zararlilarla ve mantar veya
bakteriyel bitki hastaliklariyla mücadele için de kullanilabilirler. Bunlar, ayni zamanda,
baska etkin maddelerin sentezinde ara ürün veya öncül ürün olarak da kullanilabilir.
Etkin maddeler/etkin madde kombinasyonlari çözelti, emülsiyon, sprey tozu,
süspansiyon, toz, serpme tozu, macun, çözünür toz, granül, süspansiyon-emülsiyon
konsantresi, etkin madde emdirilmis dogal ve sentetik maddeler gibi alisilageldik
formülasyonlara ve ayrica polimerik maddeler içerisinde mikroenkapsülasyonlara
dönüstürülebilir.
Bu formülasyonlar bilinen sekilde örnegin etkin maddelerin çogalticilar ile, yani sivi
solventler ve/veya kati tasiyici maddeler ile karistirilmasi yoluyla, gerektiginde yüzey
aktif maddeler, ayrica emülgatörler ve/veya dispersanlar ve/veya köpük meydana
getirici maddeler kullanilarak hazirlanabilir.
Çogaltici olarak su kullanilan durumlarda, örnegin organik solventler de yardimci
solvent olarak kullanilabilir. Sivi solventler olarak esasen asagidakiler degerlendirilir:
Ksilen, tolüen veya alkil naftalinler gibi aromatik bilesikler, örnegin klorobenzenler,
kloroetilenler veya metilen klorür gibi klorlu aromatik bilesikler ve klorlu alifatik
hidrokarbonlar, örnegin siklohekzan veya parafin gibi alifatik hidrokarbonlar, örnegin
petrol fraksiyonlari, mineral ve bitkisel yaglar, örnegin bütanol veya glikol gibi alkoller
ve ayrica bunlarin eterleri ve esterleri, örnegin aseton, metil etil keton, metil izobütil
keton veya siklohekzanon gibi ketonlar, örnegin dimetilformamit ve dimetilsülfoksit gibi
kuvvetli polar solventler ve ayrica su.
Kati tasiyici maddeler olarak asagidakiler degerlendilir ömegin kaolinler, killer, talk,
tebesir, kuvars, attapulgit, montmorillonit veya diatome topraklar gibi dogal kaya unlari
ve yüksek dispers silisik asit, alüminyum oksit ve silikatlar gibi sentetik kaya unlari,
granüller için kati tasiyici maddeler olarak asagidakiler degerlendirilir: örnegin kalsit,
mermer, bims, sepiolit, dolomit gibi çatlakli ve parçalanmis kayalar ve ayrica, inorganik
ve organik unlardan elde edilen sentetik granülatlar ile testere tozu, hindistan cevizi
kabuklari, misir koçanlari ve tütün saplari gibi organik granülatlardan elde edilen
sentetik granülatlar; emülgatör ve/veya köpük meydana getirici maddeler olarak
asagidakiler degerlendirilir: örnegin polioksietilen yag asidi esterleri gibi noniyonik ve
anyonik emülgatörler, örnegin alkilaril poliglikol eterler gibi polioksietilen yag alkolü
eterleri, alkilsülfonatlar, alkilsülfatlar, arilsülfonatlar ve protein hidrolizatlari; dispersanlar
olarak örnegin asagidaki maddeler degerlendirilir: Iignin sülfit atik çözeltileri ve metil
selüloz.
Formülasyonlarda, ayrica, örnegin karboksimetil selüloz, örnegin arap zamki, polivinil
alkol, polivinil asetat gibi dogal ve sentetik, toz halinde, parçacikli veya Iateks formunda
polimerler ve ayrica kefalin ve Iesitin gibi dogal fosfolipitler ve sentetik fosfolipitler gibi
yapistirici maddeler de kullanilabilir. Diger katki maddeleri mineral yaglar ve bitkisel
yaglar olabilir.
Inorganik pigmentler, örnegin demir oksit, titanyum oksit, ferrosiyanür mavisi ve organik
boyalar, örnegin alizarin, azo ve metalftalosiyanin boyar maddeler gibi boyar maddeler
ve demir, manganez, bor, bakir, kobalt, molibden ve çinko tuzlari gibi mikrobesinler
kullanilabilir.
Formülasyonlar genellikle agirlikça yüzde 0,1 ila 95 oraninda, tercihen %O,5 ila 90
oraninda etkin madde içerir.
Bulusa göre etkin maddeler/etkin madde kombinasyonlari, oldugu gibi veya
formülasyonlari içerisinde veya ayni zamanda bilinen herbisitler ve/veya kültür
bitkilerinin toleransini iyilestirdigi bilinen maddeler ("safener") ile karisim içerisinde
yabani bitki mücadelesi için kullanilabilir, burada kullanima hazir formülasyonlari veya
tarik karisimlari mümkündür. Ayrica bir veya daha fazla bilinen herbisit ve bir safener
içeren yabani ot mücadele ajanlari ile karisimlar da mümkündür.
Karisimlar için örnegin asagidakiler gibi bilinen herbisitler degerlendirilir
Asetoklor, asiflorfen (-sodyum), aklonifen, alaklor, alloksidim (-sodyum), ametrin,
amikarbazon, amidoklor, amidosülfüron, aminopiralid, anilofos, asulam, atrazin,
azafenidin, azimsülfüron, beflubütamid, benazolin (-etil), benfuresat, bensülfüron (-
metil), bentazon, benzkarbazon, benzfendizon, benzobisiklon, benzofenap, benzoilprop
(-etil), bialafos, bifenoks, bispiribak (-sodyum), bromobütid, bromofenoksim,
bromoksinil, bütaklor, bütafenasil (-alil), bütroksidim, bütilat, kafenstrol, kaloksidim,
karbetamit, karfentrazon (-etil), klometoksifen, kloramben, kloridazon, klorimuron (-etil),
klornitrofen, klorsülfüron, klortolüron, sinidon (-etil), sinmetilin, sinosülfüron, klefoksidim,
kletodim, klodinafop (-proparjil), klomazon, klomeprop, klopiralid, klopirasülfüron (-
metil), kloransulam (-metil), kumiluron, siyanazin, sibütrin, sikloat, siklosülfamuron,
sikloksidim, sihalofop (-büti|), 2,4-D, 2,4-DB, desmedifam, diallat, dikamba, diklorprop (-
p), diklofop (-metil), diklosulam, dietatil (-etil), difenzokuat. diflufenikan, diflufenzopir,
dimefuron, dimepiperat, dimetaklor, dimetametrin, dimetenamit, dimeksiflam,
dinitramin, difenamit, dikuat, ditiyopir, diuron, dimiron, epropodan, EPTC, esprokarb,
etalfluralin, etametsülfüron (-metil), etofumesat, etoksifen, etoksisülfüron, etobenzanid,
fenoksaprop (-p-etil), fentrazamit, flamprop (-izopropil, -izopropiI-L, -metil),
flazasülfüron, florasulam, fluazifop (-P-bütil), fluazolat, flukarbazon (-sodyum),
flufenaset, flumetsulam, flumiklorak (-pentil), flumioksazin, flumipropin, flumetsulam,
fluometuron, florokloridon, floroglikofen (-etil), flupoksam, flupropasil, flurpirsülfüron (-
metil, -sodyum), flurenol (-bütil), fluridon, fluroksipir (-büt0ksipropil, -meptil), flurprimidol,
flurtamon, flutiyaset (-metil), flutiyamit, fomesafen, foramsülfüron, glufosinat (-
amonyum), glifosat (-izopr0pilam0nyum), halosafen, haloksifop (-etoksietil, -P-metil),
hekzazinon, HOK-201, imazametabenz-metil), imazametapir, imazamoks, imazapik,
imazapir, imazakuin, imazetapir, imazosülfüron, iyodosülfüron (-metil, -sodyum),
iyoksinil, izopropalin, izoproturon, izouron, izoksaben, izoksaklortol, izoksaflutol,
izoksapirifop, KIH 485, Iaktofen, Ienasil, Iinuron, MCPA, mekoprop, mefenaset,
mesosülfüron, mesotrion, metamifop, metamitron, metazaklor, metabenztiyazuron,
metobenzuron, metobromuron, (alfa-) met0|aklor, metosulam, metoksuron, metribuzin,
metsülfüron (-metil), molinat, monolinuron, naproanilid, napropamit, neburon,
nikosülfüron, norflurazon, orbenkarb, ortosülfamuron, orizalin, oksadiarjil, oksadiazon,
oksasülfüron, oksaziklomefon, oksiflorfen, parakuat, pelarjonik asit, pendimetalin,
pendralin, penokssulam, pentoksazon, fenmedifam, pikolinafen, pinoksaden, piperofos,
pretilaklor, primisülfüron (-metil), profluazol, prometrin, propaklor, propanil,
propakuizafop, propizoklor, propoksikarbazon (-sodyum), propizamit, prosülfokarb,
prosülfüron, piraflufen (-etil), pirasülfotol, pirazogil, pireizolati pirazosülfüron (-etil),
pirazoksifen, piribenzoksim, piribütikarb, piridat, piridatol, piriftalid, piriminobak (-metil),
pirimisülfan, piritiyobak (-sodyum), kuinklorak, kuinmerak, kuinoklamin, kuizalofop (-P-
etil, -P-tefuril), rimsülfüron, setoksidim, simazin, simetrin, sülkotrion, sülfentrazon,
sülfometuron (-metil), sülfosat, sülfosülfüron, tebütam, tebütiuron, tembotrion,
tepraloksidim, terbütilazin, terbütrin, tenilklor, tiyafluamit, tiyazopir, tidiazimin,
tifensülfüron (-metil), tiyobenkarb, tiokarbazil, topramezon, tralkoksidim, triallat,
triasülfüron, tribenuron (-metil), triklopir, tridifan, triflurailini trifloksisülfüron, triflusülfüron
(-metil), tritosülfüron ve
2.-- .I ^
Ayrica örnegin fungusitler, insektisitler, akarisitler, nematisitler, kuslarin yemesini
önlemeye yönelik maddeler, bitki besinleri ve toprak yapisini iyilestirici ajanlar gibi diger
bilinen etkin maddelerle bir karisim da mümkündür
Etkin maddeler veya etkin madde kombinasyonlari olduklari gibi, formülasyonlari
seklinde veya örnegin kullanima hazir solüsyonlar, süspansiyonlar, emülsiyonlar,
tozlar, macunlar ve granüller gibi bunlarin daha fazla seyreltilmesiyle hazirlanan
uygulama formlari seklinde uygulanabilirler. Uygulama alisildik sekilde, örnegin dökme,
sprey, püskürtme, saçma yoluyla gerçeklestirilir.
