HRP931151A2 - Indazole derivatives - Google Patents
Indazole derivatives Download PDFInfo
- Publication number
- HRP931151A2 HRP931151A2 HR931151A HRP931151A HRP931151A2 HR P931151 A2 HRP931151 A2 HR P931151A2 HR 931151 A HR931151 A HR 931151A HR P931151 A HRP931151 A HR P931151A HR P931151 A2 HRP931151 A2 HR P931151A2
- Authority
- HR
- Croatia
- Prior art keywords
- alkyl
- hydrogen
- formula
- phenyl
- haloalkyl
- Prior art date
Links
- 125000003453 indazolyl group Chemical class N1N=C(C2=C1C=CC=C2)* 0.000 title description 2
- 150000001875 compounds Chemical group 0.000 claims description 143
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 108
- 239000013543 active substance Substances 0.000 claims description 92
- 229910052739 hydrogen Inorganic materials 0.000 claims description 80
- 239000001257 hydrogen Substances 0.000 claims description 80
- -1 R2hydrogen Chemical group 0.000 claims description 75
- 150000002431 hydrogen Chemical class 0.000 claims description 68
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 63
- 150000003839 salts Chemical group 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 54
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 44
- 229910052736 halogen Inorganic materials 0.000 claims description 39
- 150000002367 halogens Chemical class 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 28
- 125000001624 naphthyl group Chemical group 0.000 claims description 26
- 125000001424 substituent group Chemical group 0.000 claims description 25
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 24
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 23
- 125000004769 (C1-C4) alkylsulfonyl group Chemical group 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- 241000607479 Yersinia pestis Species 0.000 claims description 20
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 18
- 229910052801 chlorine Inorganic materials 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 18
- 125000004768 (C1-C4) alkylsulfinyl group Chemical group 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 16
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 15
- 241000244206 Nematoda Species 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 241000233866 Fungi Species 0.000 claims description 13
- 229910052794 bromium Inorganic materials 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 125000004771 (C1-C4) haloalkylsulfinyl group Chemical group 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 230000006378 damage Effects 0.000 claims description 11
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 11
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- 241000238631 Hexapoda Species 0.000 claims description 9
- 125000005059 halophenyl group Chemical group 0.000 claims description 8
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 claims description 8
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 8
- 230000008635 plant growth Effects 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical group O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 125000006125 ethylsulfonyl group Chemical group 0.000 claims description 6
- 230000003032 phytopathogenic effect Effects 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- DITBWPUMEUDVLU-UHFFFAOYSA-N 1h-indazole-3-carboxamide Chemical class C1=CC=C2C(C(=O)N)=NNC2=C1 DITBWPUMEUDVLU-UHFFFAOYSA-N 0.000 claims description 5
- 241000238876 Acari Species 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 4
- BHXVYTQDWMQVBI-UHFFFAOYSA-N 1h-indazole-3-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=NNC2=C1 BHXVYTQDWMQVBI-UHFFFAOYSA-N 0.000 claims description 4
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 4
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 3
- KCNKJCHARANTIP-SNAWJCMRSA-N allyl-{4-[3-(4-bromo-phenyl)-benzofuran-6-yloxy]-but-2-enyl}-methyl-amine Chemical compound C=1OC2=CC(OC/C=C/CN(CC=C)C)=CC=C2C=1C1=CC=C(Br)C=C1 KCNKJCHARANTIP-SNAWJCMRSA-N 0.000 claims description 3
- JYNZIOFUHBJABQ-UHFFFAOYSA-N allyl-{6-[3-(4-bromo-phenyl)-benzofuran-6-yloxy]-hexyl-}-methyl-amin Chemical compound C=1OC2=CC(OCCCCCCN(C)CC=C)=CC=C2C=1C1=CC=C(Br)C=C1 JYNZIOFUHBJABQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 125000004969 haloethyl group Chemical group 0.000 claims description 3
- 125000004970 halomethyl group Chemical group 0.000 claims description 3
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 3
- AKDOCDDFJFPONT-UHFFFAOYSA-N 1-(2-ethylhexanoyl)-2-methyl-N-[[4-[4-(trifluoromethyl)phenoxy]phenyl]methyl]-3H-indazole-3-carboxamide Chemical compound FC(C1=CC=C(OC2=CC=C(CNC(=O)C3N(N(C4=CC=CC=C34)C(C(CCCC)CC)=O)C)C=C2)C=C1)(F)F AKDOCDDFJFPONT-UHFFFAOYSA-N 0.000 claims description 2
- QDJKMDVYUOUTJV-UHFFFAOYSA-N 1-acetyl-2-methyl-N-[[4-[4-(trifluoromethyl)phenoxy]phenyl]methyl]-3H-indazole-3-carboxamide Chemical compound FC(C1=CC=C(OC2=CC=C(CNC(=O)C3N(N(C4=CC=CC=C34)C(C)=O)C)C=C2)C=C1)(F)F QDJKMDVYUOUTJV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 4
- SYGWYBOJXOGMRU-UHFFFAOYSA-N chembl233051 Chemical compound C1=CC=C2C3=CC(C(N(CCN(C)C)C4=O)=O)=C5C4=CC=CC5=C3SC2=C1 SYGWYBOJXOGMRU-UHFFFAOYSA-N 0.000 claims 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims 1
- 241000196324 Embryophyta Species 0.000 description 61
- 235000002639 sodium chloride Nutrition 0.000 description 54
- 230000000694 effects Effects 0.000 description 46
- 239000000839 emulsion Substances 0.000 description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 29
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 25
- 230000009471 action Effects 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000843 powder Substances 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 230000009467 reduction Effects 0.000 description 17
- 125000000217 alkyl group Chemical group 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 235000013601 eggs Nutrition 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- ABRISPFTOZIXMP-UHFFFAOYSA-N 2-methylindazole-3-carboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)N(C)N=C21 ABRISPFTOZIXMP-UHFFFAOYSA-N 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 206010017533 Fungal infection Diseases 0.000 description 10
- 208000031888 Mycoses Diseases 0.000 description 10
- 240000001307 Myosotis scorpioides Species 0.000 description 10
- 240000007594 Oryza sativa Species 0.000 description 10
- 150000001408 amides Chemical class 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- 230000002538 fungal effect Effects 0.000 description 10
- 239000008187 granular material Substances 0.000 description 10
- 239000002689 soil Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 9
- 239000005995 Aluminium silicate Substances 0.000 description 8
- 241000256244 Heliothis virescens Species 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 235000012211 aluminium silicate Nutrition 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 150000002168 ethanoic acid esters Chemical class 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 238000011534 incubation Methods 0.000 description 8
- 208000015181 infectious disease Diseases 0.000 description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 7
- 244000068988 Glycine max Species 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 240000005979 Hordeum vulgare Species 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 240000003768 Solanum lycopersicum Species 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000010410 dusting Methods 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 5
- 241000254127 Bemisia tabaci Species 0.000 description 5
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 5
- 244000188595 Brassica sinapistrum Species 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 241001465754 Metazoa Species 0.000 description 5
- 241000500437 Plutella xylostella Species 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 5
- 230000012447 hatching Effects 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000002825 nitriles Chemical class 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 230000009885 systemic effect Effects 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- 241000254175 Anthonomus grandis Species 0.000 description 4
- 244000105624 Arachis hypogaea Species 0.000 description 4
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 description 4
- 235000006008 Brassica napus var napus Nutrition 0.000 description 4
- 240000007124 Brassica oleracea Species 0.000 description 4
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 241000464975 Crocidolomia pavonana Species 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 241001529600 Diabrotica balteata Species 0.000 description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 4
- 235000010469 Glycine max Nutrition 0.000 description 4
- 241000498254 Heterodera glycines Species 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 241000209140 Triticum Species 0.000 description 4
- 240000008042 Zea mays Species 0.000 description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000004414 alkyl thio group Chemical group 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000004359 castor oil Substances 0.000 description 4
- 235000019438 castor oil Nutrition 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 235000005822 corn Nutrition 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 229960004132 diethyl ether Drugs 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 230000035784 germination Effects 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 4
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical class CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 239000012047 saturated solution Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000004546 suspension concentrate Substances 0.000 description 4
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- BCPLOUPYBKETHO-UHFFFAOYSA-N 2-methyl-1-oxidoindazol-1-ium-3-carbonitrile Chemical compound C1=CC=CC2=[N+]([O-])N(C)C(C#N)=C21 BCPLOUPYBKETHO-UHFFFAOYSA-N 0.000 description 3
- ZRCUSWGKZMCOJM-UHFFFAOYSA-N 2-methylindazole-3-carbonitrile Chemical compound C1=CC=CC2=C(C#N)N(C)N=C21 ZRCUSWGKZMCOJM-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 241000952611 Aphis craccivora Species 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- 241000255925 Diptera Species 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 244000299507 Gossypium hirsutum Species 0.000 description 3
- 241000256257 Heliothis Species 0.000 description 3
- 241000257303 Hymenoptera Species 0.000 description 3
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 241000243786 Meloidogyne incognita Species 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 241000238814 Orthoptera Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 3
- 241000233614 Phytophthora Species 0.000 description 3
- 241000221300 Puccinia Species 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 241000256250 Spodoptera littoralis Species 0.000 description 3
- 241001454293 Tetranychus urticae Species 0.000 description 3
- 230000000895 acaricidal effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000009395 breeding Methods 0.000 description 3
- 230000001488 breeding effect Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 3
- VXFOIEINQYXLGF-UHFFFAOYSA-N n-methyl-1-(2-nitrophenyl)methanimine Chemical compound CN=CC1=CC=CC=C1[N+]([O-])=O VXFOIEINQYXLGF-UHFFFAOYSA-N 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 229950011008 tetrachloroethylene Drugs 0.000 description 3
- 238000007280 thionation reaction Methods 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- PUTBIJNBJIIJFS-UHFFFAOYSA-N 1-acetyl-2-methyl-3h-indazole-3-carboxylic acid Chemical compound C1=CC=C2N(C(C)=O)N(C)C(C(O)=O)C2=C1 PUTBIJNBJIIJFS-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- 244000291564 Allium cepa Species 0.000 description 2
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 2
- 241001600407 Aphis <genus> Species 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- 235000002566 Capsicum Nutrition 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 241001157813 Cercospora Species 0.000 description 2
- 241000489975 Diabrotica Species 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- 241000060469 Eupoecilia ambiguella Species 0.000 description 2
- 235000004341 Gossypium herbaceum Nutrition 0.000 description 2
- 240000002024 Gossypium herbaceum Species 0.000 description 2
- 241000258937 Hemiptera Species 0.000 description 2
- 235000007340 Hordeum vulgare Nutrition 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- 244000070406 Malus silvestris Species 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 241000406465 Neodiprion Species 0.000 description 2
- 241001556089 Nilaparvata lugens Species 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 241000721454 Pemphigus Species 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 235000010582 Pisum sativum Nutrition 0.000 description 2
- 240000004713 Pisum sativum Species 0.000 description 2
- 241000233626 Plasmopara Species 0.000 description 2
- 241001281803 Plasmopara viticola Species 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 241001481703 Rhipicephalus <genus> Species 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 241000256248 Spodoptera Species 0.000 description 2
- 241001454294 Tetranychus Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 241000317942 Venturia <ichneumonid wasp> Species 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 230000009435 amidation Effects 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940043232 butyl acetate Drugs 0.000 description 2
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 235000020971 citrus fruits Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 208000031513 cyst Diseases 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 150000001983 dialkylethers Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229940052303 ethers for general anesthesia Drugs 0.000 description 2
- 229940093499 ethyl acetate Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001640 fractional crystallisation Methods 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000004692 haloalkylcarbonyl group Chemical group 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 230000002140 halogenating effect Effects 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- CFHGBZLNZZVTAY-UHFFFAOYSA-N lawesson's reagent Chemical compound C1=CC(OC)=CC=C1P1(=S)SP(=S)(C=2C=CC(OC)=CC=2)S1 CFHGBZLNZZVTAY-UHFFFAOYSA-N 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical compound COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- QHUUCJZTRKURPW-UHFFFAOYSA-N n-[[3-(4-fluorophenoxy)phenyl]methyl]-2-methylindazole-3-carboxamide Chemical compound CN1N=C2C=CC=CC2=C1C(=O)NCC(C=1)=CC=CC=1OC1=CC=C(F)C=C1 QHUUCJZTRKURPW-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- ZVTQDOIPKNCMAR-UHFFFAOYSA-N sulfanylidene(sulfanylideneboranylsulfanyl)borane Chemical compound S=BSB=S ZVTQDOIPKNCMAR-UHFFFAOYSA-N 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000005270 trialkylamine group Chemical group 0.000 description 2
- WTVXIBRMWGUIMI-UHFFFAOYSA-N trifluoro($l^{1}-oxidanylsulfonyl)methane Chemical group [O]S(=O)(=O)C(F)(F)F WTVXIBRMWGUIMI-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical compound C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- FTTATHOUSOIFOQ-UHFFFAOYSA-N 1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrazine Chemical compound C1NCCN2CCCC21 FTTATHOUSOIFOQ-UHFFFAOYSA-N 0.000 description 1