Bulusa göre etkin maddeler veya etkin madde kombinasyonlari bitkilerin çikmasindan
hem önce hem de sonra uygulanabilir. Ayrica tohumlamadan önce topraga da
karistirilabilirler.
Kullanilan etkin madde miktari genis bir aralikta degisiklik gösterebilir. Esasen istenen
etki türüne baglidir. Uygulama miktarlari genellikle arazi alaninin her hektari için 1 9 ile
kg etkin madde arasinda, tercihen ha basina 5 9 ile 5 kg arasinda yer alir.
Bulusa göre etkin madde kombinasyonlarinin avantajli kültür bitkisi toleransi belirli
konsantrasyon oranlarinda özellikle belirgindir. Bununla birlikte etkin madde
kombinasyOnlarindaki etkin madde agirlik oranlari oldukça genis bir aralikta
degistirilebilir. Genel olarak, formül (I) ile gösterilen etkin maddenin agirlikça 1 kismi
basina, yukarida (b') altinda belirtilen, kültür bitkilerinin toleransini iyilestiren bilesiklerin
100 kisim, özellikle tercihen agirlikça 0,05 ile 20 kisim düser.
Bulusa göre etkin madde kombinasyonlari genellikle hazir formülasyonlar seklinde
kullanima sunulur. Etkin madde kombinasyonlarinda bulunan etkin maddeler tekli
formülasyonlari halinde uygulama sirasinda da karistirilabilir, yani tank karisimlari
olarak da uygulanabilir.
Belirli uygulama amaçlari için, bilhassa çikis sonrasi yöntemlerde. formülasyonlara
ilave katki maddeleri olarak bitki tarafindan tolere edilebilen mineral veya bitkisel yaglar
(örnegin "Rako Binol" ticari preparati) veya örnegin amonyum sülfat veya amonyum
rodanid gibi amonyum tuzlari katilmasi da avantajli olabilir.
Yeni etkin madde formülasyonlari olduklari gibi, formülasyonlari seklinde veya örnegin
kullanima hazir solüsyonlar, süspansiyonlar, emülsiyonlar, tozlar, macunlar ve
granüller gibi bunlarin daha fazla seyreltilmesiyle hazirlanan uygulama formlari
seklinde uygulanabilirler. Uygulama alisildik sekilde, örnegin dökme, sprey, püskürtme,
serpme veya saçma yoluyla gerçeklestirilir.
Bulusa göre etkin madde kombinasyonlarinin uygulama miktarlari belirli bir aralikta
degistirilebilir; havaya ve toprakla ilgili çesitli faktörlere bagli olarak degisir. Genel
olarak uygulama miktarlari ha basina 0,001 ile 5 kg arasinda, tercihen ha basina 0,005
ile 2 kg arasinda, özellikle tercihen ha basina 0,01 ile 0,5 kg arasinda yer alir.
Bulusa göre etkin madde kombinasyonlari bitkilerin çikmasindan hem önce hem de
sonra, yani çikis öncesi ve çikis sonrasi yöntemlerde uygulanabilir.
Bulusa göre kullanilacak safenerler özelliklerine bagli olarak kültür bitkisi tohumunun
ön islemden geçirilmesi (tohumun islaçlanmasi) için kullanilabilir veya tohumdan önce
kariga uygulanabilir veya herbisitten ayri olarak veya herbisit ile birlikte bitkinin uç
vermesinden önce veya sonra uygulanabilir.
Etkin maddelerin bitki hastaliklariyla mücadelede gerekli olan konsantrasyonlarda bitki
toleransinin iyi olmasi, toprak üstü bitki kisimlarinin, fidan ve tohumlarin ve topragin
Bulusa göre etkin maddeler ayrica mahsul veriminin yükseltilmesi için de uygundur.
Ayrica toksisiteleri düsüktür ve bitki toleranslari iyidir.
Bulusa göre etkin maddeler gerektiginde belirli konsantrasyonlarda ve uygulama
miktarlarinda herbisitler olarak, bitki büyümesini etkilemek amaciyla ve ayrica hayvani
zararlilarla mücadele için de kullanilabilirler. Bunlar gerektiginde baska etkin
maddelerin sentezinde ara ürün ve öncül ürün olarak da kullanilabilir.
Etkin madde ifadesi belirtilen etkin madde kombinasyonlarini da kapsar.
Bulusa göre etkin maddelerin hazirlanmasi ve kullanimi asagidaki örneklerde
gösterilmektedir.
Hazirlama örnekleri
Örnek l-1-a-1
Yöntem A
6 ml N,N-dimetil asetamit içerisinde 1,83 9 (15,5 mmol) potasyum tert-bütilata, 6 ml
N,N-dimetil asetamit içerisindeki Örnek II-1'e göre bilesikten 2,4 9 80°C'de damlatilarak
ilave edilir ve bir saat süreyle 80°C'de karistirilir.
Ince tabaka kromatografisi numunesinin ardindan, reaksiyon karisimi 80 ml buzlu SU
üzerine ilave edilir ve 0-10°C'de 1 N hidroklorik asit ile pH 2'ye getirilir. Çökelti aspire
edilir, yikanir ve kurutulur.
Ham verim: 2,35 9 bej renkli toz
Preparatif HPLC ile ayirmanin ardindan asagidaki ürün elde edilir
Verim: 173 mg (teorinin %7,7'si) erime sicakligi 94°C
Örnek l-1-a-2
Yöntem A
4 ml N,N-dimetil asetamit içerisinde 1,3 9 (10,5 mmol) potasyum tert-bütilata, 4,0 ml
N,N-dimetil asetamit içerisindeki Örnek II-2`ye göre bilesikten 1,95 9 (4,7 mmol)
60°C'de damlatilarak ilave edilir ve bir saat süreyle 60°C'de karistirilir.
Ince tabaka kromatografisi numunesinin ardindan, reaksiyon karisimi 80 ml buzlu su
üzerine ilave edilir ve 0-10°C'de 1 N hidroklorik asit ile pH 2'ye getirilir, aspire edilir,
yikanir ve kurutulur. Saflastirma mobil faz olarak asetik asit etil esteri kullanilarak silika
jel üzerinde kolon kromatografisi ile gerçeklestirilir.
Örnek l-1-a-24
Yöntem C
0,8 9 sodyum karbonat 15 ml su içerisine konur, 0,05 9 paladyum (ll) nitrat dihidrat
ilave edilir ve 20 dakika süreyle 144°C'de mikrodalgada karistirilir. Sogutmanin
ardindan seyreltik hidroklorik asit ile asitlendirilir ve aspire edilir.
Elüsyon gradyani olarak siklohekzan + %50-80 asetik asit etil esteri ile silika jel
üzerinde MPLC ile ayirma gerçeklestirilir
Verim: 0,31 9 (teorinin %34'ü), erime sicakligi 257°C
Örnekler (I-1-a-1) ve (l-1-a-2)'ye benzer sekilde ve üretime iliskin genel verilere göre formül (I-1-a) ile gösterilen asagidaki bilesikler elde
Örnek W X Y F V1 V2 A B Erime sicakligi °C Izomer
Numarasi
Örnek W X Y F V1 V2 A B Erime sicakligi °C
Numarasi
7.61-7.66 (m, 2H, Ar-H)
Izomer
Numarasi
3-CH3
3-CF3
3-CF3
3-CF3
2-CH3
2-CH3
- -(CH2)2-O-(CH2)2-
' '(CH2)2'O'(CH2)2'
Erime sicakligi 'C
Izomer
Numarasi
CH3 CH3
CH3 CH3
CH3 CH3
2-CH3
Erime sicakligi °C
Izomer
Örnek W X Y F V1 V2 A B Erime sicakligi °C
Numarasi
Izomer
cis/trans
Örnek W X Y F V1 V2 A B Erime sicakligi °C Izomer
Numarasi
yaklasik 1:1
Örnek W X Y F V1 V2 A B Erime sicakligi °C Izomer
Numarasi
7.26-7.44 (m, 6H, ArH)
7.05 (d, 1H, ArH)
7.16 (d, 1H, ArH)
Numarasi
CH3 CH3 H
4 2-i=
Erime sicakligi °C Izomer
*222 (s, SH, Arws)
3.68-376 (m, 2H, o-Qg)
729-737 (m, 4H, Aru)
3.65-3.72 (m, 2H, O-Qg)
7.07-7.11 (m, 2H, Arü)
* 1H-NMR (: ö degerindeki kaymalar, ppm olarak
Ornek (l-1-b-1)
50 ml asetik asit etil esteri içerisinde Örnek (I-1-a-4)'e göre bilesikten 0,78 g'a (2 mmol)
0,28 ml (2 mmol) trietilamin ve 20 mg 4-N,N-dimetilamino piridin ilave edilir. Geri akis
altinda 5 ml asetik asit esteri içerisindeki 0,19 9 (2 mmol) propiyonik asit klorür
damlatilarak ilave edilir. Reaksiyonun sona ermesinin ardindan (ince tabaka ile kontrol)
reaksiyon karisimi vakum altinda uçurulur ve kalinti su/asetonitril mobil faz sistemiyle
Ters Faz Kromatografi ile saflastirilir. 0,5 9 (iteorinin %58'i), erime sicakligi 234°C
Örnek (I-1-b-1)'e benzer sekilde ve üretime iliskin genel verilere göre formül (I-1-b) ile gösterilen asagidaki bilesikler elde edilir:
Örnek Numarasi
Erime sicakligi °C
Izomer
Örnek Numarasi
* Ph = Fenil
4-CI-Ph*
4-Cl-Ph*
Erime sicakligi °C
Izomer
Ornek (l-1-c-1i
ml (2 mmol) trietilamin ilave edilir. Yaklasik 30°C'de 5 ml diklorometan içerisinde 0,19
ml (2 mmol) kloroformik asit etil esteri damlatilarak ilave edilir 30 - 40°C'de karistirilir.
Reaksiyonun sona ermesinin ardindan (ince tabaka ile kontrol) reaksiyon karisimi
vakum altinda uçurulur ve kalinti su/asetonitril mobil faz sistemiyle Ters Faz
Kromatografi ile saflastirilir. 0,18 9 (iteorinin %20'si), erime sicakligi 206°C elde edilir.
Örnek (I-1-C-1)'e benzer sekilde ve üretime iliskin genel verilere göre formül (I-1-c) ile gösterilen asagidaki bilesikler elde edilir:
Örnek Numarasi
l-1-c-4
*Ph = Fenil
Erime sicakligi °C
Izomer
Ornek (l-1-f-1)
3 ml 1 N sodyum hidroksit solüsyonu ve 7 ml su saglanir, ardindan Örnek l-1-a-4'e
göre bilesikten 1,1 9 kisimlar halinde ilave edilir, çözülür, akabinde döner evaporatörde
kuruluga kadar uçurulur.
Verim: 1 g (teorinin %80'i)
1H-NMR (, 2,02,
Örnek (I-1-f-1)'e benzer sekilde ve üretime iliskin genel verilere göre formül (I-1-f) ile gösterilen asagidaki bilesikler elde edilir:
Örnek Numarasi W X Y F V1 V2 A B E NMRVeriIeri Izomer
6.75-6.77(m,1H,Ar-u)
6.89-6.91(m,1H,Ar-u)
2.23(s,3H,Ar-%3)
3.56-3.63(m,2H,O%2)
7.02-7.08(m,2H,Ar-h)
Örnek Numarasi W X Y F V1 V2 A B
* 1H-NMR (: ö degerindeki kaymalar, ppm olarak
NMR Verileri IZOme'
2.23(s,3H,Ar-%3)
3.56-3.62(m,2H,OC_H2)
7.01-7.07(m,2H,Ar-u)
* 1.88-1.96(m,2H,C_Hg)
3.56-3.62(m,2H,O-%2)
7.56-7.61(m,3H,Ar-u)
Ornek (l-1'-a-1i
50 ml N,N-dimetil asetamit içerisinde 14,1 9 potasyum tert-bütilat saglanir, 50 ml DMA
içerisinde çözünmüs Örnek lI-1'-1'e göre bilesikten 22,3 9 50°C'de damlatilarak ilave
edilir ve 1 saat süreyle 50°C'de karistirilir. Reaksiyon karisimi buzlu su üzerine
dökülür, seyreltik hidroklorik asit ile asitlendirilir ve aspire edilir. Önce su ile birden çok
defa yikanir ve ardindan 2 defa MTBE ile karistirilir ve aspire edilir. Ana sivi 4 gün
sonra yeniden filtre edilir ve MTBE ile yikanir.
Verim: 20 mg (teorinin %98'i), erime sicakligi 143°C
MTBE = Metil tert.-bütil eter
Örnek (I-1'-a-1)'e benzer sekilde ve giriste anilan literatürde üretime iliskin genel verilere göre formül (I-1'-a) ile gösterilen asagidaki
bilesikler elde edilir:
Örnek Numarasi W X Y Z' Erime sicakligi °C
Ornek (ll-1511
olusumunun sona ermesine kadar karistirilir ve ardindan konsantre edilir. Kalinti tolüen
içerisine alinir ve yeniden döner evaporatörde uçurulur (= asit klorür). 21,5 9 4-amino-
tetrahidropiran-4-karboksilik asit metil esteri hidroklorür 80 ml asetik asit esteri
içerisinde saglanir, O°C'de 110 ml sodyum hidroksit solüsyonu ilave edilir ve ardindan,
hizla karistirilirken ayni zamanda asit klorür asetik asit esteri ile 100 ml'de tamamlanir
ve sodyum hidroksit solüsyonunun kalani damlatilarak ilave edilir. Reaksiyonun sona
ermesinin ardindan ürün aspire edilir (1). Filtrat su ve asetik asit esteri ile çalkalanir,
organik faz sodyum sülfat üzerinde kurutulur, filtre edilir ve konsantre edilir. Kalinti az
miktarda asetik asit esteri ile karistirilir ve aspire edilir (2).
Argon altinda 3,23 9 4-amino-tetrahidropiran-4-karboksilik asit metil esteri hidroklorür
(16,5 mmol) ve 75 ml aköz tetrahidrofuran saglanir.
°C'de 4,6 ml (33 mmol) trietilamin damlatilarak ilave edilir.
dakika süreyle daha karistirilir ve 20°C'de 4,2 9 2-metiI-5-(4-florofeniI)-fenil asetik asit
(15 mmol) ile karistirilir. 15 dakika sonra buna 3,45 ml trietilamin (25 mmol) ve hemen
ardindan 0,93 ml fosfor oksiklorür (10 mmol) damlatilarak ilave edilir ve solüsyon orta
derecede kaynatilir. 30 dakika süreyle geri akis altinda karistirilir.
Ince tabaka kromatografisiyle kontrolün ardindan solvent döner evaporatörde uçurulur
ve silika jel üzerinde kolon kromatografisiyle saflastirilir (diklorometan: asetik asit etil
Verim: 2,19 mg (teorinin %33'ü), erime sicakligi 113°C
Örnek (II-1)'e benzer sekilde ve üretime iliskin genel verilere göre formül (II) ile gösterilen asagidaki bilesikler elde edilir:
Örnek W X Y FV1 VZA B R3 Erimesicakligi°C
Numarasi
”-6 H CH3 H 4 H H -CHz-CHCHg-O- CH3 camsi kati
Izomer
Numarasi
V1 V2A B
Erime sicakligi DC
Izomer
Numarasi
CH3 CH3
V1 V2A B
*(71l:*(`.llý((`.ll:lr
(ilCHOyOCII:
-Cllg-îl I-(Cllcls-
( 7((I`llg)270(`,lls
Erime sicakligi DC
COüg), 7.02-7.07 (m,1H,Ar-u).
725-730 (m, 2H, Ar-H)
Izomer
karisim
karisim
cisztrans
yaklasik 2:1
cisztrans
yaklasik 1:1
cisztrans
yaklasik 1:1
Numarasi
V1 V2A B
Re Erime sicakligi DC Izomer
CH3 vaks -
CH3 111 _
CZH5 yag cisztrans
yaklasik 1:1
C2H5 yag cisztrans
yaklasik 1:1
(a, 2H, Ogg-cm)
C2H5 * 3.66 (m,2H,%-Ar), 4.15 (m, SH, O-wg-CHg, CHO- trans
* 1H-NMR (: ö degerindeki kaymalar, ppm olarak
Formüller (XIX) ve (xxiii)
ile gösterilen bilesiklerin hazirlanmasi
ile gösterilen
asagidaki bilesikler elde edilmistir:
Örnek Numarasi W X
v1 Erime sicakligi °c
3-F * Yag
4-ci * Yag
3-F * Yag
4-CI * Yag
* Bilesikler (XIX) bilesiklerini verecek sekilde ilave karakterizasyon olmadan dogrudan
esterlestirilmistir.
Örnek Numarasi W X
H 3 4-CI
1H-NMR
*2.28 (3, 3H, Ar-gg)
365 (s, 2H, %2)
7.25 (d. 1H, Ar-H)
*2.28 (s, 3H, Ar-g3)
3.66 (5, 2H, Ar-wg
Örnek Numarasi w x Y F v1 1H-NMR
747-750 (m, 1H, Ar-ü)
2.31 (3, 3H, Ar-wg)
3.68 (8, 2H, %2)
6.98 (d. 1H, Ar-H)
7.39-7.46 (m, 1H, Ar-u)
2.31 (8, 3H, Ar-ws)
3.68 (8, 2H, Ar-gz)
7.08-7.12 (m, 2H, Ar-g)
725-728 (m, 1H, Ar-u)
7.59 (t, 1H, Ar-H)
*1H-NMR (: ö degerindeki kaymalar, ppm olarak
LogP degerlerinin tayini
Tabloda verilen logP degerleri, EEC Direktifi 79/831 Ek V.A8'e göre HPLC (High
Performance Liquid Chromatography) ile bir ters faz kolon (018) üzerinde tayin
edilmistir. Sicaklik: 43°C
Asidik bölgede (pH 2,3) tayin için elüentler: %O,1 aköz fosforik asit, asetonitril; dogrusal
gradyan: %10 asetonitrilden %90 asetonitrile
Kalibrasyon IogP degerleri bilinen (3 ila 16 karbon atomuna sahip) dallanmamis alkan-
2-0nlar ile gerçeklestirilmistir (logP degerlerini birbirini takip eden iki alkanon arasinda
dogrusal interpolasyon ile alikonma zamanlarina dayanarak belirlenir).
Lambda maks degerleri, kromatografik sinyallerin maksimumlarinda 200 nm'den 400
nm'ye UV spektrumlarina göre tayin edilmistir.
Uygulama örnekleri
Örnek A: Bitkiye penetrasyonun amonyum veya fosfonyum tuzlariyla artirilmasi veya
bitkiye penetrasyonun penetrasyon artiricilar ile kombine amonyum/fosfonyum
tuzlariyla sinerjik olarak artirilmasi
Bu testte etkin maddelerin elma agaci yapraklarinin enzimatik olarak izole edilen
kütikulalarindan penetrasyonu ölçülmüstür.
Golden Delicious çesidi elma agaçlarinin tam geliskin durumunda kesilen yapraklar
kullanilmistir. Kütikulalarin izolasyonu
- önce alti boya ile isaretlenmis ve zimbalanarak çikartilmis yaprak diskleri
vakum infiltrasyonuyla 3 ile 4 arasindaki bir pH degerinde tamponlanmis
pektinaz solüsyonu (%02 ila 2'lik) ile doldurularak,
- ardindan sodyum azid ilave edilerek ve
- bu sekilde muamele edilen yaprak diskleri orijinal yaprak yapisi çözünene ve
selüler olmayan kütikula uzaklastirilana kadar bekletilerek gerçeklestirilmistir.