- FLZPTLSRDKJVLE-UHFFFAOYSA-N 1,2-dimethoxyethane-1,2-diol Chemical compound COC(O)C(O)OC FLZPTLSRDKJVLE-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- REHRQXVEAXFIML-UHFFFAOYSA-N 1h-indazole-3-carbonitrile Chemical compound C1=CC=C2C(C#N)=NNC2=C1 REHRQXVEAXFIML-UHFFFAOYSA-N 0.000 description 1
- BNYCHCAYYYRJSH-UHFFFAOYSA-N 1h-pyrazole-5-carboxamide Chemical class NC(=O)C1=CC=NN1 BNYCHCAYYYRJSH-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- QQGRFMIMXPWKPM-UHFFFAOYSA-N 2,3,4-tributylphenol Chemical compound CCCCC1=CC=C(O)C(CCCC)=C1CCCC QQGRFMIMXPWKPM-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical group CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- ABFPKTQEQNICFT-UHFFFAOYSA-M 2-chloro-1-methylpyridin-1-ium;iodide Chemical compound [I-].C[N+]1=CC=CC=C1Cl ABFPKTQEQNICFT-UHFFFAOYSA-M 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- SATVWPWUVVQOPD-UHFFFAOYSA-N 2-methyl-n-[[4-[4-(trifluoromethyl)phenoxy]phenyl]methyl]indazole-3-carboxamide Chemical compound CN1N=C2C=CC=CC2=C1C(=O)NCC(C=C1)=CC=C1OC1=CC=C(C(F)(F)F)C=C1 SATVWPWUVVQOPD-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical group COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-UHFFFAOYSA-N 0.000 description 1
- UGYHYQIDXZGMAX-UHFFFAOYSA-N 4-methylmorpholine;morpholine Chemical compound C1COCCN1.CN1CCOCC1 UGYHYQIDXZGMAX-UHFFFAOYSA-N 0.000 description 1
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 description 1
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 241000934064 Acarus siro Species 0.000 description 1
- 241000208140 Acer Species 0.000 description 1
- 241001558864 Aceria Species 0.000 description 1
- 241001204086 Acleris Species 0.000 description 1
- 241000908424 Acromyrmex Species 0.000 description 1
- 241001506414 Aculus Species 0.000 description 1
- 241001672675 Adoxophyes Species 0.000 description 1
- 241000256111 Aedes <genus> Species 0.000 description 1
- 241001136265 Agriotes Species 0.000 description 1
- 241000218473 Agrotis Species 0.000 description 1
- 241000307865 Aleurothrixus floccosus Species 0.000 description 1
- 241000223600 Alternaria Species 0.000 description 1
- 241000238679 Amblyomma Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 244000144725 Amygdalus communis Species 0.000 description 1
- 241000380490 Anguina Species 0.000 description 1
- 241001427556 Anoplura Species 0.000 description 1
- 241000254177 Anthonomus Species 0.000 description 1
- 241000625764 Anticarsia gemmatalis Species 0.000 description 1
- 241001414827 Aonidiella Species 0.000 description 1
- 241000294569 Aphelenchoides Species 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 241001002469 Archips Species 0.000 description 1
- 241001480748 Argas Species 0.000 description 1
- 241000384127 Argyrotaenia Species 0.000 description 1
- 244000003416 Asparagus officinalis Species 0.000 description 1
- 235000005340 Asparagus officinalis Nutrition 0.000 description 1
- 241000387313 Aspidiotus Species 0.000 description 1
- 241001174347 Atomaria Species 0.000 description 1
- 241000726103 Atta Species 0.000 description 1
- 241001367049 Autographa Species 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- 235000000832 Ayote Nutrition 0.000 description 1
- 241000193388 Bacillus thuringiensis Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- 241001142392 Bibio Species 0.000 description 1
- 241000238659 Blatta Species 0.000 description 1
- 241000238658 Blattella Species 0.000 description 1
- 241001465180 Botrytis Species 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 241000219198 Brassica Species 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
- 241001643374 Brevipalpus Species 0.000 description 1
- 241000398201 Bryobia praetiosa Species 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical compound CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- MQBKPLMUVFPVDC-UHFFFAOYSA-N C(#N)C=1N[N+](=C2C=CC=CC12)[O-] Chemical compound C(#N)C=1N[N+](=C2C=CC=CC12)[O-] MQBKPLMUVFPVDC-UHFFFAOYSA-N 0.000 description 1
- 241000726763 Cadra Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000257163 Calliphora vicina Species 0.000 description 1
- LSPHULWDVZXLIL-UHFFFAOYSA-N Camphoric acid Natural products CC1(C)C(C(O)=O)CCC1(C)C(O)=O LSPHULWDVZXLIL-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 241001347512 Carposina Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 241000717851 Cephus Species 0.000 description 1
- 241000255580 Ceratitis <genus> Species 0.000 description 1
- 241001098608 Ceratophyllus Species 0.000 description 1
- 241001087583 Chaetocnema tibialis Species 0.000 description 1
- 241000426499 Chilo Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000359266 Chorioptes Species 0.000 description 1
- 241000255945 Choristoneura Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000669072 Chrysomphalus dictyospermi Species 0.000 description 1
- 241001414836 Cimex Species 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 244000223760 Cinnamomum zeylanicum Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- DBPRUZCKPFOVDV-UHFFFAOYSA-N Clorprenaline hydrochloride Chemical compound O.Cl.CC(C)NCC(O)C1=CC=CC=C1Cl DBPRUZCKPFOVDV-UHFFFAOYSA-N 0.000 description 1
- 241000098277 Cnaphalocrocis Species 0.000 description 1
- 241001350387 Cnephasia Species 0.000 description 1
- 241001479447 Coccus hesperidum Species 0.000 description 1
- 241001362579 Cochylis Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 240000007154 Coffea arabica Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241001212536 Cosmopolites Species 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 235000009849 Cucumis sativus Nutrition 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 240000004244 Cucurbita moschata Species 0.000 description 1
- 235000009854 Cucurbita moschata Nutrition 0.000 description 1
- 235000009804 Cucurbita pepo subsp pepo Nutrition 0.000 description 1
- 241000256054 Culex <genus> Species 0.000 description 1
- 241000721021 Curculio Species 0.000 description 1
- 241000371644 Curvularia ravenelii Species 0.000 description 1
- 241000692095 Cuterebra Species 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 241001634817 Cydia Species 0.000 description 1
- 206010011732 Cyst Diseases 0.000 description 1
- 241000157278 Dacus <genus> Species 0.000 description 1
- 235000002767 Daucus carota Nutrition 0.000 description 1
- 244000000626 Daucus carota Species 0.000 description 1
- 241001481695 Dermanyssus gallinae Species 0.000 description 1
- 241001641895 Dermestes Species 0.000 description 1
- 241000122105 Diatraea Species 0.000 description 1
- 241000511318 Diprion Species 0.000 description 1
- 241000511320 Diprionidae Species 0.000 description 1
- 241000399934 Ditylenchus Species 0.000 description 1
- 241000255601 Drosophila melanogaster Species 0.000 description 1
- 241001425477 Dysdercus Species 0.000 description 1
- 241000241133 Earias Species 0.000 description 1
- 241000995023 Empoasca Species 0.000 description 1
- 241000488563 Eotetranychus carpini Species 0.000 description 1
- 241000630736 Ephestia Species 0.000 description 1
- 241001301805 Epilachna Species 0.000 description 1
- 241001558857 Eriophyes Species 0.000 description 1
- 241000917109 Eriosoma Species 0.000 description 1
- 201000000297 Erysipelas Diseases 0.000 description 1
- 241000221787 Erysiphe Species 0.000 description 1
- 241001515686 Erythroneura Species 0.000 description 1
- 241001573987 Eucosma Species 0.000 description 1
- 241001331999 Euproctis Species 0.000 description 1
- 241000515838 Eurygaster Species 0.000 description 1
- 241001585293 Euxoa Species 0.000 description 1
- JNCMHMUGTWEVOZ-UHFFFAOYSA-N F[CH]F Chemical compound F[CH]F JNCMHMUGTWEVOZ-UHFFFAOYSA-N 0.000 description 1
- 241000371383 Fannia Species 0.000 description 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical class NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 241000189565 Frankliniella Species 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 241000291751 Gilpinia polytoma Species 0.000 description 1
- 241001442498 Globodera Species 0.000 description 1
- 241000257324 Glossina <genus> Species 0.000 description 1
- 241001150406 Grapholita Species 0.000 description 1
- 241001243091 Gryllotalpa Species 0.000 description 1
- 108010081348 HRT1 protein Hairy Proteins 0.000 description 1
- 241000790933 Haematopinus Species 0.000 description 1
- 102100021881 Hairy/enhancer-of-split related with YRPW motif protein 1 Human genes 0.000 description 1
- 241001201676 Hedya nubiferana Species 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 241001581044 Hellula undalis Species 0.000 description 1
- 241001181537 Hemileia Species 0.000 description 1
- 241001659689 Hercinothrips Species 0.000 description 1
- 241001480224 Heterodera Species 0.000 description 1
- 241001466007 Heteroptera Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241001417351 Hoplocampa Species 0.000 description 1
- 235000008694 Humulus lupulus Nutrition 0.000 description 1
- 244000025221 Humulus lupulus Species 0.000 description 1
- 241001480803 Hyalomma Species 0.000 description 1
- 241001531327 Hyphantria cunea Species 0.000 description 1
- 241000257176 Hypoderma <fly> Species 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- 241001495069 Ischnocera Species 0.000 description 1
- 241000238681 Ixodes Species 0.000 description 1
- 241000758791 Juglandaceae Species 0.000 description 1
- 241000400431 Keiferia lycopersicella Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000003228 Lactuca sativa Nutrition 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 241001470016 Laodelphax Species 0.000 description 1
- 241000256686 Lasius <genus> Species 0.000 description 1
- 241000218195 Lauraceae Species 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- 240000004322 Lens culinaris Species 0.000 description 1
- 235000014647 Lens culinaris subsp culinaris Nutrition 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 241000669027 Lepidosaphes Species 0.000 description 1
- 241000500881 Lepisma Species 0.000 description 1
- 241000258916 Leptinotarsa decemlineata Species 0.000 description 1
- 241000661345 Leptocorisa Species 0.000 description 1
- 241001578972 Leucoptera malifoliella Species 0.000 description 1
- 241001113970 Linognathus Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 241000322707 Liposcelis Species 0.000 description 1
- 241000594036 Liriomyza Species 0.000 description 1
- 241000396080 Lissorhoptrus Species 0.000 description 1
- 241001261104 Lobesia botrana Species 0.000 description 1
- 241000254023 Locusta Species 0.000 description 1
- 241001220360 Longidorus Species 0.000 description 1
- 241000157554 Luculia Species 0.000 description 1
- 241000721696 Lymantria Species 0.000 description 1
- 241001190211 Lyonetia Species 0.000 description 1
- 241001330975 Magnaporthe oryzae Species 0.000 description 1
- 241000255676 Malacosoma Species 0.000 description 1
- 244000081841 Malus domestica Species 0.000 description 1
- 241000555303 Mamestra brassicae Species 0.000 description 1
- 241000255908 Manduca sexta Species 0.000 description 1
- 241000824682 Melanagromyza Species 0.000 description 1
- 241001143352 Meloidogyne Species 0.000 description 1
- 241000254071 Melolontha Species 0.000 description 1
- 241001518729 Monilinia Species 0.000 description 1
- 240000005561 Musa balbisiana Species 0.000 description 1
- 241000257229 Musca <genus> Species 0.000 description 1
- 241000721623 Myzus Species 0.000 description 1
- AHEKQBSEKFWPTN-UHFFFAOYSA-N N-[[4-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]methyl]-2-methylindazole-3-carboxamide Chemical compound ClC1=C(OC2=CC=C(CNC(=O)C=3N(N=C4C=CC=CC=34)C)C=C2)C=CC(=C1)C(F)(F)F AHEKQBSEKFWPTN-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 241000359016 Nephotettix Species 0.000 description 1
- 241001671714 Nezara Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 241001556090 Nilaparvata Species 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 241001491890 Operophtera Species 0.000 description 1
- 241000238887 Ornithodoros Species 0.000 description 1
- 241001465829 Orseolia Species 0.000 description 1
- 241000975417 Oscinella frit Species 0.000 description 1
- 241001147398 Ostrinia nubilalis Species 0.000 description 1
- 241000131737 Otiorhynchus Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241001575015 Pammene Species 0.000 description 1
- 241001441428 Pandemis Species 0.000 description 1
- 241000486438 Panolis flammea Species 0.000 description 1
- 241000488585 Panonychus Species 0.000 description 1
- 240000001090 Papaver somniferum Species 0.000 description 1
- 235000008753 Papaver somniferum Nutrition 0.000 description 1
- 241001450657 Parthenolecanium corni Species 0.000 description 1
- 241000315044 Passalora arachidicola Species 0.000 description 1
- 241000721452 Pectinophora Species 0.000 description 1
- 241000517325 Pediculus Species 0.000 description 1
- 239000006002 Pepper Substances 0.000 description 1
- 241000238661 Periplaneta Species 0.000 description 1
- 244000025272 Persea americana Species 0.000 description 1
- 235000008673 Persea americana Nutrition 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 241001439019 Phthorimaea operculella Species 0.000 description 1
- 241000497192 Phyllocoptruta oleivora Species 0.000 description 1
- 241001516577 Phylloxera Species 0.000 description 1
- 241000255972 Pieris <butterfly> Species 0.000 description 1
- 241000907661 Pieris rapae Species 0.000 description 1
- 241000690748 Piesma Species 0.000 description 1
- 235000016761 Piper aduncum Nutrition 0.000 description 1
- 240000003889 Piper guineense Species 0.000 description 1
- 235000017804 Piper guineense Nutrition 0.000 description 1
- 235000008184 Piper nigrum Nutrition 0.000 description 1
- 241000758706 Piperaceae Species 0.000 description 1
- 241000193804 Planococcus <bacterium> Species 0.000 description 1
- 241000896242 Podosphaera Species 0.000 description 1
- 241000952063 Polyphagotarsonemus latus Species 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 241000254103 Popillia Species 0.000 description 1
- 241000193943 Pratylenchus Species 0.000 description 1
- 241001201614 Prays Species 0.000 description 1
- 235000005805 Prunus cerasus Nutrition 0.000 description 1
- 240000005809 Prunus persica Species 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 241000668989 Pseudaulacaspis Species 0.000 description 1
- 241000722234 Pseudococcus Species 0.000 description 1
- 241001649229 Psoroptes Species 0.000 description 1
- 241000526145 Psylla Species 0.000 description 1
- 241001160824 Psylliodes Species 0.000 description 1
- 241000221301 Puccinia graminis Species 0.000 description 1
- 241000531582 Pulvinaria <Pelagophyceae> Species 0.000 description 1
- 241000231139 Pyricularia Species 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- 241000233639 Pythium Species 0.000 description 1
- 241000201377 Radopholus Species 0.000 description 1
- 241001509970 Reticulitermes <genus> Species 0.000 description 1
- 241001136903 Rhagoletis pomonella Species 0.000 description 1
- 241001617044 Rhizoglyphus Species 0.000 description 1
- 241000722251 Rhodnius Species 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 240000007651 Rubus glaucus Species 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 241000914334 Sahlbergella singularis Species 0.000 description 1
- 241001450655 Saissetia Species 0.000 description 1
- 241000509416 Sarcoptes Species 0.000 description 1
- 241001315546 Scaphoideus Species 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 241000254026 Schistocerca Species 0.000 description 1