Ardindan yalnizca artik yapraklarin üst yüzlerinin stoma ve tüy içermeyen kütikulalari
kullanilmistir. Bunlar birden fazla defa degismeli olarak su ve pH degeri 7 olan bir
tampon solüsyon ile yikanmistir. Elde edilen temiz kütikulalar daha sonra teflon
plakalar üzerine konmustur ve hafif bir hava akimi ile düzlestirilmis ve kurutulmustur.
Sonraki adimda bu sekilde elde edilen kütikula membranlari membran transportu
incelemeleri için paslanmaz çelikten mamul difüzyon hücrelerine (= transport
odaciklari) konmustur. Bu amaçla kütikulalar pensle alinarak difüzyon hücresinin silikon
yagi sürülmüs kenarlarinin ortasina yerlestirilmistir ve yine yaglanmis bir halka ile
kapatilmistir. Düzenleme, kütikulalarin morfolojik dis yüzleri disariya, yani havaya
bakacak sekilde ve orijinal iç yüzleri difüzyon hücresinin içine dönük olacak sekilde
yapilmistir.
Difüzyon hücreleri oA›30'Iuk bir etilen glikol/ su solüsyonu ile doldurulmustur.
Penetrasyonun tayin edilmesi amaciyla, kütikulalarin dis yüzeylerine asagidaki
bilesime sahip püskürtme sivisindan 10'ar pl uygulanmistir. Püskürtme sivisi orta
sertlikteki yerel sebeke suyu kullanilarak hazirlanmistir.
Püskürtme sivisinin uygulanmasinin ardindan suyun buharlasmasi beklenmistir,
odaciklar döndürülmüstür ve kütikula üzerindeki sicakligin ve nemin, püskürtme
kalintisi tasiyan kütikulalar üzerine hafif bir hava akimi ile ayarlanabildigi termostatli
düzenli araliklarla alikuotlar alinmistir ve etkin madde içerigi HPLC ile tayin edilmistir.
Deney sonuçlari asagidaki tabloda gösterilmektedir. Belirtilen sayilar 8 ila 10 ölçümden
elde edilen ortalama degerlerdir. Tek basina amonyum sülfatin bile penetrasyonu
belirgin sekilde iyilestirdigi ve RME ile birlikte aditifin üzerinde (sinerjik) bir etkinin
ortaya çiktigi açikça görülmektedir.
Tablo A
Etkin madde
24 saatin ardindan penetrasyon / %
Örnek I-1-a-4 3 8 30
DMF içerisinde 500 ppm / Emülgatör W
7:1 (w/w)
RME = Kolza yagi metil esteri (500 EW olarak formüle edilmis sekilde kullanilir,
konsantrasyon g etkin madde /I olarak verilmistir)
AS = Amonyum sülfat
EC = Emülsifiye edilebilir konsantre
Phaedon testi (PHAECO sprey islemi)
Solvent: 78,0 Agirlikça kisim aseton
1,5 Agirlikça kisim dimetilformamit
Emülgatör: 0,5 Agirlikça kisim alkilaril poliglikol eter
Amaca uygun bir etkin madde preparatini hazirlamak amaciyla, agirlikça 1 kisim etkin
madde, belirtilen miktarlarda solvent ve emülgatör ile karistirilir ve konsantre,
emülgatör içeren su ile istenen konsantrasyona seyreltilir.
Çin Iahanasi yaprak disklerine (Brassica pekinensis) istenen konsantrasyonda etkin
madde preparati püskürtülür ve kurumasinin ardindan yaban turpu yaprak böcegi
(Phaedon cochleariae) larvalari ile kaplanir.
Istenen sürenin ardindan % olarak etki tayin edilir. Burada, %100 bütün böcek
Bu testte örnegin hazirlama örneklerindeki asagidaki bilesikler 500 g/ha uygulama
miktarinda 7 günün ardindan 2 %80 oraninda etki göstermektedir: I-1-a-1, l-1-a-2, I-1-
,1-1-f-1
Bu testte örnegin hazirlama örneklerindeki asagidaki bilesikler 100 g/ha uygulama
miktarinda 7 günün ardindan 2 %80 oraninda etki göstermektedir: I-1-a-7.
Spodoptera frugiperda testi (SPODFR sprey islemi)
Solvent: 78,0 Agirlikça kisim aseton
1,5 Agirlikça kisim dimetilformamit
Emülgatör: 0,5 Agirlikça kisim alkilaril poliglikol eter
Amaca uygun bir etkin madde preparatini hazirlamak amaciyla, agirlikça 1 kisim etkin
madde, belirtilen miktarlarda solvent ve emülgatör ile karistirilir ve konsantre,
emülgatör içeren su ile istenen konsantrasyona seyreltilir.
Misir yapragi disklerine (Zea mays), istenen konsantrasyonda etkin madde preparati
püskürtülür ve kurumasinin ardindan sonbahar tirtil ordusu tirtillari (Spodoptera
frugiperda) ile kaplanir.
Istenen sürenin ardindan % olarak etki tayin edilir. Burada, %100, bütün tirtillarin
öldügü anlamina gelir; %0 ise hiçbir tirtilin ölmedigi anlamina gelir.
Bu testte örnegin hazirlama örneklerindeki asagidaki bilesikler 500 g/ha uygulama
miktarinda 7 günün ardindan 2 %80 oraninda etki göstermektedir: I-1-a-1, I-1-a-3, I-1-
Myzus testi (MYZUPE sprey islemi)
Solvent: 78,0 Agirlikça kisim aseton
1,5 Agirlikça kisim dimetilformamit
Emülgatör: 0,5 Agirlikça kisim alkilaril poliglikol eter
Amaca uygun bir etkin madde preparatini hazirlamak amaciyla, agirlikça 1 kisim etkin
madde, belirtilen miktarlarda solvent ve emülgatör ile karistirilir ve konsantre,
emülgatör içeren su ile istenen konsantrasyona seyreltilir.
Yesil seftali yaprak bitinin (Myzus persicae) bütün evreleri tarafindan istila edilmis olan
Çin Iahanasi yaprak disklerine (Brassica pekinensis) istenen konsantrasyonda etkin
madde preparati püskürtülür.
Istenen sürenin ardindan % olarak etki tayin edilir. Burada, %100, bütün yaprak
bitlerinin öldügü anlamina gelir; %0 ise hiçbir yaprak bitinin ölmedigi anlamina gelir.
Bu testte örnegin hazirlama örneklerindeki asagidaki bilesikler 500 g/ha uygulama
miktarinda 6 günün ardindan 2 %80 oraninda etki göstermektedir: I-1-a-1. I-1-a-2. I-1-
Tetranychus testi; OP dirençli (TETRUR sprey islemi)
Solvent: 78,0 Agirlikça kisim aseton
1,5 Agirlikça kisim dimetilformamit
Emülgatör: 0,5 Agirlikça kisim alkilaril poliglikol eter
Amaca uygun bir etkin madde preparatini hazirlamak amaciyla, agirlikça 1 kisim etkin
madde, belirtilen miktarlarda solvent ve emülgatör ile karistirilir ve konsantre,
emülgatör içeren su ile istenen konsantrasyona seyreltilir.
Iki benekli örümcek akarinin (Tetranychus urticae) bütün evreleri tarafindan istila
edilmis olan fasulye yaprak disklerine (Phaseol'us vu/gari's), istenen konsantrasyonda
etkin madde preparati püskürtülür.
Istenen sürenin ardindan % olarak etki tayin edilir. Burada, %100 bütün örümcek
akarlarinin öldügü anlamina gelir; %0 hiçbir örümcek akarinin ölmedigi anlamina gelir.
Bu testte örnegin hazirlama örneklerindeki asagidaki bilesikler 100 g/ha uygulama
miktarinda 6 günün ardindan 2 %80 oraninda etki göstermektedir: I-1-a-3, I-1-a-7, H-
Bu testte örnegin hazirlama örneklerindeki asagidaki bilesikler 20 g/ha uygulama
miktarinda 6 günün ardindan 2 %80 oraninda etki göstermektedir: I-1-a-1, I-1-a-4, I-1-
a-5, I-1-a-6.
Meloidogyne testi (MELGIN sprey islemi)
Solvent: Agirlikça 80 kisim aseton
Amaca uygun bir etkin madde bilesimini hazirlamak amaciyla agirlikça 1 kisim etkin
madde belirtilen miktarda solvent ile karistirilir ve konsantre, su ile istenen
konsantrasyona seyreltilir.
Kaplar, kum, etkin madde solüsyonu, Meloidogyne incognita'nin yumurta-larva
süspansiyonu ve marul tohumu ile doldurulur. Marul tohumlari çimlenir ve bitkiler
Istenen sürenin ardindan gal olusumu temelinde % olarak nematisit etki tayin edilir.
Burada, %100, hiç gal bulunmadigi anlamina gelir; %0 ise muamele edilen bitkilerdeki
gal sayisinin muamele edilmemis kontrollerdekine karsilik geldigini gösterir.
Bu testte örnegin hazirlama örneklerindeki asagidaki bilesikler 20 ppm uygulama
Aphis gossypii testi; (APHIGO G)
Solvent: 7 Agirlikça kisim dimetilformamit
Emülgatör: 2 Agirlikça kisim alkilaril poliglikol eter
Amaca uygun bir etkin madde preparatini hazirlamak amaciyla, agirlikça 1 kisim etkin
madde belirtilen miktarda solvent ve emülgatör ile karistirilir ve konsantre, su ile
istenen konsantrasyona seyreltilir.
Pamuk yaprak biti (Aphis gossypii) tarafindan siddetli sekilde istila edilmis olan pamuk
bitkilerine (Gossypium hirsutum) istenen konsantrasyonda bir etkin madde preparati
uygulanir.
Istenen sürenin ardindan % olarak ölüm orani tayin edilir. Burada, %100, bütün yaprak
bitlerinin öldügü anlamina gelir; %0 ise hiçbir yaprak bitinin ölmedigi anlamina gelir.