- 241000722272 Schizaphis Species 0.000 description 1
- 241001635185 Sciara Species 0.000 description 1
- 241001249127 Scirpophaga Species 0.000 description 1
- 241000924322 Scirtothrips aurantii Species 0.000 description 1
- 241000893388 Scotinophara Species 0.000 description 1
- 241000209056 Secale Species 0.000 description 1
- 235000007238 Secale cereale Nutrition 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 241001533598 Septoria Species 0.000 description 1
- 241000931987 Sesamia Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 241000258242 Siphonaptera Species 0.000 description 1
- 241000180197 Sitobion Species 0.000 description 1
- 241000254181 Sitophilus Species 0.000 description 1
- 241000753143 Sitotroga Species 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 241001492664 Solenopsis <angiosperm> Species 0.000 description 1
- 235000009337 Spinacia oleracea Nutrition 0.000 description 1
- 244000300264 Spinacia oleracea Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 241001494139 Stomoxys Species 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- 241001528589 Synanthedon Species 0.000 description 1
- 241000255626 Tabanus <genus> Species 0.000 description 1
- 241000189578 Taeniothrips Species 0.000 description 1
- 241000254105 Tenebrio Species 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- 241001137073 Thaumatotibia leucotreta Species 0.000 description 1
- 241001231951 Thaumetopoea Species 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 240000006474 Theobroma bicolor Species 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- 244000299461 Theobroma cacao Species 0.000 description 1
- 241000339373 Thrips palmi Species 0.000 description 1
- 241000339374 Thrips tabaci Species 0.000 description 1
- 241001414989 Thysanoptera Species 0.000 description 1
- 241001238452 Tortrix Species 0.000 description 1
- 241000018137 Trialeurodes vaporariorum Species 0.000 description 1
- 241001414833 Triatoma Species 0.000 description 1
- 241000254086 Tribolium <beetle> Species 0.000 description 1
- 241001259047 Trichodectes Species 0.000 description 1
- 241000255993 Trichoplusia ni Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241000462092 Trioza erytreae Species 0.000 description 1
- 241000267823 Trogoderma Species 0.000 description 1
- 241001267618 Tylenchulus Species 0.000 description 1
- 241000368303 Unaspis citri Species 0.000 description 1
- 241000510929 Uncinula Species 0.000 description 1
- 244000078534 Vaccinium myrtillus Species 0.000 description 1
- 235000013447 Xanthosoma atrovirens Nutrition 0.000 description 1
- 240000001781 Xanthosoma sagittifolium Species 0.000 description 1
- 241000353223 Xenopsylla cheopis Species 0.000 description 1
- 241000201423 Xiphinema Species 0.000 description 1
- 241001466337 Yponomeuta Species 0.000 description 1
- 241001414985 Zygentoma Species 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- DUVFUYQHKUSTFB-UHFFFAOYSA-N [3-(4-fluorophenoxy)phenyl]methanamine Chemical compound NCC1=CC=CC(OC=2C=CC(F)=CC=2)=C1 DUVFUYQHKUSTFB-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 235000020224 almond Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- AVKUERGKIZMTKX-NJBDSQKTSA-N ampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=CC=C1 AVKUERGKIZMTKX-NJBDSQKTSA-N 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229940097012 bacillus thuringiensis Drugs 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 235000021015 bananas Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- PDBLJVROGRYXEU-UHFFFAOYSA-N benzo[g][1,3]benzodioxole Chemical class C1=CC=CC2=C(OCO3)C3=CC=C21 PDBLJVROGRYXEU-UHFFFAOYSA-N 0.000 description 1
- 150000005528 benzodioxoles Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- BCOZLGOHQFNXBI-UHFFFAOYSA-M benzyl-bis(2-chloroethyl)-ethylazanium;bromide Chemical compound [Br-].ClCC[N+](CC)(CCCl)CC1=CC=CC=C1 BCOZLGOHQFNXBI-UHFFFAOYSA-M 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- 235000021029 blackberry Nutrition 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- HTRXGEPDTFSKLI-UHFFFAOYSA-N butanoic acid;ethyl acetate Chemical compound CCCC(O)=O.CCOC(C)=O HTRXGEPDTFSKLI-UHFFFAOYSA-N 0.000 description 1
- 125000006251 butylcarbonyl group Chemical group 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- LSPHULWDVZXLIL-QUBYGPBYSA-N camphoric acid Chemical compound CC1(C)[C@H](C(O)=O)CC[C@]1(C)C(O)=O LSPHULWDVZXLIL-QUBYGPBYSA-N 0.000 description 1
- MIOPJNTWMNEORI-UHFFFAOYSA-N camphorsulfonic acid Chemical compound C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-N 0.000 description 1
- 239000000828 canola oil Substances 0.000 description 1
- 235000019519 canola oil Nutrition 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002026 chloroform extract Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 235000017803 cinnamon Nutrition 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000037416 cystogenesis Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- IRDLUHRVLVEUHA-UHFFFAOYSA-N diethyl dithiophosphate Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 description 1
- PQZTVWVYCLIIJY-UHFFFAOYSA-N diethyl(propyl)amine Chemical group CCCN(CC)CC PQZTVWVYCLIIJY-UHFFFAOYSA-N 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000012173 estrus Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 150000005452 ethyl sulfates Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000004440 haloalkylsulfinyl group Chemical group 0.000 description 1
- 125000004441 haloalkylsulfonyl group Chemical group 0.000 description 1
- 125000004995 haloalkylthio group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 125000006341 heptafluoro n-propyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000000974 larvacidal effect Effects 0.000 description 1
- 235000021374 legumes Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 150000005451 methyl sulfates Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003750 molluscacide Substances 0.000 description 1
- 230000002013 molluscicidal effect Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- JLRUPNZFCQDCRL-UHFFFAOYSA-N n-[[4-(4-fluorophenoxy)phenyl]methyl]-2-methylindazole-3-carboxamide Chemical compound CN1N=C2C=CC=CC2=C1C(=O)NCC(C=C1)=CC=C1OC1=CC=C(F)C=C1 JLRUPNZFCQDCRL-UHFFFAOYSA-N 0.000 description 1
- PPHQUIPUBYPZLD-UHFFFAOYSA-N n-ethyl-n-methylaniline Chemical compound CCN(C)C1=CC=CC=C1 PPHQUIPUBYPZLD-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- KPADFPAILITQBG-UHFFFAOYSA-N non-4-ene Chemical compound CCCCC=CCCC KPADFPAILITQBG-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical class C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003151 ovacidal effect Effects 0.000 description 1
- 230000017448 oviposition Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000021018 plums Nutrition 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 235000015136 pumpkin Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000010499 rapseed oil Substances 0.000 description 1
- 235000021013 raspberries Nutrition 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 125000005624 silicic acid group Chemical class 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000021012 strawberries Nutrition 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical class OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
- C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Izum se odnosi na spojeve formule The invention relates to compounds of the formula
[image] [image]
u kojoj where
R1 znači vodik, C1-C4-alkil ili C3-C6-cikloalkil, R1 means hydrogen, C1-C4-alkyl or C3-C6-cycloalkyl,
R2znači vodik, C1-C4-alkil, C3-C6-cikloalkil, benzil, -CHO, -CH2-O-D, -CO-D, -CO-O-D, -CO-CO-O-D, -S-Y, -SO-Y ili -SO2-Y, R2 is hydrogen, C1-C4-alkyl, C3-C6-cycloalkyl, benzyl, -CHO, -CH2-O-D, -CO-D, -CO-O-D, -CO-CO-O-D, -S-Y, -SO-Y or -SO2-Y,
R3 i R4 znače neovisno jedan od drugoga vodik, C1-C4-alkil, C3-C6-cikloalkil ili C1-C4-halogenalkil, R3 and R4 are independently hydrogen, C1-C4-alkyl, C3-C6-cycloalkyl or C1-C4-haloalkyl,
E neovisno jedan od drugoga znače halogen, C1-C4-alkoksil, C1-C4-alkiltio, C1-C4-halogenalkoksil, C1-C4-halogenalkiltio, cijano ili nitro, E, independently of each other, means halogen, C1-C4-alkylthio, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-haloalkylthio, cyano or nitro,
n broj nulu, jedan, dva ili tri, n number zero, one, two or three,
X znači kisik ili sumpor X stands for oxygen or sulfur
A fenil, naftil, supstituirani fenil ili supstituirani naftil, A phenyl, naphthyl, substituted phenyl or substituted naphthyl,
D C1-C10-alkil, fenil ili supstituirani fenil, D C1-C10-alkyl, phenyl or substituted phenyl,
Y znači C1-C4-alkil, C1-C4-halogenalkil, C1-C4-cijanoalkil, Y means C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl,
[image] [image]
fenil ili supstituirani fenil, phenyl or substituted phenyl,
Z vodik, C1-C10-alkil, C1-C4-halogenalkil, C1-C10-alkoksil, [image] fenil, fenoksil, supstituirani fenil ili nesupstituirani fenoksil, Z is hydrogen, C1-C10-alkyl, C1-C4-haloalkyl, C1-C10-alkyl, [image] phenyl, phenoxyl, substituted phenyl or unsubstituted phenoxyl,
R14 i R15 neovisno jedan od drugoga znače C1-C4-alkil ili C3-C6-cikloalkil, R14 and R15 independently of each other mean C1-C4-alkyl or C3-C6-cycloalkyl,
R16 i R17 neovisno jedan od drugoga znače C1-C4-alkil, C3-C6-cikloalkil, fenil ili supstituirani fenil, R16 and R17 independently of each other mean C1-C4-alkyl, C3-C6-cycloalkyl, phenyl or substituted phenyl,
R18 C1-C4-alkil ili C3-C6-cikloalkil, a R18 C1-C4-alkyl or C3-C6-cycloalkyl, a
R19 i R20 neovisno jedan od drugoga znače C1-C4-alkil, C3-C6-cikloalkil, fenil ili supstituirani fenil, u slobodnom obliku ili u obliku soli, postupak za proizvodnju i primjenu tih spojeva, sredstvo za uništavanje štetnika čija aktivna tvar je odabrana iz tih spojeva u slobodnom obliku ili u obliku agrokemijski primjenljivih soli, postupak za proizvodnju i primjenu tih sredstava, sa tim sredstvima tretirano bilje i postupak za uništavanje štetnika. R19 and R20 independently of each other mean C1-C4-alkyl, C3-C6-cycloalkyl, phenyl or substituted phenyl, in free form or in the form of salts, a process for the production and application of these compounds, an agent for destroying pests whose active substance is selected from these compounds in free form or in the form of agrochemically applicable salts, the procedure for the production and application of these agents, plants treated with these agents and the procedure for destroying pests.
U literaturi su predloženi određeni 3-karbamoilpirazol-derivati kao aktivne tvari u sredstvima za uništavanje štetnika, koje djeluju akaricidno, insekticidno i fungicidno. No, biološka svojstva tih poznatih spojeva na području uništavanja štetnika ne zadovoljavaju u potpunosti, zbog čega postoji potreba, da se stave na raspolaganje daljnji spojevi sa svojstvima za uništavanje štetnika, naročito za uništavanje insekata, reprezentanata reda reda akarina, nematoda i fitopatogenih gljivica, pri čemu se taj zadatak prema izumu rješava korištenjem predmetnih spojeva I. Certain 3-carbamoylpyrazole derivatives have been proposed in the literature as active substances in means for destroying pests, which have acaricidal, insecticidal and fungicidal effects. However, the biological properties of these known compounds in the field of pest destruction are not fully satisfactory, which is why there is a need to make available further compounds with pest-killing properties, especially for the destruction of insects, representatives of the acarine order, nematodes and phytopathogenic fungi, while according to the invention, this task is solved using the subject compounds I.
Spojevi I. koji imaju barem jedan bazični centar, mogu npr. činiti adicione soli kiseline. One nastaju primjerice sa jakim anorganskim kiselinama kao mineralne kiseline, npr. perklorna, sumporna, dušična, dušikasta kiselina, sa fosfornom kiselinom ili halogenom vodikovom kiselinom, sa jakim organskim karbonskim kiselinama kao primjerice halogenom supstituiranom C1-C4-alkankarbonskom kiselinom, npr. octenom kiselinom kao eventualno nezasićene dikarbonske kiseline, npr. oksalna, malonska, jantarna, maleinska, fumarna ili ftalanska kiselina, kao hidroksikarbonske kiseline, npr. askorbinska, mliječna, jabučna, vinska ili limunska kiselina ili benzojeva kiselina ili sa organskim sulfonskim kiselinama kao eventualno npr. halogenom supstituiranim C1-C4-alkanskim ili aril-sulfonskim kiselinama, npr. metanska ili p-toluolsulfonska kiselina. Nadalje spojevi I mogu sa najmanje jednom acidnom grupom činiti soj sa bazama. Prikladne soli sa bazama su primjerice metalne soli kao alkalne ili zemnoalkalne soli, npr. natrijeva, kalijeva ili magnezijeva sol ili soli sa amonijakom ili jednim organskim amonom kao morfolin, piperidin, pirolidin, mono-, di- ili tri-niskim alkilaminom, npr. etil-, dietil-, trietil- ili dimetil-propilamin ili mono-, di- ili trihidroksi-niski alkilamin, npr. mono- di- ili trietanolamin. Nadalje se mogu eventualno stvarati odgovarajuće unutrašnje soli. U okviru izuma preporučaju se agrokemijski primjenljive soli; no, obuhvaćene su i agrokemijske primjene koje su štetne, npr. soli koje su toksične za pčele ili ribe, koje se koriste za izolaciju odn. pročišćavanje slobodnih spojeva I ili njihovih agrokemijski primjenljivih soli. Uslijed uske povezanosti između spojeva I u slobodnom obliku i u obliku njihovih soli, u gornjem i daljnjem tekstu pod slobodnim spojevima I odn. njihovim solima trebaju podrazumijevati eventualno i odgovarajuće soli odn. slobodni spojevi I. Compounds I, which have at least one basic center, can, for example, form acid addition salts. They are formed, for example, with strong inorganic acids such as mineral acids, e.g. perchloric, sulfuric, nitric, nitrous acid, with phosphoric acid or hydrohalic acid, with strong organic carboxylic acids such as halogen-substituted C1-C4-alkanecarboxylic acid, e.g. acetic acid as possibly unsaturated dicarboxylic acids, e.g. oxalic, malonic, succinic, maleic, fumaric or phthalic acid, as hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid or benzoic acid or with organic sulfonic acids as possibly e.g. halogen substituted C1-C4-alkanoic or aryl-sulfonic acids, eg methane or p-toluenesulfonic acid. Furthermore, compounds I can form a strain with bases with at least one acid group. Suitable salts with bases are, for example, metal salts such as alkali or alkaline earth salts, e.g. sodium, potassium or magnesium salts or salts with ammonia or an organic ammonium such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propylamine or mono-, di- or trihydroxy-lower alkylamine, eg mono-di- or triethanolamine. Furthermore, appropriate internal salts can eventually be formed. Within the scope of the invention, agrochemically applicable salts are recommended; however, agrochemical applications that are harmful are also covered, for example, salts that are toxic to bees or fish, that are used for isolation or purification of free compounds I or their agrochemically applicable salts. Due to the close connection between compounds I in free form and in the form of their salts, in the above and further text under free compounds I or their salts should possibly mean corresponding salts or free compounds I.
U gornjem i daljnjem tekstu korišteni opći pojmovi imaju, ukoliko nije drugačije definirano, dolje navedena značenja. In the above and further text, the general terms used have, unless otherwise defined, the following meanings.