Bu testte örnegin hazirlama örneklerindeki asagidaki bilesikler 20 ppm uygulama
miktarinda 10 günün ardindan 2 %80 oraninda etki göstermektedir:
Myzus persicae testi (MYZUPE G)
Solvent: 7 Agirlikça kisim dimetilformamit
Emülgatör: 2 Agirlikça kisim alkilaril poliglikol eter
Amaca uygun bir etkin madde preparatini hazirlamak amaciyla. agirlikça 1 kisim etkin
madde belirtilen miktarda solvent ve emülgatör ile karistirilir ve konsantre. su ile
istenen konsantrasyona seyreltilir.
Yesil seftali yaprak biti (Myzus persicae) tarafindan yogun bir sekilde istila edilmis olan
lahana bitkisi yaprak disklerine (Brassica oleracea) istenen konsantrasyonda etkin
madde preparati uygulanir.
Istenen sürenin ardindan % olarak ölüm orani tayin edilir. Burada, %100, bütün yaprak
bitlerinin öldügü anlamina gelir; %0 ise hiçbir yaprak bitinin ölmedigi anlamina gelir.
Bu testte örnegin hazirlama örneklerindeki asagidaki bilesikler 20 ppm uygulama
miktarinda 10 günün ardindan 2 %80 oraninda etki göstermektedir:
Tetranychus testi; OP dirençli (TETRUR G)
Solvent: 7 Agirlikça kisim dimetilformamit
Emülgatör: 2 Agirlikça kisim alkilaril poliglikol eter
Amaca uygun bir etkin madde preparatini hazirlamak amaciyla, agirlikça 1 kisim etkin
madde preparati, belirtilen miktarlarda solvent ve emülgatör ile karistirilir ve konsantre,
emülgatör içeren su ile istenen konsantrasyona seyreltilir.
Iki benekll örümcek akarinin (Tetranychus urticae) bütün evreleri tarafindan istila
edilmis olan fasulye bitkilerine (Phaseolus vu/garis), istenen konsantrasyonda etkin
madde preparati uygulanir.
Istenen sürenin ardindan % olarak etki tayin edilir. Burada, %100 bütün örümcek
akarlarinin öldügü anlamina gelir; %0 hiçbir örümcek akarinin ölmedigi anlamina gelir.
Bu testte örnegin hazirlama örneklerindeki asagidaki bilesikler 20 ppm uygulama
miktarinda 14 günün ardindan 2 %80 oraninda etki göstermektedir:
Solvent: Dimetilsülfoksit
Amaca uygun bir etkin madde bilesimini hazirlamak amaciyla agirlikça 1 kisim etkin
madde preparati belirtilen miktarda solvent ile karistirilir ve konsantre, su ile istenen
konsantrasyona seyreltilir.
Istenen konsantrasyonda etkin madde preparati ile muamele edilmis olan at eti içeren
kaplara Luci/ia cuprina larvalari konur.
Istenen sürenin ardindan % olarak ölüm orani tayin edilir. Burada, %100, bütün
Bu testte örnegin hazirlama örneklerindeki asagidaki bilesikler 100 ppm uygulama
Boophilus microplus testi (BOOPMI enjeksiyonu)
Solvent: Dimetilsülfoksit
Amaca uygun bir etkin madde bilesimini hazirlamak amaciyla, agirlikça 1 kisim etkin
madde preparati belirtilen miktarda solvent ile karistirilir ve konsantre, solvent ile
istenen konsantrasyona seyreltilir.
Etkin madde solüsyonu karin içine (Boophilus microp/us) enjekte edilir, hayvanlar
plastik kaplardaki filtre diskleri üzerine aktarilir ve iklimlenmis bir odada saklanir.
Istenen sürenin ardindan % olarak etki tayin edilir. Burada %100 hiçbir kenenin fertil
yumurta birakmadigi anlamina gelir.
Bu testte örnegin hazirlama örneklerindeki asagidaki bilesikler 20 ug/hayvan uygulama
Heliothis virescens testi - transgenik bitkilerin muamelesi
Solvent: Agirlikça 7 kisim aseton
Emülgatör: Agirlikça 1 kisim alkilaril poliglikol eter
Amaca uygun bir etkin madde bilesimini hazirlamak amaciyla, agirlikça 1 kisim etkin
madde, belirtilen miktarda solvent ve belirtilen miktarda emülgatör ile karistirilir ve
konsantre, su ile istenen konsantrasyona seyreltilir.
Roundup Ready (Monsanto Comp. USA ticari markasi) türü soya filizleri (Glycine max)
istenen konsantrasyonda etkin madde preparatina daldirilarak muamele edilir ve
yapraklar henüz islak iken tütün kapsül kurdu Heliothis virescens ile kaplanir.
Istenen sürenin ardindan insektlerin ölüm orani tayin edilir.
Sinir konsantrasyonu testi/ toprak insektleri - transgenik bitkilerin muamelesi
Test insekti: Diabrotica balteata - toprakta larvalar
Solvent: Agirlikça 7 kisim aseton
Emülgatör: Agirlikça 1 kisim alkilaril poliglikol eter
Amaca uygun bir etkin madde preparatini hazirlamak amaciyla, agirlikça 1 kisim etkin
madde, belirtilen miktarda çözücü ve belirtilen miktarda emülgatör ile karistirilir ve
konsantre, su ile istenen konsantrasyona seyreltilir.
Etkin madde preparati topraga dökülür. Burada etkin maddenin preparat içerisindeki
konsantrasyonu pratikte herhangi bir rol oynamaz, belirleyici olan, ppm (mg/I) olarak
verilen, birim hacimde toprak basina etkin madde miktaridir. Toprak 0,25 I'lik saksilara
doldurulur ve bunlar 20°C'de beklemeye birakilir.
Karistirmanin hemen ardindan, her saksiya YIELD GUARD çesidinden (Monsanto
Comp., USA ticari markasi) önceden çimlendirilmis 5 adet misir tanesi yerlestirilir. 2
gün sonra, muamele edilen topraga ilgili test insektleri konur. 7 günün daha ardindan,
etkin maddenin etki derecesi çikan misir bitkileri sayilarak belirlenir (1 bitki = %20 etki).
Örnek 13: Etkinin penetrasyon artiricilar ile kombine amonyum/fosfonyum tuzlari
ile artirilmasi
Myzus persicae testi
Solvent: Agirlikça 7 kisim dimetilformamit
Emülgatör: Agirlikça 2 kisim alkilaril poliglikol eter
Amaca uygun bir etkin madde preparatini hazirlamak amaciyla, agirlikça 1 kisim etkin
madde belirtilen miktarda solvent ve emülgatör ile karistirilir ve konsantre, su ile
istenen konsantrasyona seyreltilir. Amonyum veya fosfonyum tuzlari ve penetrasyon
artiricilar (Kolza yagi metil esteri ile uygulama için, bunlar her biri 1000 ppm
konsantrasyonunda püskürtme sivisina ilave edilir.
Yesil seftali yaprak biti (Myzus persicae) tarafindan yogun bir sekilde istila edilmis olan
biber bitkisi yaprak diskleri (Capsicum annuum) istenen konsantrasyonda etkin madde
preparati ile iyice islanana kadar püskürtülerek muamele edilir.
Istenen sürenin ardindan % olarak ölüm orani tayin edilir. Burada, %100, bütün
hayvanlarin öldügü anlamina gelir; %0 ise hiçbir hayvanin ölmedigi anlamina gelir.
Etkin Konsantrasyon Ölüm (%), 6 + AS + RME + AS + RME,
0,8 0 0 O 15
0,8 0 0 O 5
Aphis gossypii testi
Solvent: agirlikça 7 kisim dimetilformamit
Emülgatör: agirlikça 2 kisim alkilaril poliglikol eter
Amaca uygun bir etkin madde preparatini hazirlamak amaciyla, agirlikça 1 kisim etkin
madde, belirtilen miktarlarda solvent ve emülgatör ile karistirilir ve konsantre,
emülgatör içeren su ile istenen konsantrasyona seyreltilir. Amonyum veya fosfonyum
tuzlari ve penetrasyon artiricilar (Kolza yagi metil esteri ile uygulama için,
bunlar her biri 1000 ppm a.i. konsantrasyonunda püskürtme sivisina ilave edilir.
Pamuk yaprak biti (Aphi's gossypii) tarafindan siddetli sekilde istila edilmis olan pamuk
bitkileri (Gossypium hirsutum) istenen konsantrasyonda etkin madde preparati ile iyice
islanana kadar püskürtülerek muamele edilir.
Istenen sürenin ardindan % olarak ölüm orani tayin edilir. Burada, %100, bütün yaprak
bitlerinin öldügü anlamina gelir; %0 ise hiçbir yaprak bitinin ölmedigi anlamina gelir.
Etkin Konsantrasyon Ölüm ('70), 6 -I- AS -I- RME + AS + RME,
4 0 0 0 60
Çikis öncesi dönemde herbisit etki
Tek veya çift çenekli yabani bitkilerin ve kültür bitkilerinin tohumlari agaç lifinden
saksilarda kumlu killi topraga konur ve toprak ile örtülür. Daha sonra, islanabilir toz
(WP) seklinde formüle edilmis olan test bilesikleri sulu süspansiyon olarak farkli
dozajlarda %0,2 islatici ajan ilavesi ile 600 l/ha su uygulama oranina sahip bir sulu
süspansiyon seklinde örtü topraginin yüzeyine uygulanir.
Muamelenin ardindan saksilar seraya konur ve test bitkileri için iyi büyyetistirme
kosullarinda tutulur. Deney bitkileri üzerindeki çikma zarari 3 haftalik bir çalisma
süresinin ardindan muamele edilmemis kontrollerle karsilastirilarak gözle degerlendirilir
(yüzde olarak herbisit etki: %100 etki = bitkiler öldü, %0 etki = kontrol bitkileri gibi).
Asagidaki bilesikler yukarida belirtilen bilesiklerin yaninda Echinocloa crus-galli ve
Setaria viridis'e karsi çikis öncesinde 320 g/ha a.i. uygulama miktarinda 2 %80
a-51, I-1-a-53, I-1-a-55
Çikis sonrasi dönemde herbisit etki
Tek veya çift çenekli yabani bitkilerin veya kültür bitkilerinin tohumlari agaç lifi
saksilarda kumlu killi topraga konur, toprak ile örtülür ve serada iyi yetisme kosullari
altinda yetistirilir. Ekimden 2-3 hafta sonra deney bitkileri tek yaprak asamasinda
muamele edilir. Püskürtme tozu (WP) olarak formüle edilen test bilesikleri farkli
dozajlarda 600 I/ha esdeger miktarinda su miktari ile %0,2 oraninda islatici ajan
kullanilarak bitkilerin yesil kisimlari üzerine püskürtülür. Deney bitkileri serada optimum
yetisme kosullarinda yaklasik 3 hafta süreyle bekletildikten sonra, preparatlarin etkisi
muamele edilmemis kontrollerle karsilastirilarak gözle degerlendirildi (yüzde olarak
herbisit etki: %100 etki = bitkiler öldü, %0 etki = kontrol bitkileri gibi).
Yukarida belirtilen bilesiklerin yaninda asagidaki bilesikler Echinocloa crus-galli ve
Setaria viridis'e karsi çikis sonrasinda 80 g/ha uygulama miktarinda 2 %80 oraninda
a-54.
Claims (1)
- ISTEMLER 1. Asagidaki formül (I) ile gösterilen bilesiklerdir W hidrojen veya metil anlamina gelir, X klor veya metil anlamina gelir, Y hidrojen veya metil anlamina gelir, 2 radikali anlamina gelir V1 hidrojen, flor, klor, metil, metoksi veya triflorometil anlamina gelir, V2 hidrojen veya flor anlamina gelir, CKE grubu anlamina gelir` A, B ve bunlarin bagli oldugu karbon atomu doymus Cö-sikloalkil anlamina gelir, burada bir halka üyesinin yerini oksijen almistir ve bu gerektiginde metil veya etil ile bir defa sübstitüe edilmistir, G hidrojen (8) veya asagidaki gruplardan biri JL M/Rzio) veya E (f) anlamina gelir, L oksijen anlamina gelir, M oksijen anlamina gelir ve E bir metal iyonu esdegeri veya bir amonyum iyonu anlamina gelir, R1 her biri gerektiginde flor veya klor ile bir defa sübstitüe edilmis 01-06- alkil, Cz-CG-alkenil, C1-C2-alk0ksi-Cq-alkil, C1-Cz-alkiltiy0-C1-alkil veya her biri gerektiginde flor, klor, metil veya metoksi ile bir defa sübstitüe edilmis siklopropil veya siklohekzil anlamina, gerektiginde flor, klor, brom, siyano, nitro, metil, metoksi, triflorometil veya triflorometoksi ile bir defa sübstitüe edilmis fenil anlamina gelir, R2 her biri gerektiginde flor ile bir defa sübstitüe edilmis C1-Cg-alkil, Cg-Cß- alkenil veya C1-C4-alkoksi-Cg-C3-alkil, fenil veya benzil anlamina gelir. 2. istem 1'e göre formül (I) ile gösterilen bilesiklerin hazirlanmasi için yöntem olup, özelligi, (A) formül (I-1-a) ile gösterilen bilesikleri elde etmek için A, B, W, X, Y ve Z istem 1'de belirtilen anlamlara sahiptir, formül (II) ile gösterilen N-asilamino asit esterlerinin H (11) A, B, W, X, Y ve Z istem 1'de belirtilen anlamlara sahiptir, R8 alkil anlamina gelir, bir seyreltici varliginda ve bir baz varliginda intramoleküler olarak kondanse edilmesi, (C) yukarida gösterilen formüller (l-1-a), (l-1-b), (l-1-c), (l-1-f) ile gösterilen bilesikleri elde etmek için, burada A, B, G, W, X, Y ve Z istem 1'de belirtilen anlama sahiptir, formül (l-1'-a), (I-1'-b), (I-1'-c), (I-1'-f), (l-1'-a), (I-1'-b), (I-1'-c), (I-1'-f) ile gösterilen bilesiklerin A, B, G, W, X ve Y istem 1'de belirtilen anlama sahiptir ve Z' klor, brom, iyot, tercihen brom anlamina gelir, formül (IV) ile gösterilen boronik asitler veya boronik asit türevleri ile 25 (IV) R9 hidrojen, C1-CG-alkil veya Cz-CB-alkandiil anlamina gelir Z istem 1'de verilen anlama sahiptir, bir solvent, bir baz ve bir katalizör varliginda reaksiyona sokulmasi ile, burada katalizör olarak özellikle paladyum tuzlari veya paladyum kompleksleri degerlendirilir, (D) yukarida gösterilen formül (I-1-b) ile gösterilen bilesikleri elde etmek için, burada A, B, R1, W, X, Y ve Z istem 1'de belirtilen anlamlara sahiptir, yukarida gösterilen formül (l-1-a) ile gösterilen bilesiklerin, burada A, B, W, X, Y ve Z istem 1'de belirtilen anlamlara sahiptir, (0) formül (V) ile gösterilen asit halojenürler ile R1 istem 1'de verilen anlama sahiptir ve Hal halojen anlamina gelir (8) formül (VI) ile gösterilen karboksilik asit anhidritler ile R1-CO-O-CO-R1 (vi) R1 istem 1'de belirtilen anlama sahiptir, gerektiginde bir seyreltici varliginda ve gerektiginde bir asit baglayici madde varliginda reaksiyona sokulmasi ile; (E) yukarida gösterilen formül (l-1-c) ile gösterilen bilesikleri elde etmek için, burada A, B, R2, M, W, X, Y ve Z istem 1'de belirtilen anlamlara sahiptir ve L oksijen anlamina gelir, yukarida gösterilen formüller (I-1-a) ile gösterilen bilesiklerin, burada A, B, W, X, Y ve Z istem 1'de belirtilen anlamlara sahiptir, formül (VII) ile gösterilen kloroformik asit esterleri ile R2-M-CO-CI (VII) R2 ve M istem 1'de verilen anlamlara sahiptir, gerektiginde bir seyreltici varliginda ve gerektiginde bir asit baglayici madde varliginda reaksiyona sokulmasi ile; (I) yukarida gösterilen formül (I-1-f) ile gösterilen bilesikleri elde etmek için, burada A, B, E, W, X, Y ve Z istem 1'de belirtilen anlamlara sahiptir, yukarida gösterilen formül (l-1-a) ile gösterilen bilesiklerin, burada A, B, W, X, Y ve Z istem 1'de belirtilen anlamlara sahiptir, formüller (XI) veya (XII) ile gösterilen metal bilesikleri veya aminler ile Me(OR1°)t (xi) R12 ( ) Me bir veya iki degerlikli bir metal, t 1 veya 2 sayisi ve R”, R”, R12 birbirlerinden bagimsiz olarak hidrojen veya alkil anlamina gerektiginde bir seyreltici varliginda reaksiyona sokulmasi ile karakterize edilmesidir. 3. Bilesenler olarak asagidaki içeren bir etkin madde kombinasyonunun etkili bir miktarini içeren selektif herbisit ajanlardir (a') formül (I) ile gösterilen en az bir bifenil sübstitüe edilmis, spirosiklik ketoenol, burada CKE, W, X, Y ve Z istem 1'de belirtilen anlama sahiptir (b') kültür bitkilerinin toleransini iyilestiren ve asagidaki bilesik grubundan seçilen en az bir bilesik: 4-dikl0roasetiI-, 1- benzoksazin (benoksakor), 5-kl0r-kinolin-8-oksi-asetik asit-(i-metiI-hekzil metiI-1-feniI-etil) üre (kumiluron), a-(siyanometoksimin0)-fenilasetonitril (siyometrinil), 2,4-dikl0r-fenoksiasetik asit (2,4-D), 4-(2.4-diklor-fenoksi)- bütirik asit (2,4-DB), 1-(1-metiI-1-feniI-etiI)-3-(4-metII-fenil) üre (Daimuron, Dimiron), 3,6-diklor-2-met0ksi-benzoik asit (dikamba), piperidin-1- tiyokarboksilik asit-S-1-metiI-1-feniI-etil esteri (dimepiperat), 2,2-diklor-N-(2- 0kso-2-(2-pr0penil-amino)-etil)-N-(2-propeniI)-asetamit (DKA-24), 2,2-diklor- N,N-di-2-propeniI-asetamit (diklormid), 4,6-diklor-2-fenil-pirimidin (fenklorim), bilesikler), 2-klor-4-triflorometIl-tiyazoi-S-karboksilik asit fenil metil esteri (flurazol), 4-kIor-N-(1,3-dioksolan-2-iI-metoksi)-a-trifl0r-asetofenonoksim (fluksofenim), 3-dikloroasetiI-S-(Z-furaniI)-2,2-dimetiI-oksazolidin (furilazol, etil - ayrica bakiniz WO-A-95/07897'deki baglantili bilesikler), 1- (etoksikarbonil)-etiI-3,6-diklor-2-metoksibenzoat (Iaktidiklor), (4-klor-o- toliloksi)-asetik asit (MCPA), 2-(4-kl0r-o-toliIoksi)-pr0piyonik asit (mekoprop), (mefenpir-dietil - ayrica bakiniz WO-A-91/07874'teki baglantili bilesikler) 2- dioksolan-2-iI-metoksimino)-fenil asetonitril (oksabetrinil), 2,2-dikl0r-N-(1,3- dimetil-oksazolidin (R-28725), 3-dikloroasetiI-Z,2,5-trimetil-oksazolidin (R- difenilmetoksiasetik asit, difenilmetoksiasetik asit metil esteri, difenilmetoksiasetik asit etil esteri, 1-(2-klor-feniI)-5-feniI-1H-pirazoI-3- karboksilik asit-metil esteri, 1-(2,4-diklor-feniI)-5-metil-1H-pirazoI-S- karboksilik asit etil esteri, 