Naročito se gornja definicija radikala A mora shvatiti tako, da A u poželjnom obliku izvedbe stoji za fenil, naftil ili stoji za fenil ili naftil supstituiran nulom, jedan, dva ili tri ostatka iz grupe halogena, C1-C4-alkilom, C1-C4-halogenalkilom, C1-C4-alkoksilom, C1-C4-halogenalkoksilom, C1-C4-alkiltio, C1-C4-halogenalkiltio, C1-C4-alkilsulfonilom, C1-C4-alkilsulfonilom, C1-C4-halogenalkilsulfinilom, C1-C4-halogenalkilsulfonilom, C1-C4-alkilsulfoniloksilom, halogen-C1-C4-alkilsulfoniloksilom, formilom, nitro, cijano, C1-C4-alkilkarbonilom, C1-C4-halogenalkilkarbonilom, C1-C4-alkoksikarbonilom ili C1-C4-halogenalkoksikarbonilom, pri čemu i dva vicinalna ostatka mogu stajati za -O-CH2-O-, -O-CF2-O-, -O-CH2-CH-2-O- ili -O-CF2-CFz-O i nulom ili jednim radikalom -Y-R5 supstituirani fenil ili naftil, pri čemu Y znači kisik, sumpor ili mosni lanac -SO-, -SO2-, -CO-, -CR6R7-, NR8- ili direktnu jednostavnu vezu, R5fenil, naftil ili piridil ili nulom, jedan, dva ili tri ostatka iz grupe halogena, C1-C4-alkilom, C1-C4-halogenalkilom, C1-C4-alkoksilom, C1-C4-halogenalkoksilom, C1-C4-alkiltio, C1-C4-halogenalkiltio, C1-C4-alkilsulfinilom, C1-C4-alkilsulfonilom, C1-C4-halogenalkilsulfinilom, C1-C4-halogenalkilsulfonilom, C1-C4-alkilsulfoniloksilom, halogen-C1-C4-alkilsulfoniloksilom, formilom, nitro, cijano, C1-C4-alkilkarbonilom, C1-C4-alkoksikarbonilom ili C1-C4-haloenalkoksikarbonilom supstituirani fenil, naftil ili piridil, pri čemu i dva od ovih ostataka u vicinalnoj poziciji mogu činiti most strukture -O-CH2-O, -O-CF2-O-, -O-CH2-CH2-O- ili -O-CF2-CF2-O-. R6 i R7 neovisno jedan od drugoga znače vodik ili C1-C4-alkil, a R8 vodik, C1-C4-alkil, formil, C1-C4-alkilkarbonil ili C1-C4-alkoksikarbonil. In particular, the above definition of the radical A must be understood so that A in the preferred form of embodiment stands for phenyl, naphthyl or stands for phenyl or naphthyl substituted by zero, one, two or three residues from the halogen group, C1-C4-alkyl, C1-C4- Haloalkyl, C1-C4-Alkoxyl, C1-C4-Haloalkyloxy, C1-C4-Alkylthio, C1-C4-Haloalkylthio, C1-C4-Alkylsulfonyl, C1-C4-Alkylsulfonyl, C1-C4-Haloalkylsulfinyl, C1-C4-Haloalkylsulfonyl, C1-C4-alkylsulfonyloxyl, halo-C1-C4-alkylsulfonyloxyl, formyl, nitro, cyano, C1-C4-alkylcarbonyl, C1-C4-haloalkylcarbonyl, C1-C4-alkoxycarbonyl or C1-C4-haloalkoxycarbonyl, wherein two vicinal residues can stand for -O-CH2-O-, -O-CF2-O-, -O-CH2-CH-2-O- or -O-CF2-CFz-O and zero or one radical -Y-R5 substituted phenyl or naphthyl, where Y means oxygen, sulfur or a bridge chain -SO-, -SO2-, -CO-, -CR6R7-, NR8- or a direct single bond, R5phenyl, naphthyl or pyridyl or zero, one, two or three residues from the halo group ene, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkyloxy, C1-C4-haloalkyloxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, Substituted by C1-C4-haloalkylsulfinyl, C1-C4-haloalkylsulfonyl, C1-C4-alkylsulfonyloxy, halo-C1-C4-alkylsulfonyloxy, formyl, nitro, cyano, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl or C1-C4-haloenalkoxycarbonyl phenyl, naphthyl or pyridyl, whereby two of these residues in the vicinal position can form a bridge of the structure -O-CH2-O, -O-CF2-O-, -O-CH2-CH2-O- or -O-CF2- CF2-O-. R 6 and R 7 independently of each other mean hydrogen or C 1 -C 4 -alkyl, and R 8 hydrogen, C 1 -C 4 -alkyl, formyl, C 1 -C 4 -alkylcarbonyl or C 1 -C 4 -alkoxycarbonyl.
Kod halogenih atoma koji dolaze u obzir kao supstituenti radi se kako o fluoru i kloru, tako i o bromu i jodu, pri čemu se preferiraju fluor, klor i brom. Halogen se pri tome smatra samostalnim supstituentom ili dijelom supstituenta kao u halogenalkilu, halogenalkoksilu, halogenalkiltio, halogenalkilsulfinilu, halogenalkilsulfonilu, halogenalkilkarbonilu ili halogenalkoksikarbonilu. The halogen atoms that come into consideration as substituents are both fluorine and chlorine, as well as bromine and iodine, whereby fluorine, chlorine and bromine are preferred. Halogen is considered to be an independent substituent or part of a substituent as in haloalkyl, haloalkyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, haloalkylcarbonyl or haloalkylcarbonyl.
Alkilni, alkiltlo i alkoksilni ostaci mogu biti ravnolančani ili razgranati. Kao primjeri takovih alkila spomenimo alkil, metil, etil, propil, izopropil, butil, i-butil, sekundarni butil, heptil i njegovi izomeri, n-oktil i n-dodecil. Kao prikladne alkoksilne ostatke između ostalog spominjemo: metoksil, etoksil, propoksil. izopropoksil, butoksil i njihove izomere, kao i n-heksoksil i n-oktiloksil. Kao primjeri za alkiltio su metiltio, etiltio, propiltio, kao i četiri izomera butiltio. Alkyl, alkyl and alkyl radicals can be straight-chain or branched. Examples of such alkyls are alkyl, methyl, ethyl, propyl, isopropyl, butyl, i-butyl, secondary butyl, heptyl and its isomers, n-octyl and n-dodecyl. Examples of suitable alkyl radicals include: methoxyl, ethoxyl, propoxyl. isopropoxyl, butoxyl and their isomers, as well as n-hexoxyl and n-octyloxyl. Examples of alkylthio are methylthio, ethylthio, propylthio, as well as the four isomers of butylthio.
Ostaci alkilsulfinila i alkilsulfonila izvode se od odgovarajućih alkiltio-ostataka i razlikuju se jedni od drugih samo po stupnjevima oksidiranja atoma sumpora. The alkylsulfinyl and alkylsulfonyl residues are derived from the corresponding alkylthio residues and differ from each other only by the degrees of oxidation of the sulfur atom.
Ako su alkilne, alkiltio ili alkoksilne grupe koje dolaze u obzir kao supstituenti supstituirane halogenom, mogu se samo djelomično halogenirati ili i perhalogenirati. Pri tome za halogen, alkil, alkiltio i alkoksil važe gore navedene definicije. Primjeri alkilnih elemenata tih grupa su jedno- do trostruko fluorom, klorom i/ili bromom supstituirani metili kao primjerice CHF2 ili CF3; jedno- do peterostruko fluorom, klorom i/ili bromom supstituirani etil kao npr. CH2CF3, CF2CF3, CF2CCl3, CF2CHCl2, CF2CHF2, CF2CHF2, CF2CFCl2, CF2CHBr3, CF2CHClF, CF2ClBrF ili CClFCHClD; jedno- do sedmerostruko fluorom, klorom i/ili bromom supstituirani propil ili izopropil kao na primjer CH2CHBrCH2Br, CF2CHCFCF3, CH2CF2CF3, CF2CF2CF3 ili CH(CF3)2; jedno- do deveterostruko fluorom, klorom i/ili bromom supstituirani butil ili jedan od njegovih izomera kao na primjer CF(CF3)CHFCF3, -(CF2)3CF3 ili CH2(CF2)2CF3. If the alkyl, alkylthio or alkoxyl groups that come into consideration as substituents are substituted by halogen, they can only be partially halogenated or even perhalogenated. The above definitions apply to halogen, alkyl, alkylthio and alkyl. Examples of alkyl elements of these groups are methyls substituted one to three times by fluorine, chlorine and/or bromine, such as CHF2 or CF3; one- to five-fold fluorine-, chlorine- and/or bromine-substituted ethyl such as CH2CF3, CF2CF3, CF2CCl3, CF2CHCl2, CF2CHF2, CF2CHF2, CF2CFCl2, CF2CHBr3, CF2CHClF, CF2ClBrF or CClFCClD; propyl or isopropyl substituted one- to seven-fold with fluorine, chlorine and/or bromine such as CH2CHBrCH2Br, CF2CHCFCF3, CH2CF2CF3, CF2CF2CF3 or CH(CF3)2; one- to nine-fold fluorine-, chlorine- and/or bromine-substituted butyl or one of its isomers, for example CF(CF3)CHFCF3, -(CF2)3CF3 or CH2(CF2)2CF3.
Kod ostataka cikloalkila koji dolaze u obzir kao supstituenti radi se primjerice o ciklopropilu, ciklobutilu, ciklopentilu ili cikloheksilu. The cycloalkyl residues that come into consideration as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Primjeri za ostatke alkoksikarbona su metoksikarbonil, etoksikarbonil, propoksikarbonil, izopropoksikarbonil, butoksikarbonil ili terc. butoksikarbonil. Alkilkarbonik stoji za acil, propionil, butiroil ili butilkarbonil. Examples of alkoxycarbonyl radicals are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl or tert. butoxycarbonyl. Alkylcarbonic stands for acyl, propionyl, butyroyl or butylcarbonyl.
Ukoliko dva od supstituenata ostatka A ili ostatka R5 zajedno čine navedene mostove, nastaju kao nova osnovna tijela sa bicikličnim strukturama benzodioksoli, dioksolpiridini, benzodioksini, dioksinopiridini, naftodioksoli ili naftodioksini. Kao supstituenti radikala A i ostatka R5 nabrojene grupe mogu neovisno jedne od drugih imati ista ili različita značenja. If two of the substituents of residue A or residue R5 together form the mentioned bridges, they are formed as new basic bodies with bicyclic structures benzodioxoles, dioxolpyridines, benzodioxins, dioxynopyridines, naphthodioxoles or naphthodioxins. As substituents of the radical A and the residue R5, the enumerated groups can independently have the same or different meanings.
Kod spojeva formule I razlikujemo dvije grupe. U prvoj grupi sažeti su takovi spojevi kod kojih R2 ima različito značenje od vodika, C1-C4-alkila, benzila i C3-C6cikloalkila. Ovdje se naročito preporučaju spojevi formule I, kod kojih ili With compounds of formula I, we distinguish two groups. The first group summarizes such compounds where R2 has a different meaning than hydrogen, C1-C4-alkyl, benzyl and C3-C6cycloalkyl. Compounds of formula I are particularly recommended here, in which or
a) D znači C1-C10-alkil, fenil, C1-C4-alkilfenil ili halogenfenil, a) D means C1-C10-alkyl, phenyl, C1-C4-alkylphenyl or halophenyl,
Y znači C1-C4-alkil, C1-C4-halogenalkil, C1-C4-cijanoalkil, fenil, C1-C4-alkilfenil, halogenfenil, Y means C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, phenyl, C1-C4-alkylphenyl, halophenyl,
[image] [image]
Z vodik, C1-C4-alkil, fenil, C1-C4-alkilfenil, halogenfenil, C1-C10-alkoksil, fenoksil, C1-C4-alkilfenoksil, halogenfenoksil ili Z is hydrogen, C1-C4-alkyl, phenyl, C1-C4-alkylphenyl, halophenyl, C1-C10-alkoxy, phenoxyl, C1-C4-alkylphenoxyl, halophenoxyl or
[image] [image]
R16 i R17 neovisno jedan od drugoga znače C1-C4-alkil, C3-C6-cikloalkil. fenil, C1-C4-alkilfenil ili halogenfenil, a R16 and R17 independently of each other mean C1-C4-alkyl, C3-C6-cycloalkyl. phenyl, C1-C4-alkylphenyl or halophenyl, a
R19 i R20 neovisno jedan od drugoga znače C1-C4-alkil, pri tome se kod ove podgrupe posebno moraju naglasiti oni spojevi, kod kojih R19 and R20 independently of each other mean C1-C4-alkyl, while in this subgroup, those compounds in which
D znači C1-C10-alkil, fenil ili 4-klorfenil, D means C1-C10-alkyl, phenyl or 4-chlorophenyl,
Y C1-C4-alkil, C1-C4-halogenalkil, C1-C4-cijanoalkil, fenil, 4-metilfenil, 4-klorfenil, 3,4-diklorfenil, Y C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, phenyl, 4-methylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl,
[image] [image]
Z znači vodik, C1-C4-alkil, fenil, 4-klorfenil, C1-C10-alkoksil, fenoksii, 4-klorfenoksil ili Z stands for hydrogen, C1-C4-alkyl, phenyl, 4-chlorophenyl, C1-C10-alkoxy, phenoxy, 4-chlorophenoxyl or
[image] [image]
R14 i R15 neovisno jedan od drugoga znače C1-C4-alkil, R14 and R15 independently of each other mean C1-C4-alkyl,
R16 C1-C4-alkil, fenil, 4-klorfenil, R16 C1-C4-alkyl, phenyl, 4-chlorophenyl,
R17 metil, a R17 methyl, a
R18 znači alkil-alkil ili ciklopropil ili R 18 means alkyl-alkyl or cyclopropyl or
b) R1 je metil ili etil, a R3 i R4 vodik ili b) R1 is methyl or ethyl, and R3 and R4 are hydrogen or
c) A znači eventualno supstituiranu fenoksifenilnu grupu formule c) A means a possibly substituted phenoxyphenyl group of the formula
[image] [image]
u kojoj where
R9, R10, R11, R12 neovisno jedan od drugoga znače vodik, halogen, C1-C4-alkil, C1-C4-halogenalkil ili C1-C4-alkoksil, a R13 znači vodik, halogen, C1-C4-alkil, C1-C4-haloganalkil, C1-C4-alkoksil, C1-C4-halogenalkoksil, C1-C4-halogenalkiltio, C1-C4-alkiltio, C1-C4-alkilsulfinil, C1-C4-alkilsulfonil, C1-C4-halogenalkilsulfinil, C1-C4-halogenalkilsulfonil, C1-C4-alkilsulfoniloksil, halogen-C1-C4-alkilsulfoniloksil, cijano ili nitro, a R12 i R13 zajedno znače -O-CH2-O-, pri čemu su kod tih podgrupa naročito interesantni spojevi kod kojih R9, i R10 znače vodik, R9, R10, R11, R12 independently of each other mean hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkyl, and R13 means hydrogen, halogen, C1-C4-alkyl, C1-C4 -Haloalkyl, C1-C4-Alkoxyl, C1-C4-Haloalkylthio, C1-C4-Haloalkylthio, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4-Haloalkylsulfinyl, C1-C4-Haloalkylsulfonyl . ,
R11 i R12 neovisno jedan od drugoga znače vodik, fiuor, klor ili trifluormetil, R11 and R12 independently of each other mean hydrogen, fluorine, chlorine or trifluoromethyl,
R13 znači vodik, C1-C4-alkil, C1-C4-halogenalkil, C1-C4-alkoksil, C1-C4-halogenalkoksil, C1-C4-alkiltio, C1-C4-halogenalkiltio, C1-C4-halogenalkiltio, C1-C4-alkilsulfonil, C1-C4-alkilsulfoniloksil, halogen- C1-C4-alkilsulfonoloksil, fluor, klor, brom cijan, ili nitro, a R12 i R13 zajedno znače -O-CH2O-posebno se moraju istaknuti spojevi kod kojih R11 i R12 neovisno jedan od drugoga znače vodik, fluor, klor ili trifluormetil, R13 vodik, C1-C4-alkil, fluor, klor, brom, cijan, metoksil, metiltio, trifluormetil, metilsulfonil, metilsulfoniloksil ili trifluormetilsulfoniloksil, a R12 i R13 su zajedno -O-CH2-O-, dok n znači brojku nula, jedan ili dva, a supstituenti E neovisno jedan od drugoga znače halogen, C1-C4-alkil, C1-C4-halogenalkil ili C1-C4-alkoksil, R1 metil ili etil, a R3 i R4 znače vodik. R13 stands for hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-haloalkylthio, C1-C4- alkylsulfonyl, C1-C4-alkylsulfonyloxyl, halogen-C1-C4-alkylsulfonoloxyl, fluorine, chlorine, bromine cyano, or nitro, and R12 and R13 together mean -O-CH2O- especially the compounds where R11 and R12 independently one of the second is hydrogen, fluorine, chlorine or trifluoromethyl, R13 is hydrogen, C1-C4-alkyl, fluorine, chlorine, bromine, cyano, methoxy, methylthio, trifluoromethyl, methylsulfonyl, methylsulfonyloxyl or trifluoromethylsulfonyloxyl, and R12 and R13 together are -O-CH2- O-, while n means the number zero, one or two, and the substituents E independently of each other mean halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkyl, R1 is methyl or ethyl, and R3 and R4 mean hydrogen.
U jednoj drugoj grupi sažeti su ono spojevi formule I, kod kojih R2 znači vodik, C1-C4-alkil, C3-C6-cikloalkil ili benzil, pri čemu se ovdje trebaju naglasiti takovi spojevi, kod kojih A stoji za fenil, naftil ili nulom, jednim ili dva ostatka iz grupe halogena. C1-C4-alkila, C1-C4-halogenalkila, C1-C4-alkoksila, C1-C4-halogenalkoksila, C1-C4-alkiltio, C1-C4-halogenalkiltio, C1-C4-alkilsulfinila, C1-C4-alkilsulfonila, C1-C4-halogenalkilsulfinila, C1-C4-halogenalkilsulfonila, C1-C4-alkilsulfoniloksila, halogen-C1-C4-alkilsulfoniloksila, formila, nitro, cijano, C1-C4-alkilkarbonila, C1-C4halogenalkilkarbnnila, C1-C4-alkoksikarbonila ili C1-C4-halogenalkoksikarbonila, pri čemu i dva vicinalna ostatka mogu stajati za -O-CH2-O-, -O-CF2-O-, -O-CH2-CH2-O- ili -O-CF2-CF2-O- ili radikalom -Y-R5 supstituirani fenil ili naftil, pri čemu Y znači kisik, sumpor ili mosni lanac -SO-, -SO2, -CO-, -CR6R7-, -NR8 ili direktnu vezu, R5 znači fenil, naftil ili piridil ili nulom, jednim ili dva ostatka iz grupe halogen, C1-C4-alkil, C1-C4-halogenalkil, C1-C4-alkoksil, C1-C4-alkoksil, C1-C4-halogenalkoksil, C1-C4-alkiltio, C1-C4-halogenalkiltio, C1-C4-alkilsulfinil, C1-C4-alkilsulfonil, C1-C4-halogenalkilsulfinil, C1-C4-halogenalkilsulfonil, C1-C4-alkilsulfoniloksil, halogen-C1-C4-alkilsulfoniloksil, formil, nitro, cijano, C1-C4-alkilkarbonil, C1-C4-halogenalkilkarbonil, C1-C4-alkoksikarbonil ili C1-C4-halogenalkoksikarbonil supstituirani fenil, naftil ili piridil, pri čemu i dva tih ostataka u vicinalnoj poziciji mogu činiti most strukture -O-CH2-O-, -O-CF2-O-, -O-CH2-CH2-O- ili -O-CF2-CF2-O-, R6 i R7 neovisno jedan od drugoga znače vodik ili C1-C4-alkinil, a R8 vodik, C1-C4-alkil, formil, C1-C4-alkilkarbonil ili C1-C4-alkoksikarbonil, In another group, those compounds of formula I, where R2 means hydrogen, C1-C4-alkyl, C3-C6-cycloalkyl or benzyl, are summarized, whereby such compounds should be emphasized here, where A stands for phenyl, naphthyl or zero , one or two residues from the halogen group. C1-C4-Alkyl, C1-C4-Haloalkyl, C1-C4-Alkoxyl, C1-C4-Haloalkyl, C1-C4-Alkylthio, C1-C4-Haloalkylthio, C1-C4-Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1- C4-haloalkylsulfinyl, C1-C4-haloalkylsulfonyl, C1-C4-alkylsulfonyloxy, halogen-C1-C4-alkylsulfonyloxyl, formyl, nitro, cyano, C1-C4-alkylcarbonyl, C1-C4haloalkylcarbonyl, C1-C4-alkoxycarbonyl or C1-C4- haloalkoxycarbonyl, whereby two vicinal residues can stand for -O-CH2-O-, -O-CF2-O-, -O-CH2-CH2-O- or -O-CF2-CF2-O- or the radical -Y -R5 substituted phenyl or naphthyl, where Y means oxygen, sulfur or a bridge chain -SO-, -SO2, -CO-, -CR6R7-, -NR8 or a direct bond, R5 means phenyl, naphthyl or pyridyl or zero, one or two residues from the group halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4- alkoxyl, C1-C4-alkoxyl, C1-C4-halogenalkoxyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1- C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-halogenalkylsulfinyl, C1-C4-halogenalkylsulfonyl, C1-C4-alkylsulfonyloxyl , halo-C1-C4-alkylsulfonyloxyl, formyl, nitro, cyano, C1-C4-alkylcarbonyl, C1-C4-haloalkylcarbonyl, C1-C4-alkoxycarbonyl or C1-C4-haloalkoxycarbonyl substituted phenyl, naphthyl or pyridyl, wherein both of these residues in the vicinal position can form a bridge structure -O-CH2-O-, -O-CF2-O-, -O-CH2-CH2-O- or -O-CF2-CF2-O-, R6 and R7 independently one of the second one is hydrogen or C1-C4-alkynyl, and R8 is hydrogen, C1-C4-alkyl, formyl, C1-C4-alkylcarbonyl or C1-C4-alkoxycarbonyl,
pri čemu se kod tih podgrupa naročito preferiraju takovi spojevi, kod kojih su definirani radikali naftila spojeni u 1- ili 2-poziciji, a definirani radikali piridila u 1-, 3- ili 4-poziciji. whereby in these subgroups such compounds are particularly preferred, in which the defined naphthyl radicals are connected in the 1- or 2-position, and the defined pyridyl radicals are in the 1-, 3- or 4-position.
S druge strane kod ove druge grupe spojeva formule I prema izumu, pažnju zaslužuju takove tvari, kod kojih On the other hand, with this second group of compounds of formula I according to the invention, such substances deserve attention, in which
d) n stoji za brojke nula,jedan ili dva, a supstituenti E neovisno jedan od drugoga stoje za halogen, C1-C4-alkil, C1-C4-halogenalkil ili C1-C4-alkoksil ili d) n stands for the numbers zero, one or two, and the substituents E independently of each other stand for halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkyl or
e) R1 stoji za metil ili etil, a R2, R3 i R4 za vodik ili e) R1 stands for methyl or ethyl, and R2, R3 and R4 for hydrogen or
f) A stoji za eventualno supstituirano fenoksifenilnu grupu formule f) A stands for a possibly substituted phenoxyphenyl group of the formula
[image] [image]
u kojoj where
R9, R10, R11, R12 neovisno jedan od drugoga znače vodik, halogen, C1-C4-alkil, C1-C4-halogenalkil ili C1-C4-alkoksil, a R13 znači vodik, halogen, C1-C4-alkil, C1-C4-halogenalkil, C1-C4-alkoksil, C1-C4-halogenalkoksil, C1-C4-alkilsulfinil, C1-C4-alkilsulfonil, C1-C4-halogenalkilsulfinil, C1-C4-halogenalkilsulfonil, C1-C4-alkilsulfoniloksil, halogen-C1-C4-alkilsulfoniloksil, cijano ili nitro. R9, R10, R11, R12 independently of each other mean hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkyl, and R13 means hydrogen, halogen, C1-C4-alkyl, C1-C4 -Haloalkyl, C1-C4-Alkoxyl, C1-C4-Haloalkyl, C1-C4-Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4-Haloalkylsulfinyl, C1-C4-Haloalkylsulfonyl, C1-C4-Alkylsulfonyloxy, Halogen-C1-C4 -alkylsulfonyloxy, cyano or nitro.
Među spojevima podgrupe f) preferiraju se takovi derivati, u kojima R9, R10, R11 i R12 znače vodik, a R13 vodik, C1-C4-alkil, C1-C4-halogenalkil, C1-C4-alkoksil, C1-C4-halogenalkoksil, C1-C4-alkiltio, C1-C4-halogenalkiltio, C1-C4-alkilsulfonil, C1-C4-halogenalkilsulfonil, cijan ili nitro, a naročito oni spojevi, u kojima R13 znači vodik, halogenmetil, halogenetil, cijan, nitro, metiltio, etiltio, metilsulfonil, etilsulfonil, metilsulfoniloksil ili trifluormetilsulfoniloksil. Among the compounds of subgroup f), such derivatives are preferred, in which R9, R10, R11 and R12 are hydrogen, and R13 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4- alkoxyl, C1-C4-halogenalkoxyl, C1-C4-alkylthio, C1-C4-halogenalkylthio, C1-C4-alkylsulfonyl, C1-C4-halogenalkylsulfonyl, cyano or nitro, and especially those compounds in which R13 means hydrogen, halomethyl, haloethyl, cyano, nitro, methylthio, ethylthio , methylsulfonyl, ethylsulfonyl, methylsulfonyloxy or trifluoromethylsulfonyloxy.
Grupa aktivnih tvari prema izumu koja se naročito treba istaknuti zbog njenih dobrih bioloških svojstava odlikuje se time, da n stoji za brojku nula, dva ili tri, supstituenti Eneovisno jedan od drugoga stoje za halogen, C1-C4-alkil, C1-C4-halogenalkil ili C1-C4-alkoksil, R1 za metil ili etil, R2, R3 i R4 vodik, a A za grupu formule The group of active substances according to the invention, which should be particularly highlighted due to its good biological properties, is distinguished by the fact that n stands for the number zero, two or three, the substituents Ene, depending on each other, stand for halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-Alkoxyl, R1 for methyl or ethyl, R2, R3 and R4 hydrogen, and A for a group of the formula
[image] [image]
u kojoj R9, R10, R11, R12 neovisno jedan od drugoga znače halogen, C1-C4-alkil, C1-C4-halogenalkil, C1-C4-halogenalkoksil ili C1-C4-alkoksil, a R13 vodik, halogen, C1-C4-alkil, C1-C4-halogenalkil, C1-C4-alkoksil, C1-C4-halogenalkoksil, C1-C4-halogenalkiltio, C1-C4-alkiltio, C1-C4-alkilsulfinil, C1-C4-alkilsulfonil, C1-C4-halogenalkilsulfinll, C1-C4-halogenalkilsulfonil, C1-C4-alkilsulfoniloksil, halogen-C1-C4-alkilsulfoniloksil, cijano ili nitro. in which R9, R10, R11, R12 independently of each other mean halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-halogenalkoxyl or C1-C4-alkyl, and R13 is hydrogen, halogen, C1-C4- Alkyl, C1-C4-Haloalkyl, C1-C4-Alkoxyl, C1-C4-Haloalkyl, C1-C4-Haloalkylthio, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4-Haloalkylsulfinyl, C1-C4-haloalkylsulfonyl, C1-C4-alkylsulfonyloxy, halo-C1-C4-alkylsulfonyloxy, cyano or nitro.
Isto tako mora se istaknuti grupa spojeva formule I, u kojoj n stoji za brojeve nula, jedan ili dva, supstituenti E neovisno jedan od drugoga stoje za halogen, C1-C4-alkil, C1-C4-halogenalkil, C1-C4-alkoksil, C1-C4-halogenalkoksil; R1 stoji za metil ili etil; R2, R3, R4 stoje za vodik, a A za fenil, naftil ili nulom, jedan, dva ili tri ostatka iz grupe halogen, C1-C4-alkil, C1-C4-halogenalkil, C1-C4-alkoksil, C1-C4-halogenalkoksil, C1-C4-alkiltio, C1-C4-halogenalkiltio, C1-C4-alkilsulfinil, C^ C^ C1-C4-halogenalkilsulfinil, C1-C4-alkilsulfonil, C1-C4-halogenalkilsulfonil, C1-C4-alkilsulfoniloksil, halogen-C1-C4-alkilsulfoniloksil, formil, cijan, nitro, C1-C4-alkilkarbonil, C1-C4-halogenalkilkarbonil, C1-C4-alkoksikarbonil, C1-C4-halogenalkoksikarbonil, supstituirani fenil ili naftil, pri čemu i dva od tih ostataka u vicinalnoj poziciji mogu stajati za -O-CH2-O-, -O-CF2-O-, -O-CH2-CH2-O- ili –O-CF2-CF2-O-. The group of compounds of formula I, in which n stands for the numbers zero, one or two, the substituents E independently of each other stand for halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkyl, C1-C4-halogenalkoxyl; R 1 stands for methyl or ethyl; R2, R3, R4 stand for hydrogen, and A for phenyl, naphthyl or zero, one, two or three residues from the group halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkyl, C1-C4- haloalkyl, C1-C4-alkylthio, C1-C4-halogenalkylthio, C1-C4-alkylsulfinyl, C^ C^ C1-C4-halogenalkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-halogenalkylsulfonyl, C1-C4-alkylsulfonyloxy, halogen- C1-C4-alkylsulfonyloxy, formyl, cyano, nitro, C1-C4-alkylcarbonyl, C1-C4-haloalkylcarbonyl, C1-C4-alkoxycarbonyl, C1-C4-haloalkoxycarbonyl, substituted phenyl or naphthyl, wherein two of these residues in the vicinal position can stand for -O-CH2-O-, -O-CF2-O-, -O-CH2-CH2-O- or –O-CF2-CF2-O-.