1-(2,4-diklor-feniI)-5-izopropiI-1H-pirazoI-S- karboksilik asit etil esteri, 1-(2,4-dikl0r-feniI)-5-(1,1-dimetiI-etiI)-1H-pirazoI-3- karboksilik asit etil esteri, 1-(2,4-diklor-feniI)-5-feniI-1H-pirazoI-3-karboksilik bilesikler), 5-(2,4-dikIor-benzil)-2-izoksazolin-3-karboksilik asit etil esteri, 5- feniI-2-izoksazolin-3-karboksilik asit etil esteri, 5-(4-fl0r-feniI)-5-feniI-2- izoksazolin-ß-karboksiIik asit etil esteri (ayrica bakiniz WO-A-91/08202'deki baglantili bilesikler), 5-kI0r-kin0lin-8-0ksI-asetik asit-(1,3-dimetiI-büt-1-II) esteri, 5-klor-kin0lin-8-oksi-asetik asit-4-aliloksi-bütil esteri, 5-klor-kin0lin-8- oksi-asetik asit-1-aliloksi-prop-Z-il esteri, 5-klor-kin0ksalin-8-0ksi-asetik asit- metil esteri, 5-klor-kinolin-8-oksi-asetik asit etil esteri, 5-klor-kinoksalin-8- oksi-asetik asit-alil esteri, 5-kl0r-kinoIin-8-0ksi-asetik asit-2-0kso-prop-1-il esteri, 5-klor-kinoIIn-8-oksi-malonik asit-dietil esteri, 5-kl0r-kin0ksalin-8-0ksi- malonik asit-dialil esteri, 5-klor-kin0lin-8-oksi-malonik asit-dietil esteri (ayrica 3,3'-dimetiI-4-metoksi-benzofenon, 1-brom-4-kl0rometilsülf0niI-benzen, 1-[4- (N-2-met0ksibenzoilsüIfamoiI)-feniI]-3-metil üre (diger adiyla N-(2-metoksi- benzoil)-4-[(metilamin0-karbonil)-amino]-benzensülf0namit), 1-[4-(N-2- metoksibenzoilsülfanoiI)-feniI]-3.3-dimetil üre, 1-[4-(N-4.5- dimetilbenzoilsulfamoil)-feniI]-3-metil üre, 1-[4-(N-naftilsülfamoiI)-feniI]-3,3- dimetil üre, N-(2-metoksi-5-metil-benzoiI)-4-(sikl0propilaminokarbonil)- benzensülfonamit, ve/veya asagidaki genel formüller ile tanimlanan bilesiklerden biri genel formül (Ila) ile gösterilen veya genel formül (Ilb) ile gösterilen veya genel formül (Ilc) ile gösterilen m 0, 1, 2, 3, 4 veya 5 sayilari anlamina gelir, A1 asagida kabaca çizimi gösterilen divalent heterosiklik gruplardan biri anlamina gelir, n 0, 1, 2, 3, 4 veya 5 sayilari anlamina gelir, A2 gerektiginde C1-C4-alkil ve/veya C1-C4-alkoksi-karbonil ve/veya C1-C4- alkeniloksi-karbonil ile sübstitüe edilmis, 1 veya 2 karbon atomuna sahip alkandiil anlamina gelir, R14 hidroksi, merkapto, amino, C1-C6-alkoksi, C1-C5-alkiltiy0, C1-Cs- alkilamino veya di-(C1-C4-alkiI)-amin0 anlamina gelir, alkil)-amino anlamina gelir, R16 gerektiginde flor, klor ve/veya brom ile sübstitüe edilmis C1-C4-alkil anlamina gelir, R17 hidrojen, her biri gerektiginde flor, klor ve/veya brom ile sübstitüe edilmis C1-CB-alkil, C2-C6-alkenil veya Cz-Cö-alkinil, C1-C4-alkoksi-C1-C4-alkil, dioksolaniI-C1-C4-alkil, furil. furiI-Ci-C4-alkil, tiyenil. tiyazolil, piperidinil veya gerektiginde flor, klor ve/veya brom veya C1-C4-alkil ile sübstitüe edilmis fenil anlamina gelir, R18 hidrojen, her biri gerektiginde flor, klor ve/veya brom ile sübstitüe edilmis C1-Cs-alkil, CZ-Ce-alkenil veya Cz-Cs-alkinil, C1-C4-aIkoksi-C1-C4-alkil, dioksolanil-C1-C4-alkil, furil, furiI-C1-C4-alkil, tiyenil, tiyazolil, piperidinil veya gerektiginde flor, klor ve/veya brom veya Ci-C4-alkil ile sübstitüe edilmis fenil anlamina gelir, R17 ve R18 ayni zamanda birlikte her biri gerektiginde C1-C4-alkil, fenil, furil, kaynasik bir benzen halkasi ile veya bagli olduklari C atomu ile birlikte bir 5- veya 6-üyeli karbosiklus olusturan iki sübstitüent ile sübstitüe edilmis Ca-Ce-alkandiil veya 02-05-oksaalkandiil anlamina gelir, R19 hidrojen, siyano, halojen veya istege bagli olarak her biri flor, klor ve/veya brom ile sübstitüe edilmis C1-C4-alkil, Cs-Cs-sikloalkil veya fenil anlamina gelir, R20 hidrojen, her biri gerektiginde hidroksi, siyano, halojen veya 01-04- alkoksi ile sübstitüe edilmis C1-Cs-alkil, Ca-Cs-sikloalkil veya tri-(C1-C4-alkil)- silil anlamina gelir, R21 hidrojen, siyano, halojen veya istege bagli olarak her biri flor, klor ve/veya brom ile sübstitüe edilmis C1-C4-alkil, Cs-Cö-sikloalkil veya fenil anlamina gelir, X1 nitro, siyano, halojen, C1-C4-alkil, C1-C4-halojen alkil, C1-C4-alk0ksi veya C1-C4-halojen alkoksi anlamina gelir. X2 hidrojen, siyano, nitro, halojen, C1-C4-alkil, C1-C4-halojen alkil, C1-C4- alkoksi veya Ci-C4-halojen alkoksi anlamina gelir, X3 hidrojen, siyano, nitro, halojen, C1-C4-alkil, C1-C4-halojen alkil, C1-C4- alkoksi veya C1-C4-hal0jen alkoksi anlamina gelir, ve/veya asagidaki genel formüller ile tanimlanan bilesikler genel formül (Ild) ile gösterilen IO, 1, 2, 3, 4 veya 5 sayilari anlamina gelir, v 0, 1, 2, 3, 4 veya 5 sayilari anlamina gelir, R22 hidrojen veya C1-C4-alkil anlamina gelir, R23 hidrojen veya C1-C4-alkil anlamina gelir, R24 hidrojen, gerektiginde her biri siyano, halonen veya C1-C4-alk0ksi ile sübstitüe edilmis C1-Ce-alkil, C1-Ce-alk0ksi, C1-Cs-alkiltiyo, C1-CB-alkilamino veya di-(C1-C4-alkiI)-amino veya her biri gerektiginde siyano, halojen veya C1-C4-alkil ile sübstitüe edilmis Cg-Cs-sikloalkil, Cg-Cs-sikloalkoksi, Cg-Cß- sikloalkil-tiyo veya C3-CG-sikloalkilamino anlamina gelir, R25 hidrojen, gerektiginde siyano, hidroksi, halojen veya C1-C4-alkoksi ile sübstitüe edilmis C1-Cs-alkil, her biri gerektiginde siyano veya halojen ile sübstitüe edilmis Ca-CG-alkenil veya C3-Cö-alkinil veya gerektiginde siyano, halojen veya C1-C4-alkil ile sübstitüe edilmis Cg-CG-sikloalkil anlamina gelir, R26 hidrojen, gerektiginde siyano, hidroksi, halojen veya C1-C4-alk0ksi ile sübstitüe edilmis C1-C5-alkil, her biri gerektiginde siyano veya halojen ile sübstitüe edilmis Cg-CB-alkenil veya Cg-CG-alkinil, gerektiginde siyano, halojen veya C1-C4-alkil ile sübstitüe edilmis Cg-Cs-sikloalkil veya gerektiginde nitro, siyano, halojen, C1-C4-alkil, C1-C4-halojen alkil, C1-C4- alkoksi veya C1-C4-halojen alkoksi ile sübstitüe edilmis fenil anlamina gelir veya R25 ile birlikte her biri gerektiginde C1-C4-alkil ile sübstitüe edilmis C2- Cs-alkandiil veya C2-C5-oksaalkandiil anlamina gelir, X4 nitro, siyano, karboksi, karbamoil, formil, sülfamoil, hidroksi, amino, halojen, C1-C4-alkil, C1-C4-halojen alkil, C1-C4-alkoksi veya C1-C4-halojen alkoksi anlamina gelir ve X5 nitro, siyano. karboksi, karbamoil, formil, sülfamoil, hidroksii amino, halojen, C1-C4-alkil, C1-C4-halojen alkil, C1-C4-alk0ksi veya C1-C4-halojen alkoksi anlamina gelir. istem 3'e göre ajan olup, özelligi kültür bitkilerinin toleransini iyilestiren bilesigin asagidaki bilesik grubundan seçilmesidir: KIokuintoset-meksil, fenklorazol-etil, izoksadifen-etil, mefenpir-dietil, furilazol, fenklorim, kumiluron, dimiron veya bilesikler Istem 3 veya 4'ten birine göre ajan olup, özelligi kültür bitkilerinin toleransini iyilestiren bilesigin klokuintoset-meksil olmasidir. istem 3 veya 4'ten birine göre ajan olup, özelligi kültür bitkilerinin toleransini iyilestiren bilesigin mefenpir-dietil olmasidir. . Asagidakileri kapsayan bilesimdir istem 1'e göre formül (I) ile gösterilen en az bir bilesigi veya istem 3'e göre bir ajani ve formül (III') ile gösterilen en az bir tuzu D azot veya fosfor anlamina gelir, R26, R27, R28 ve R29 birbirlerinden bagimsiz olarak hidrojen veya her biri gerektiginde sübstitüe edilmis C1-Cg-alkil veya bir veya birden fazla defa doymamis, gerektiginde sübstitüe edilmis C1-Cg-alkilen anlamina gelir, burada sübstitüentler halojen, nitro ve siyano içerisinden seçilebilir, n 1, 2, 3 veya 4 anlamina gelir, R30 bir inorganik veya organik anyon anlamina gelir. istem 7'e göre bilesim olup, özelligi, en az bir penetrasyon artirici içermesi ile karakterize edilmesidir. istem 1'e göre formül (I) ile gösterilen bilesiklerin zararlilarla mücadele ajanlari ve/veya herbisitler hazirlamak amaciyla kullanilmasidir. Zararlilarla mücadele ajanlari ve/veya herbisitler olup, özelligi, istem 1'e göre formül (I) ile gösterilen en az bir bilesik içermesi ile karakterize