Na kraju se mora spomenuti još ona grupa spojeva formule I, u kojoj n stoji za broj nula, jedan ili dva, supstituenti E neovisno jedan od drugoga za halogen, C1-C4-alkil, C1-C4-halogenalkil, C1-C4-halogenalkoksil ili C1-C4-alkoksil, R1 za metil ili etil, R2, R3 i R4 za vodik, a A za jednu grupu formule Finally, we must mention the group of compounds of formula I, in which n stands for the number zero, one or two, the substituents E independently of each other for halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-halogenalkoxyl or C1-C4-Alkoxyl, R1 for methyl or ethyl, R2, R3 and R4 for hydrogen, and A for one group of the formula
[image] [image]
u kojoj where
R13 znači vodik, halogen, C1-C4-alkil, halogenmetil, halogenetil, C1-C4-alkoksil, halogenmetoksil, halogenetoksil, C1-C4-alkilsulfinil, metilsulfonil, etilsulfonil, halogenmetilsulfonil, metilsulfoniloksil, trifluormetilsulfoniloksil, cijano ili nitro. Kod te grupe se preferiraju naročito takovi spojevi u kojima R13 znači vodik, halogenmetil, halogenetil, cijan, nitro, metiltio, etiltio, metilsulfonil ili etilsulfonil. R 13 means hydrogen, halogen, C1-C4-alkyl, halomethyl, haloethyl, C1-C4-alkoxy, halomethoxy, halogenethoxy, C1-C4-alkylsulfinyl, methylsulfonyl, ethylsulfonyl, halomethylsulfonyl, methylsulfonyloxy, trifluoromethylsulfonyloxy, cyano or nitro. In this group, compounds in which R13 means hydrogen, halogenmethyl, halogenethyl, cyano, nitro, methylthio, ethylthio, methylsulfonyl or ethylsulfonyl are particularly preferred.
U okviru izuma posebno se preferiraju In the context of the invention, they are particularly preferred
2-metil-2H-indazol-3-karbonska kiselina-(4-tert.-butil-benzil)-amid, 2-methyl-2H-indazole-3-carboxylic acid-(4-tert.-butyl-benzyl)-amide,
2-metil-2H-indazol-3-karbonska kiselina-(4-(4-fluorfenoksil)-benzil)-amid, 2-methyl-2H-indazole-3-carboxylic acid-(4-(4-fluorophenoxyl)-benzyl)-amide,
2-metil-2H-indazol-3-karbonska kiselina-(3-(4-fluorfenoksil)-benzil)-amid, 2-methyl-2H-indazole-3-carboxylic acid-(3-(4-fluorophenoxyl)-benzyl)-amide,
2-metil-2H-indazol-3-karbonska kiselina-(4-(4-trifluormetilfenoksil)-benzil)-amid, 2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxyl)-benzyl)-amide,
2-metil-2H-indazol-3-karbonska kiselina-(4-(4-metiltiofanoksil)-benzil)-amid, 2-methyl-2H-indazole-3-carboxylic acid-(4-(4-methylthiophanoxyl)-benzyl)-amide,
2-metil-2H-indazol-3-karbonska kiselina-(4-(2-klor-4-trifluormetilfenoksil)-benzil)-amid, 2-methyl-2H-indazole-3-carboxylic acid-(4-(2-chloro-4-trifluoromethylphenoxyl)-benzyl)-amide,
N-acetil-2-metil-2H-indazol-3-karbonska kiselina-(4-(4-trifluormetil-fenoksil)-benzil)-amid, N-acetyl-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethyl-phenoxyl)-benzyl)-amide,
N-(tert.-butoksioksali)-2-metil-2H-indazol-3-karbonska kiselina-(4_(4-trifluormetilfenoksi)-benzil)-amid, N-(tert.-butoxyoxaly)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxy)-benzyl)-amide,
N-(3,3-dipropil-1-metilureido-1-sulfenil)-2-metil-2H-indazol-3-karbonska kiselina-(4-(4-trifluormetil-fenoksil)-benzil)-amid i N-(3,3-dipropyl-1-methylureido-1-sulfenyl)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethyl-phenoxyl)-benzyl)-amide and
N-(2-etilheksanoil)-2-metil-2H-indazol-3--karbonska kiselina-(4-(4-trifluormetilfenoksil)-benzil)-amid. N-(2-ethylhexanoyl)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxyl)-benzyl)-amide.
Spojevi formule I prema izumu mogu se dobiti prema poznatim postupcima. Spoj formule I u kojem R2 znači vodik, C1-C4-alkil, benzil ili C1-C4-cikloalkil, a R1, R3, R4, A,E, n i x imaju naprijed navedeno značenje dobiva se primjerice tako, da se prvo ili Compounds of formula I according to the invention can be obtained according to known procedures. The compound of formula I in which R2 means hydrogen, C1-C4-alkyl, benzyl or C1-C4-cycloalkyl, and R1, R3, R4, A, E, n and x have the aforementioned meaning is obtained, for example, by first or
a) 2H-indazol-3-karbonska kiselina formule II a) 2H-indazole-3-carboxylic acid of formula II
[image] [image]
u kojoj E, n i R1 Imaju značenje kao u formuli I, kondenzira sa aminom formule III in which E, n and R1 have the meaning as in formula I, condenses with an amine of formula III
[image] [image]
u kojoj R2 znači vodik, C1-C4-alkil, benzil ili C1-C4-cikloalkil, a R3, R4 i A imaju značenje navedeno u formuli I, ili se in which R2 means hydrogen, C1-C4-alkyl, benzyl or C1-C4-cycloalkyl, and R3, R4 and A have the meaning given in formula I, or
b) 2H-indazol-3-karbonska kiselina formule II prevede u halogenid kiseline, imidazolid ili alkilni ester formule IV b) 2H-indazole-3-carboxylic acid of formula II is converted into acid halide, imidazolide or alkyl ester of formula IV
[image] [image]
u kojoj R1, E i n imaju značenje navedeno u formuli I, a Q stoji za klor, hrom, 1-imidazolil, metoksil ili etoksil, taj aktivirani derivat reagira se sa aminom formule III i po želji se dobiveni 3-karbamoil-2H-indazol derivat podformule Ia in which R1, E and n have the meaning given in formula I, and Q stands for chlorine, chromium, 1-imidazolyl, methoxyl or ethoxyl, this activated derivative is reacted with an amine of formula III and, if desired, 3-carbamoyl-2H-indazole is obtained derivative of subformula Ia
[image] [image]
u kojoj R2 znači vodik, C1-C4-alkil, benzil ili C3-C6-cikloalkil, a R1, R3, R4, A, E i n imaju značenje navedeno u formuli I, tretiranjem sa tionirajućim sredstvom prevede u spoj podformule Ib in which R2 means hydrogen, C1-C4-alkyl, benzyl or C3-C6-cycloalkyl, and R1, R3, R4, A, E and n have the meaning given in formula I, by treatment with a thionating agent it is converted into a compound of subformula Ib
[image] [image]
u kojoj je R2 vodik, C1-C4-alkil, benzil ili C1-C4-cikloalkil, a R1, R3, R4, A, E i n imaju značenje navedeno u formuli I i/ili po želji se spoj formule I koji se dobiva prema izumu ili na neki drugi način, u slobodnom obliku ili u obliku soli, prevede u drugi spoj formule I, mješavina izomera koja se dobiva prema postupku se odvoji i željeni izomeri se izoliraju i/ili se slobodni spoj formule I koji se dobiva prema postupku ili na neki drugi način, prevede u sol ili se sol jednog spoja formule I koji se dobiva prema izumu ili na neki drugi način, prevede u slobodni spoj formule I ili u jednu drugu sol. in which R 2 is hydrogen, C 1 -C 4 -alkyl, benzyl or C 1 -C 4 -cycloalkyl, and R 1 , R 3 , R 4 , A, E and n have the meaning given in formula I and/or optionally the compound of formula I obtained by invention or in some other way, in free form or in the form of a salt, converted into another compound of formula I, the mixture of isomers obtained according to the process is separated and the desired isomers are isolated and/or the free compound of formula I obtained according to the process or in some other way, it is converted into a salt or a salt of one compound of formula I which is obtained according to the invention or in some other way, is converted into a free compound of formula I or into another salt.
U daljnjem postupku (varijanta c) dobiva se spoj formule I, u kojoj R2 ima drugačije značenje od vodika, C1-C4-alkila, benzila ili C3-C6-cikloalkila, pri čemu se prvo spoj podformule Ic In a further procedure (variant c), a compound of formula I is obtained, in which R2 has a different meaning than hydrogen, C1-C4-alkyl, benzyl or C3-C6-cycloalkyl, whereby first the compound of subformula Ic
[image] [image]
u kojoj R1, R3, R4, A, E i n imaju značenja navedena u Formuli I u prisustvu jedne baze reagira sa spojem Hal-CH2-O-D, Hal-CHO, Hal-CO-D, Hal-CO-O-D, Hal-CO-CO-D, Hal-CO-CO-O-D, Hal-S-Y, SO-Y ili Hal-SO2-Y, gdje hal znači atom klora, broma ili joda, a D i Y imaju značenja navedena u formuli I i po želji se dobiveni 3-karbamoil-2H-indazolderivat podformule Ia, u kojoj R2 ima značenje drugačije od vodika, C1-C4-alkila, benzila ili C3-C6-cikloalkil, a R1, R3, R4, A, E i n imaju značenja navedena u formuli I, sa tionirajućim sredstvom prevede u spoj podformule Ib, u kojoj R2 znači -CH2-O-D, -CHO, -CO-D, -CO-O-D, -CO-CO-D, CO-CO-O-D, -S-Y, -SO-Y ili -SO2-Y, pri čemu D i Y kao i R1, R3, R4, A, E i n imaju značenja navedena u formuli I, a po želji se spoj formule I u slobodnom obliku ili u obliku soli, koji se može dobiti prema postupku ili na neki drugi način, prevede u jedan drugi spoj formule I, mješavina izomera dobivena prema postupku se odvoji i željeni izomeri se izoliraju i/ili se slobodni spoj formule I koji se dobiva prema postupku prevede u sol ili se sol jednog spoja formule I, dobivena prema izumu prevede u slobodni spoj formule I ili u jednu drugu sol. in which R1, R3, R4, A, E and n have the meanings given in Formula I in the presence of one base reacts with the compound Hal-CH2-O-D, Hal-CHO, Hal-CO-D, Hal-CO-O-D, Hal-CO -CO-D, Hal-CO-CO-O-D, Hal-S-Y, SO-Y or Hal-SO2-Y, where hal means a chlorine, bromine or iodine atom, and D and Y have the meanings given in formula I and optionally is the obtained 3-carbamoyl-2H-indazole derivative of subformula Ia, in which R2 has a meaning other than hydrogen, C1-C4-alkyl, benzyl or C3-C6-cycloalkyl, and R1, R3, R4, A, E and n have the meanings given in formula I, with a thionating agent is converted into a compound of subformula Ib, in which R2 means -CH2-O-D, -CHO, -CO-D, -CO-O-D, -CO-CO-D, CO-CO-O-D, -S-Y, -SO-Y or -SO2-Y, where D and Y as well as R1, R3, R4, A, E and n have the meanings given in formula I, and optionally the compound of formula I in free form or in the form of a salt, which can be obtained according to the process or in some other way, converted into another compound of formula I, the mixture of isomers obtained according to the process is separated and the desired isomers are isolated and/or combined the point compound of formula I obtained according to the process is converted into a salt or the salt of one compound of formula I obtained according to the invention is converted into a free compound of formula I or into another salt.
Kod varijante postupka a) (II + III - Ia) se reakcija provodi u prisustvu reagensa koji cijepaju vodu, a koji se obično koriste za amidiranja, kao na primjer u prisustvu karbodiimida (dicikloheksilkarbodiimid (DCC)) ili 1-alkil-2-halogen piridinijeve soli kao 1-metil-2-klorpiridinijev jodid. Pri tome se radi u prisustvu reakciono inertnog otapala ili mješavine otapala na temperaturama od -30ºC do +70°C, preporučljivo na 10ºC do +50°C. Postupak se provodi u prisustvu jedne baze kao primjerice u prisustvu organskog amina kao što je trialkilamin (trimetilamin, trietilamin, tripropilamin ili diizopropiletilamin), piridina (sam piridin, 4-dimetilaminopiridin ili 4-pirolidinopiridin), morfolina (N-metilmorfolin) ili N,N-dialkilanilina (N,N-dimetilanilin ili N-metil-N-etilanilin). Kao otapala ovdje su prikladni primjerice alifatski i aromatski ugljikovodici kao klorbenzol, metilenklorid, etilenklorid, kloroform, tetraklor ugljik, tetrakloretilen; eter i eterni spojevi kao dialkileter (dietileter, diizopropileter), tert.-butilmetileter itd.) anisol, dioksan, tetrahidrofuran; nitrili kao acetonitril, propionitrili ester kao etilacetat (etilne ester octene kiseline), propilacetat ili butilacetat, te mješavine takovih otapala jednih s drugima. In procedure variant a) (II + III - Ia), the reaction is carried out in the presence of water-splitting reagents, which are usually used for amidation, for example in the presence of carbodiimide (dicyclohexylcarbodiimide (DCC)) or 1-alkyl-2-halogen pyridinium salts as 1-methyl-2-chloropyridinium iodide. This is done in the presence of a reaction-inert solvent or solvent mixture at temperatures from -30ºC to +70°C, preferably at 10ºC to +50°C. The process is carried out in the presence of one base, for example in the presence of an organic amine such as trialkylamine (trimethylamine, triethylamine, tripropylamine or diisopropylethylamine), pyridine (pyridine itself, 4-dimethylaminopyridine or 4-pyrrolidinopyridine), morpholine (N-methylmorpholine) or N, N-dialkylaniline (N,N-dimethylaniline or N-methyl-N-ethylaniline). Suitable solvents here are, for example, aliphatic and aromatic hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ether and ether compounds such as dialkylether (diethylether, diisopropylether), tert.-butylmethylether, etc.) anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile esters such as ethylacetate (ethyl ester of acetic acid), propylacetate or butylacetate, and mixtures of such solvents with each other.
Kod varijante postupka b) (II - IV i IX+III - Ia), prvi korak prevođenja slobodnih kiselina formule I u reakciono aktivirani derivat formule IV izvodi se prema uobičajenom postupku za halogeniranje karbonskih kiselina pomoću sredstava za halogeniranje kao tionilklorid, oksalilkloid, fosforoksiklorid, fosforpentaklorid, fosforoksibromid ili fosgen, za amidiranje sa 1H-imidazolom, a za esterifikaciju sa niskim alkilnim alkoholima. Po želji se primjenjuje halogeniranje, pri čemu se u tehnici prednost daje posebno kloriranju sa tionilkloridom ili fosgenom bez otapala. Ako se koriste otapala, uglavnom se biraju iz reda ugljikovodika kao heksan, pentan, cikloheksan, benzol, toluol ili ksilol; halogeniranih ugljikovodika kao klorbenzol, metilenklorid, etilenklorid, kloroform, tetraklor-ugljik ili tetrakloretilen; etera kao dietileter, diizopropileter, tert. butilmetileter, tetrahidrofuran, dioksan, dimetoksietilenglikol ili anisol; ili nitrila kao acetonitril ili propionitril. Temperature reakcije općenito su između -15°C i 100ºC, poželjno između 0°C i +50°C. Drugi korak reakcije varijante b) (IV-UUU - Ia) vrši se uglavnom u inertnom otapalu bez hidroksilnih grupa, u prisustvu jedne organske baze, kao na primjer piridina, 4-dimetilaminopiridina, lutidina, kolidina, trialkilamina, N,N-dialkilanilina ili bicikličnih nenukleofilnih baza kao 1,4-diacabiciklo(2-2-2)-oktan(DABCO), 1,5-diazabiciklo(4.30)non-5-en (OBN) ili 1,8-diazabiciklo(5.4.0)-undec-7-en(1,5-5)(DBU). Reakcija se obično provodi ra temperaturama od -30ºC do +70ºC preporučljivo od -10°C do +50ºC. Svrhovito se radi u prisustvu reakciono inertnog otapala ili mješavine otapala. Za to su prikladni primjerice alifatski i aromatski ugljikovodici kao benzol, toluol, ksilol, petroleter, heksan; halogenirani ugljikovodici kao klorbenzol, metilenklorid, etilenklorid, kloroform, tetraklorugljik, tetrakloretilen; eter i eterni spojevi kao dialkileter (dietileter, diizopropileter, tertbutilmetileter itd.), anisol, dioksan, tetrahidrofuran; nitrili kao acetonitril, propionitril; ester kao etilacetat (etilni ester octene kiseline), propilacetat ili butilacetat; ketoni kao aceton, dietilketon, metiletilketon; spojevi kao dimetilsulfoksid (DMSO), dimetilformamid (DMF) i mješavine takovih otapala jednih s drugima. In process variant b) (II - IV and IX+III - Ia), the first step of converting free acids of formula I into a reaction-activated derivative of formula IV is performed according to the usual procedure for halogenating carboxylic acids using halogenating agents such as thionyl chloride, oxalyl chloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus oxybromide or phosgene, for amidation with 1H-imidazole, and for esterification with lower alkyl alcohols. If desired, halogenation is applied, whereby chlorination with thionyl chloride or solvent-free phosgene is especially preferred in the technique. If solvents are used, they are mainly selected from hydrocarbons such as hexane, pentane, cyclohexane, benzene, toluene or xylene; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride or tetrachloroethylene; ether as diethylether, diisopropylether, tert. butylmethylether, tetrahydrofuran, dioxane, dimethoxyethylene glycol or anisole; or nitriles such as acetonitrile or propionitrile. Reaction temperatures are generally between -15°C and 100°C, preferably between 0°C and +50°C. The second reaction step of variant b) (IV-UUU - Ia) is mainly carried out in an inert solvent without hydroxyl groups, in the presence of an organic base, such as pyridine, 4-dimethylaminopyridine, lutidine, collidine, trialkylamine, N,N-dialkylaniline or bicyclic non-nucleophilic bases such as 1,4-diazabicyclo(2-2-2)-octane (DABCO), 1,5-diazabicyclo(4.30)non-5-ene (OBN) or 1,8-diazabicyclo(5.4.0)- undec-7-ene(1,5-5)(DBU). The reaction is usually carried out at temperatures from -30°C to +70°C, preferably from -10°C to +50°C. It is purposefully done in the presence of a reaction-inert solvent or solvent mixture. Aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, petroleum ether, hexane are suitable for this; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ether and ether compounds such as dialkylether (diethylether, diisopropylether, tertbutylmethylether, etc.), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; an ester such as ethyl acetate (ethyl acetate), propyl acetate or butyl acetate; ketones such as acetone, diethyl ketone, methyl ethyl ketone; compounds such as dimethylsulfoxide (DMSO), dimethylformamide (DMF) and mixtures of such solvents with each other.
Kod varijante postupka c) (Ic - I) reakcija se provodi u prisustvu jedne jake baze kao na primjer natrijev hidrid, kalijev hidrid, kalijev terc.butilat, natrijev etilat, natrijev metilat ili butilni litij. Pri tome se radi u inertnom otapalu na -10ºC do +60ºC, preporučljivo na 0ºC do 30°C. Kao otapala prikladni su primjerice alifatski i aromatski ugljikovodici kao metilenklorid, etilenklorid, klorbenzol ili orto-diklorbenzol; eter i eterna otapala kao dietileter, diizopropileter, terc.butilmetileter, tetrahidrofuran, dioksan, dimetoksietan, dimetoksimetan; nitrili kao acetonitril i propionitril; esteri kao etilni ester octene kiseline, metilni ester octene kiseline, propilni ester octene kiseline i butilne ester octene kiseline, te mješavine takovih otapala jednih s drugima. Polazni materijal formule Ic koji je potreban za ovaj postupak, može se dobiti prema varijantama postupka a) i b). In procedure variant c) (Ic - I), the reaction is carried out in the presence of a strong base such as sodium hydride, potassium hydride, potassium tert.butylate, sodium ethylate, sodium methylate or butyllithium. This is done in an inert solvent at -10ºC to +60ºC, preferably at 0ºC to 30°C. Suitable solvents are, for example, aliphatic and aromatic hydrocarbons such as methylene chloride, ethylene chloride, chlorobenzene or ortho-dichlorobenzene; ether and ethereal solvents such as diethylether, diisopropylether, tert.butylmethylether, tetrahydrofuran, dioxane, dimethoxyethane, dimethoxymethane; nitriles such as acetonitrile and propionitrile; esters such as acetic acid ethyl ester, acetic acid methyl ester, acetic acid propyl ester and acetic acid butyl ester, and mixtures of such solvents with each other. The starting material of formula Ic, which is required for this procedure, can be obtained according to the variants of procedure a) and b).
Fakultativno prevođenje 2H-indazol-3-amida karbonske kiseline formule la u odgovarajući 2H-3-amid tiokarbonske kiseline formule Ib, izvodi se pod uvjetima uobičajenim za ovu vrstu reakcije. Postupak prema izumu provodi se u prisustvu inertnog organskog otapala. Prikladna otapala su aromatska otapala kao benzol, toluol, ksilol, mesitilen, klorbenzol, diklorbenzol, piridin ili tetralin; klorirani ugljikovodici kao metilenklorid, kloroform, tetraklor ugljikovodik, etilenklorid, trikloretan ili tetrakloretan; ili eter kao dioksan, tetrahidrofuran ili dimetiletilenglikol. Temperature reakcije obično su između 0ºC i +150°C. Preporuča se temperaturne područje između +20ºC i +120°C, pri čemu se naročito treba naglasiti područje kljucanja reakcione mješavine. Reakcija prema izumu potpomaže se i time, da se reakcija tioniranja izvodi uz korištenje ultrazvuka, a temperatura se odabere između +20° i točke vrenja mješavine. Korištenje izvora ultrazvuka za potpomaganje reakcija tioniranja opisano je u analognom postupku u J. Org. Kem. 46, 3558 (1981). The optional conversion of the 2H-indazol-3-amide of the carboxylic acid of the formula Ia into the corresponding 2H-3-amide of the thiocarboxylic acid of the formula Ib is carried out under the conditions usual for this type of reaction. The process according to the invention is carried out in the presence of an inert organic solvent. Suitable solvents are aromatic solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, pyridine or tetralin; chlorinated hydrocarbons such as methylene chloride, chloroform, tetrachloro hydrocarbon, ethylene chloride, trichloroethane or tetrachloroethane; or an ether such as dioxane, tetrahydrofuran or dimethylethylene glycol. Reaction temperatures are usually between 0ºC and +150°C. A temperature range between +20ºC and +120°C is recommended, where the boiling point of the reaction mixture should be emphasized. The reaction according to the invention is also supported by the fact that the thionation reaction is carried out with the use of ultrasound, and the temperature is chosen between +20° and the boiling point of the mixture. The use of an ultrasound source to assist thionation reactions is described in an analogous procedure in J. Org. Chem. 46, 3558 (1981).
Sredstva tioniranja u literaturi su već mnogo puta opijana. U postupku prema izumu može se koristiti većina tih sredstava. Posebno povoljnim pokazali su se kao reagensi O,O-dietilditiofosforna kiselina (C2H5O)2PS2H, borsulfid B2S3 ili B2S5, fosforpentasulfid P2S5 ili 2,4-bis-(4-metoksifenil)-1,3-ditia-2,4-difosfetan-2,4-disulfid (Lawessonov reagens). Means of thionation have already been mentioned many times in the literature. Most of these means can be used in the process according to the invention. O,O-diethyldithiophosphoric acid (C2H5O)2PS2H, boron sulfide B2S3 or B2S5, phosphorus pentasulfide P2S5 or 2,4-bis-(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane- 2,4-disulfide (Lawesson's reagent).
Polazni proizvodi formule ili opisani su u literaturi ili se mogu dobiti prema tamo opisanom postupku za proizvodnju. Od polaznih spojeva formule II pojedini pojedinačni spojevi poznati su iz DE-OS 1948793, a većina ih do sada još nije opisana. Isto tako su većim dijelom u literaturi opisani polazni proizvodi formula Hal-CH2O-O, Hal-CHO, Hal-CO-D, Hal-CO-OD, Hal-CO-CO-D, Hal-CO-CO-O-D, Hal-S-Y, Hal-SO-Y i Hal-SO2-Y, kod kojih hal znači klor, brom ili jod, naročito klor ili brom. Za sada još novi polazni materijali mogu se dobiti analogno poznatim postupcima. Neki proizvodi već se mogu kupiti na tržištu. The starting products of the formula are either described in the literature or can be obtained according to the production process described there. Of the starting compounds of formula II, some individual compounds are known from DE-OS 1948793, and most of them have not yet been described. Likewise, the starting products of the formulas Hal-CH2O-O, Hal-CHO, Hal-CO-D, Hal-CO-OD, Hal-CO-CO-D, Hal-CO-CO-O-D, Hal -S-Y, Hal-SO-Y and Hal-SO2-Y, where hal means chlorine, bromine or iodine, especially chlorine or bromine. For now, still new starting materials can be obtained analogously to known procedures. Some products can already be bought on the market.
Polazni materijali formule II mogu se sintetizirati prema sljedećem slijedu reakcije. Spojevi se dobivaju tako, da se 2-nitrobenzaldehid formule V The starting materials of formula II can be synthesized according to the following reaction sequence. The compounds are obtained in such a way that 2-nitrobenzaldehyde of the formula V
[image] [image]
u kojoj E i n imaju značenje navedeno u formuli I, eventualno u prisustvu jedne kiseline, kondenzira sa aminom formule VI in which E and n have the meaning stated in formula I, possibly in the presence of an acid, condenses with the amine of formula VI
H2N-R1 (VI) H2N-R1 (VI)
u kojoj R1 ima značenje dato u formuli I, dobivena Schiffova baza formule VII wherein R 1 has the meaning given in formula I, the resulting Schiff base of formula VII
[image] [image]
u kojoj R1, E i n imaju značenje navedeno pod formulom I, tretiranjem sa alkalicijanidom u prisustvu jedne organske kiseline ciklizira u 3-cijano-2H-indazol-1-oksid formule VIII in which R1, E and n have the meaning given under formula I, by treatment with alkali cyanide in the presence of an organic acid cyclizes to 3-cyano-2H-indazole-1-oxide of formula VIII
[image] [image]
u kojoj R1, E i n imaju značenja navedena pod formulom I, taj međuproizvod se dezoksigenira i nastali 3-cijano-2H-indazol formule IX in which R1, E and n have the meanings given under formula I, this intermediate is deoxygenated and the resulting 3-cyano-2H-indazole of formula IX
[image] [image]
u kojoj R1 u N imaju značenja data pod formulom I, se saponificira. in which R 1 and N have the meanings given under formula I, is saponified.
Za korak kondenzacije (V+VI -VII) odabere se inertno organsko otapalo iz reda aromatskih, alifatskih ili cikloalifatskih ugljikovodika kao benzol, toluol, ksilol, heksan ili cikloheksan na temperaturama između 0° i +150°C, uglavnom +25ºC i 100°C, no naročito na temperaturi vrenja reakcione mješavine. Na brzinu reakcije dobro djeluje dodatak katalitičke količine jedne kiseline kao solna kiselina, sumporna kiselina, toluolsulfonska kiselina, trifluor-octena kiselina ili metansulfonska kiselina. For the condensation step (V+VI -VII), an inert organic solvent is selected from among aromatic, aliphatic or cycloaliphatic hydrocarbons such as benzene, toluene, xylene, hexane or cyclohexane at temperatures between 0° and +150°C, mostly +25°C and 100° C, but especially at the boiling temperature of the reaction mixture. Adding a catalytic amount of an acid such as hydrochloric acid, sulfuric acid, toluenesulfonic acid, trifluoroacetic acid or methanesulfonic acid has a good effect on the reaction rate.
Za korak cikliziranja (VII - VIII) koristi se polarno organsko otapalo iz reda alkohola ili karbonskih kiselina kao metanol, etanol, izopropanol, octena kiselina ili propionska kiselina. Kao alkalicijanidi u obzir dolaze uglavnom natrijev cijanid ili kalijev cijanid. Tim solima se u reakcijsku otopinu doda u ekvivalentnim količinama organska kiselina kao što je octena kiselina ili trifluor-octena kiselina. Od prednosti može biti i ako se ta kiselina stavi u suvišku, tako da može djelovati istovremeno kao i otapalo. Temperature reakcije uglavnom se kreću između -15ºC i +100ºC, poželjno između 0ºC i +50ºC. For the cyclization step (VII - VIII) a polar organic solvent from alcohol or carboxylic acids such as methanol, ethanol, isopropanol, acetic acid or propionic acid is used. As alkali cyanides, mainly sodium cyanide or potassium cyanide come into consideration. Equivalent amounts of organic acid such as acetic acid or trifluoroacetic acid are added to these salts in the reaction solution. It can also be advantageous if this acid is added in excess, so that it can act simultaneously as a solvent. Reaction temperatures generally range between -15ºC and +100ºC, preferably between 0ºC and +50ºC.
Za korak dezoksigeniranja (VIII - IX) kao reagensi dezoksigeniranja koriste se uglavnom fosforni triklorid i fosforni tribromid. Ovaj korak reakcije dobro se izvodi u ugljikovodiku ili kloriranom ugljikovodiku kao otapalu, na temperaturama između 0°C i +150ºC, naročito između +25°C i+100ºC. Prikladna otapala su na primjer benzol, toluol, ksilol, heksan, cikloheksan, metilenklorid, kloroform ili tetraklorugljik. For the deoxygenation step (VIII - IX), phosphorus trichloride and phosphorus tribromide are mainly used as deoxygenation reagents. This reaction step is well performed in a hydrocarbon or chlorinated hydrocarbon as a solvent, at temperatures between 0°C and +150°C, especially between +25°C and +100°C. Suitable solvents are, for example, benzene, toluene, xylene, hexane, cyclohexane, methylene chloride, chloroform or carbon tetrachloride.