edilmesidir. Hayvani zararlilar ve/veya istenmeyen bitki büyümesi ile mücadele Için yöntem olup, özelligi, insan veya hayvan vücudu üzerindeki cerrahi veya terapötik tedavi amaçli yöntemler hariç, istem 1'e göre formül (I) ile gösterilen bilesiklerin zararlilar ve/veya habitatlari üzerine etki etmeye birakilmasi ile karakterize edilmesidir. istem 1'e göre formül (I) ile gösterilen bilesiklerin hayvani zararlilar ve/veya istenmeyen bitki büyümesi ile mücadele için kullanimi olup, özelligi insan veya hayvan vücudu üzerindeki cerrahi veya terapötik tedavi amaçli kullanimlarin hariç tutulmasid ir. Zararlilarla mücadele ajanlari ve/veya herbisitler hazirlamak için yöntem olup, özelligi, istem 1'e göre formül (I) ile gösterilen bilesiklerin çogalticilar ve/veya yüzey aktif maddeler ile karistirilmasi ile karakterize edilmesidir. Istenmeyen bitki büyümesi ile mücadele için yöntem olup, özelligi, istem 3'e göre bir ajanin bitkiler veya habitatlari üzerine etki etmeye birakilmasi ile karakterize edilmesidir. istem 3'e göre bir ajanin istenmeyen bitki büyümesi ile mücadele için kullanimidir. Istenmeyen bitki büyümesi ile mücadele için yöntem olup, özelligi, istem 1'e göre formül (I) ile gösterilen bilesiklerin ve istem 3'e göre kültür bitkilerinin toleransini iyilestiren bilesigin birbirine yakin sürelerle ayri ayri olarak bitkiler veya habitatlari üzerine etki etmeye birakilmasi ile karakterize edilmesidir. Istem 1'e göre formül (I) ile gösterilen bir etkin maddeyi veya istem 3'e göre bir ajani içeren zararlilarla mücadele ajanlarinin ve/veya herbisitlerin etkisinin yükseltilmesi için yöntem olup, özelligi, insan veya hayvan vücudu üzerindeki cerrahi veya terapötik tedavi amaçli yöntemler hariç, uygulamaya hazir ajanin (püskürtme sivisi) istem 7'ye göre formül (III') ile gösterilen bir tuz kullanilarak hazirlanmasi ile karakterize edilmesidir. istem 17'ye göre yöntem olup, özelligi, püskürtme sivisinin bir penetrasyon artirici kullanilarak hazirlanmasi ile karakterize edilmesidir. Formül (Il) ile gösterilen bilesiklerdir A, B, R8, W, X, Y ve Z istem 1'de veya 2'de belirtilen anlamlara sahiptir. . Formül (XVII) ile gösterilen bilesiklerdir A, B, W, X, Y ve Z istem 1'de belirtilen anlamlara sahiptir. Formül (XXI) ile gösterilen bilesiklerdir 2 W 0 X0 A, B, W, X, Y ve Z istem 1'de belirtilen anlamlara sahiptir. Formül (XXIII) ile gösterilen bilesiklerdir burada W, X, Y, F, v1 ve R8 sübstitüentleri tabloda belirtilen anlamlara sahiptir: 23. Formül (XIX) ile gösterilen bilesiklerdir burada W, X, Y, F, V1 tabloda belirtilen anlamlara sahiptir:
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DE10351646A1 (de) | 2003-11-05 | 2005-06-09 | Bayer Cropscience Ag | 2-Halogen-6-alkyl-phenyl substituierte spirocyclische Tetramsäure-Derivate |
DE10351647A1 (de) | 2003-11-05 | 2005-06-09 | Bayer Cropscience Ag | 2-Halogen-6-alkyl-phenyl substituierte Tetramsäure-Derivate |
DE10354628A1 (de) | 2003-11-22 | 2005-06-16 | Bayer Cropscience Ag | 2-Ethyl-4,6-dimethyl-phenyl-substituierte Tetramsäure-Derivate |
DE10354629A1 (de) | 2003-11-22 | 2005-06-30 | Bayer Cropscience Ag | 2-Ethyl-4,6-dimethyl-phenyl substituierte spirocyclische Tetramsäure-Derivate |
DE102004001433A1 (de) | 2004-01-09 | 2005-08-18 | Bayer Cropscience Ag | cis-Alkoxyspiro-substituierte Tetramsäure-Derivate |
DE102004014620A1 (de) | 2004-03-25 | 2005-10-06 | Bayer Cropscience Ag | 2,4,6-phenylsubstituierte cyclische Ketoenole |
DE102004030753A1 (de) | 2004-06-25 | 2006-01-19 | Bayer Cropscience Ag | 3'-Alkoxy spirocyclische Tetram- und Tretronsäuren |
DE102004032421A1 (de) | 2004-07-05 | 2006-01-26 | Bayer Cropscience Ag | Phenylsubstituierte [1.2]-Oxazin-3,5-dion-und Dihydropyron-Derivate |
DE102004044827A1 (de) | 2004-09-16 | 2006-03-23 | Bayer Cropscience Ag | Jod-phenylsubstituierte cyclische Ketoenole |
DE102004053192A1 (de) | 2004-11-04 | 2006-05-11 | Bayer Cropscience Ag | 2-Alkoxy-6-alkyl-phenyl substituierte spirocyclische Tetramsäure-Derivate |
DE102004053191A1 (de) | 2004-11-04 | 2006-05-11 | Bayer Cropscience Ag | 2,6-Diethyl-4-methyl-phenyl substituierte Tetramsäure-Derivate |
DE102005008021A1 (de) | 2005-02-22 | 2006-08-24 | Bayer Cropscience Ag | Spiroketal-substituierte cyclische Ketoenole |
DE102005051325A1 (de) | 2005-10-27 | 2007-05-03 | Bayer Cropscience Ag | Alkoxyalkyl spirocyclische Tetram- und Tetronsäuren |
DE102005059471A1 (de) | 2005-12-13 | 2007-07-12 | Bayer Cropscience Ag | Herbizide Zusammensetzungen mit verbesserter Wirkung |
DE102005059469A1 (de) | 2005-12-13 | 2007-06-14 | Bayer Cropscience Ag | Insektizide Zusammensetzungen mit verbesserter Wirkung |
DE102005059892A1 (de) | 2005-12-15 | 2007-06-28 | Bayer Cropscience Ag | Alkylthio-spirocyclische Tetramsäuren |
DE102005059891A1 (de) | 2005-12-15 | 2007-06-28 | Bayer Cropscience Ag | 3'-Alkoxy-spirocyclopentyl substituierte Tetram- und Tetronsäuren |
DE102006007882A1 (de) | 2006-02-21 | 2007-08-30 | Bayer Cropscience Ag | Cycloalkyl-phenylsubstituierte cyclische Ketoenole |
DE102006018828A1 (de) | 2006-04-22 | 2007-10-25 | Bayer Cropscience Ag | Alkoxyalkyl-substituierte cyclische Ketoenole |
DE102006025874A1 (de) | 2006-06-02 | 2007-12-06 | Bayer Cropscience Ag | Alkoxyalkyl-substituierte cyclische Ketoenole |
DE102006050148A1 (de) | 2006-10-25 | 2008-04-30 | Bayer Cropscience Ag | Trifluormethoxy-phenylsubstituierte Tetramsäure-Derivate |
DE102006057037A1 (de) | 2006-12-04 | 2008-06-05 | Bayer Cropscience Ag | cis-Alkoxyspirocyclische biphenylsubstituierte Tetramsäure-Derivate |
-
2006
- 2006-12-04 DE DE102006057036A patent/DE102006057036A1/de not_active Withdrawn
-
2007
- 2007-11-22 WO PCT/EP2007/010103 patent/WO2008067911A1/de active Application Filing
- 2007-11-22 PL PL07856209T patent/PL2099751T3/pl unknown
- 2007-11-22 MX MX2013006295A patent/MX358799B/es unknown
- 2007-11-22 DK DK07856209.7T patent/DK2099751T3/en active
- 2007-11-22 CN CN201510076567.1A patent/CN104761521A/zh active Pending
- 2007-11-22 EP EP07856209.7A patent/EP2099751B1/de not_active Not-in-force
- 2007-11-22 AU AU2007327961A patent/AU2007327961B2/en not_active Ceased
- 2007-11-22 BR BR122015014903A patent/BR122015014903B1/pt not_active IP Right Cessation
- 2007-11-22 PT PT07856209T patent/PT2099751T/pt unknown
- 2007-11-22 JP JP2009539633A patent/JP5346297B2/ja not_active Expired - Fee Related
- 2007-11-22 CN CNA2007800447649A patent/CN101547899A/zh active Pending
- 2007-11-22 RU RU2009125431/04A patent/RU2009125431A/ru not_active Application Discontinuation
- 2007-11-22 KR KR1020097012972A patent/KR101571752B1/ko active IP Right Grant
- 2007-11-22 US US12/517,419 patent/US9000189B2/en not_active Expired - Fee Related
- 2007-11-22 MX MX2013006297A patent/MX358795B/es unknown
- 2007-11-22 TR TR2018/10585T patent/TR201810585T4/tr unknown
- 2007-11-22 CA CA002671179A patent/CA2671179A1/en not_active Abandoned
- 2007-11-22 ES ES07856209.7T patent/ES2685444T3/es active Active
- 2007-11-22 BR BRPI0719717A patent/BRPI0719717B1/pt not_active IP Right Cessation
- 2007-11-22 MX MX2009004995A patent/MX2009004995A/es active IP Right Grant
- 2007-11-22 CN CN201110247662.5A patent/CN102408326B/zh not_active Expired - Fee Related
- 2007-12-03 TW TW096145820A patent/TW200838424A/zh unknown
- 2007-12-04 CL CL200703486A patent/CL2007003486A1/es unknown
- 2007-12-04 CL CL2007003485A patent/CL2007003485A1/es unknown
-
2009
- 2009-05-12 CO CO09047994A patent/CO6170404A2/es not_active Application Discontinuation
- 2009-05-29 ZA ZA200903746A patent/ZA200903746B/xx unknown
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