Korak saponifikacije (IX - II) može se provoditi kako pod kiselim, tako i pod bazičnim uvjetima u vodenom mediju. Kao otapala dolaze u obzir voda, alkoholi i sa vodom mješivi eteri. Naročito je dobro koristiti vodena otapala ili mješavine otapala. Primjeri za prikladna otapala su voda, tetrahidrofuran, dioksan, metanol, etanol ili izopropanol. Kao kiseli katalizatori saponifikacije u obzir dolaze primjerice sumporna kiselina, solna kiselina ili bromovodikova kiselina, kao bazični katalizatori saponifikacije natrijev klorid ili kalijev klorid. Temperature reakcije su kod reakcije saponifikacije općenito između 0°C i +150°C, naročito između +25°C i 100°C. The saponification step (IX - II) can be carried out both under acidic and basic conditions in an aqueous medium. Solvents include water, alcohols and water-miscible ethers. It is particularly good to use aqueous solvents or solvent mixtures. Examples of suitable solvents are water, tetrahydrofuran, dioxane, methanol, ethanol or isopropanol. Acidic saponification catalysts include, for example, sulfuric acid, hydrochloric acid or hydrobromic acid, and sodium chloride or potassium chloride as basic saponification catalysts. The reaction temperatures for the saponification reaction are generally between 0°C and +150°C, especially between +25°C and 100°C.
Spoj I koji se može dobiti prema postupku ili na neki drugi način, može se na poznati način prevesti u drugi spoj, pri čemu se jedan ili više supstituenata polaznih spojeva I na uobičajeni način zamijeni drugim supstituentima prema izumu. Compound I, which can be obtained according to the process or in some other way, can be converted into another compound in a known manner, whereby one or more substituents of the starting compounds I are replaced in the usual way by other substituents according to the invention.
Može se na primjer: For example, you can:
- zamijeniti vodik R1 i/ili R2 za alkil R1 i/ili R2 ili - replace hydrogen R1 and/or R2 with alkyl R1 and/or R2 or
- halogen E uvesti u nesupstituiranu poziciju prstena indazola. - introduce halogen E into the unsubstituted position of the indazole ring.
Prema izboru za to prikladnih reakcijskih uvjete polaznih materijala, pri tome je moguće u jednom koraku reakcije samo jedan supstituent zamijeniti drugim supstituentom prema izumu ili se u jednom koraku reakcije više supstituenata može zamijeniti drugim supstituentima prema izumu. Depending on the choice of suitable reaction conditions of the starting materials, it is possible in one step of the reaction to replace only one substituent with another substituent according to the invention, or in one step of the reaction several substituents can be replaced with other substituents according to the invention.
Soli spojeva I mogu se dobiti na zapravo poznat način. Tako se na primjer adicione soli kiseline dobivaju obradom sa prikladnom Kiselinom ili prikladnim reagensom ionske izmjene, a soli sa bazama tretiranjem sa prikladnom bazom ili prikladnim reagensom ionske izmjene. Salts of compounds I can be obtained in a known manner. Thus, for example, addition salts of acids are obtained by treatment with a suitable acid or a suitable ion exchange reagent, and salts with bases are obtained by treatment with a suitable base or a suitable ion exchange reagent.
Soli spojeva I mogu se na uobičajeni način prevesti u slobodne spojeve I, adicione soli kiseline npr. obradom sa prikladnim bazičnim sredstvom ili prikladnim reagensom ionske izmjene, a soli sa bazama npr. obradom sa prikladnom kiselinom ili prikladnim reagensom ionske izmjene. Salts of compounds I can be converted in the usual way into free compounds I, addition salts of acids, for example, by treatment with a suitable basic agent or a suitable ion exchange reagent, and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent.
Soli spojeva I mogu se zapravo na uobičajen način pretvoriti u druge soli spojeva I, adicione soli kiseline primjerice u druge adicione soli kiseline, npr. obradom soli jedne anorganske kiseline, npr. hidroklorida, sa prikladnom metalnom soli, kao što je natrijeva, barijeva ili srebrna sol, jedne kiseline npr. sa srebrnim acetatom, u prikladnom otapalu u kojem je anorganska sol, npr. srebrni Klorid netopiva i time se odvaja iz reakcijske mješavine. Salts of compounds I can actually be converted in the usual way into other salts of compounds I, acid addition salts, for example into other acid addition salts, for example by treating a salt of an inorganic acid, for example a hydrochloride, with a suitable metal salt, such as sodium, barium or silver salt, of one acid, eg with silver acetate, in a suitable solvent in which the inorganic salt, eg silver chloride, is insoluble and thus separated from the reaction mixture.
Prema vrsti postupka odn. uvjetima reakcije mogu se dobiti spojevi I sa svojstvima stvaranja soli, u slobodnom obliku ili u obliku soli. According to the type of procedure or under the reaction conditions, compounds I with salt-forming properties can be obtained, in free form or in the form of salts.
Spojevi I, u slobodnom obliku ili u obliku soli mogu se nalaziti eventualno u obliku jednog od mogućih izomera ili kao mješavina istih, npr. prema broju apsolutnih i relativnih konfiguracija asimetričnih atoma ugljika koji se eventualno pojavljuju u molekuli i/ili prema konfiguraciji nearomatskih dvostrukih veza koje se eventualno pojavljuju u molekuli, kao čisti izomeri, kao antipodi i/ili diastereomeri ili kao mješavina izomera, kao mješavine enantiomera, npr. racemati, mješavine diastereomera ili mješavine racemata; izum se odnosi kako na čiste izomere, tako i na sve moguće mješavine izomera, te se u gornjem i daljnjem tekstu treba odgovarajuće razumijevati i tada, kad stereokemijske pojedinosti neće u svakom slučaju biti posebno spomenute. Compounds I, in free form or in the form of a salt, can possibly be found in the form of one of the possible isomers or as a mixture of them, for example according to the number of absolute and relative configurations of asymmetric carbon atoms that may appear in the molecule and/or according to the configuration of non-aromatic double bonds which possibly occur in the molecule, as pure isomers, as antipodes and/or diastereomers or as a mixture of isomers, as a mixture of enantiomers, eg racemates, mixtures of diastereomers or mixtures of racemates; the invention refers both to pure isomers and to all possible mixtures of isomers, and the above and further text should be understood accordingly even when stereochemical details will not be specifically mentioned in any case.
Mješavine diastereomera i racemata spojeva I koji se mogu dobiti prema izumu ili na neki drugi način u slobodnom oliku ili u obliku soli - prema odabiru polaznih tvari i načina rada mogu se na osnovu fizikalno-kemijskih razlika sastavnih dijelova rastaviti na čiste diastereomere ili racemate, primjerice frakcioniranom kristalizacijom, destilacijom i/ili kromatografijom. Mixtures of diastereomers and racemates of compounds I, which can be obtained according to the invention or in some other way in the free form or in the form of salts - depending on the choice of starting materials and method of operation, can be separated into pure diastereomers or racemates based on the physico-chemical differences of the constituent parts, for example by fractional crystallization, distillation and/or chromatography.
Mješavine enantiomera koje se mogu dobiti na odgovarajući način, kao racemati, mogu se prema poznatim metodama razdvojiti u optičku antipode, primjerice prekristalizacijom i:, optički aktivnog otapala, kromatografijom na kiralnim adsorbentima, npr. visokotlačnom tekućom kromatografijom na acetilcelulozi, pomoću prikladnih mikroorganizama, fisijom sa specifičnim, imobiliziranim enzimima, preko stvaranja umetnutih spojeva, npr. uz korištenje kiralnog kron-etera, pri čemu se kompleksira samo jedan enantiomer ili prevođenjem u diastereomerne soli, npr. reakcijom bazičnog racemata proizvoda sa optički aktivnom kiselinom kao što je karbonska kiselina, npr. kamforna, vinska ili jabučna kiselina ili sulfonska kiselina, npr. kamforna sulfonska kiselina i odvajanjem na taj način dobivene mješavine diastereomera, npr. na osnovu njihovih različitih topivosti frakcioniranom kristalizacijom u diastereomere, iz kojih se željeni enantiomer može osloboditi djelovanjem prikladnih, npr. bazičnih sredstava. Mixtures of enantiomers that can be obtained in a suitable way, as racemates, can be separated into optical antipodes according to known methods, for example by recrystallization of an optically active solvent, by chromatography on chiral adsorbents, for example by high-pressure liquid chromatography on acetyl cellulose, by means of suitable microorganisms, by fission with specific, immobilized enzymes, via the formation of insertion compounds, e.g. using a chiral crown ether, whereby only one enantiomer is complexed, or by conversion to diastereomeric salts, e.g. reaction of a basic racemate product with an optically active acid such as carboxylic acid, e.g. .camphoric, tartaric or malic acid or sulphonic acid, e.g. camphor sulphonic acid and separating the thus obtained mixture of diastereomers, e.g. on the basis of their different solubilities by fractional crystallization into diastereomers, from which the desired enantiomer can be released by the action of suitable, e.g. basic means And.
Osim dijeljenjem odgovarajućih mješavina izomera cisti diastereomeri odn. enantiomeri prema izumu mogu se dobiti i opće poznatim metodama diastereoselektiven odn. enantioselektivne sinteze, npr. tako, da se postupak prema izumu izvodi sa eduktima sa odgovarajuće prikladnom stereokemijom. In addition to dividing the appropriate mixtures of isomers, pure diastereomers or enantiomers according to the invention can also be obtained by well-known diastereoselective methods or enantioselective syntheses, for example so that the process according to the invention is carried out with educts with correspondingly suitable stereochemistry.
Biološki djelotvorni izomeri, npr. enantiomeri i i diastereomeri ili mješavine izomera, npr. mješavina enantiomera ili diastereomera mogu se izolirati odn. sintetizirati, ukoliko pojedine komponente imaju različitu biološku djelotvornost. Biologically effective isomers, e.g. enantiomers and diastereomers or mixtures of isomers, e.g. a mixture of enantiomers or diastereomers can be isolated or synthesize, if individual components have different biological effectiveness.
Spojevi I, u slobodnom obliku ili u obliku soli mogu se dobiti i u obliku njihovih hidrata i/ili obuhvaćati druge, primjerice otapala korištena za kristalizaciju spojeva koji su u čvrstom obliku. Compounds I, in free form or in the form of salts, can also be obtained in the form of their hydrates and/or include other, for example, solvents used for crystallization of compounds that are in solid form.
Izum se odnosi na sve one oblike izvođenja postupka, prema kojima se polazi od spoja koji se na bilo kojem stupnju postupka dobiva kao polazni proizvod ili međuproizvod i provode svi ili neki od koraka koji manjkaju ili se koristi polazna tvar u obliku derivata npr. soli i/ili njenih racemata odn. antipoda ili se naročito stvaraju pod reakcijskim uvjetima. The invention refers to all those forms of carrying out the process, according to which the starting point is a compound that is obtained at any stage of the process as a starting product or an intermediate product and all or some of the missing steps are carried out or the starting substance is used in the form of a derivative, for example a salt and / or its racemates or antipodes or are especially created under reaction conditions.
Kod postupka predmetnog izuma koriste se takove polazne tvari i međuproizvodi, u slobodnom obliku ili u obliku soli, koji dovode do spojeva I odn. njihovih soli koje su na početku opisane kao posebno vrijedne. In the process of the subject invention, such starting substances and intermediate products are used, in free form or in the form of salts, which lead to compounds I or of their salts, which were described at the beginning as particularly valuable.
Izum se posebno odnosi na postupak proizvodnje opisan u primjerima H1 do H5. The invention specifically relates to the production process described in examples H1 to H5.
Polazne tvari i međuproizvodi, u slobodnom obliku ili u obliku soli, korišteni prema izumu za dobivanje spojeva I odn. njihovih soli, koji su novi, postupak za njihovu proizvodnju i njihovo korištenje kao polazne tvari i međuproizvodi za dobivanje spojeva I također su predmet izuma. Starting substances and intermediate products, in free form or in the form of salts, used according to the invention to obtain compounds I or their salts, which are new, the process for their production and their use as starting materials and intermediates for obtaining compounds I are also the subject of the invention.
Spojevi prema izumu su na području uništavanja insekata - ako ih toplokrvne životinje, ribe i biljke dobro podnose već kod niskih koncentracija primjene preventivno i/ili kurativno vrijedna.aktivne tvari sa veoma povoljnim biocidnim spektrom. Aktivne tvari prema izumu djelotvorne su kod svih razvojnih stadije normalno senzibilnih, no i rezistentnih životinjskih štetnika kao što su insekti, nematodi i reprezentanti reda acarina i fitopatogenih gljivica. Insekticidno, nematozidno i/ili akaricidno djelovanje aktivnih tvari prema izumu može se pri tome pokazati direktno t. u umrtvljenju štetnika do kojeg dolazi odmah ili tek nakon nekog vremena, primjerice kod skidanja koze ili indirektno npr. u smanjenom odlaganju jajašca i/ili smanjenoj brzini izlijeganja, pri čemu dobro djelovanje odgovara mortalitetu od najmanje 50 do 60%. The compounds according to the invention are in the field of destroying insects - if they are well tolerated by warm-blooded animals, fish and plants, even at low concentrations they can be used preventively and/or curatively. Active substances with a very favorable biocidal spectrum. The active substances according to the invention are effective in all developmental stages of normally sensitive but also resistant animal pests such as insects, nematodes and representatives of the acarina order and phytopathogenic fungi. The insecticidal, nematocidal and/or acaricidal effect of the active substances according to the invention can be demonstrated directly. in the deadening of the pest, which occurs immediately or only after some time, for example when removing the skin, or indirectly, for example, in reduced egg laying and/or reduced hatching speed, whereby a good effect corresponds to a mortality of at least 50 to 60%.
U spomenute životinjske štetnike spadaju primjerice: The mentioned animal pests include, for example:
Iz reda lepidoptera na primjer From the order of lepidoptera, for example
acleris spp., adoxophyes spp., agrotis spp., alabama argillaceae, amylois spp., anticarsia gemmatalis, archips spp.. argyrotaenia spp., autographa spp., busseula fusca, cadra cautrlia, carposina nipponensis, chilo spp., choristoneura spp., clysia ambiguella, cnaphalocrocis spp., cnephasia spp., cochylis spp., colephora spp., crocidolomia binotalis, cryptophlebia leucotreta, cydia spp., diatraea spp., diparopsis castanea, earias spp., ephestia spp., eucosma spp., eupoecilia ambiguella, euproctis spp., euxoa spp., grapholita spp., hedya nubiferana, heliothis spp , hellula undalis, hyphantria cunea, keiferia lycopersicella, leucoptera scitella, lithocollethis spp., lobesia botrana, lymantria spp., lyonetia spp., malacosoma spp., mamestra brassicae, manduca sexta, operophtera spp., ostrinia nubilalis, pammene spp., pandemis spp., panolis flammea, pectinophora gosszpiella, phthorimaea operculella, pieris rapae, pieris spp., plutella xylostella, prays spp., scirpophaga spp., sesamia spp., sparganothis spp., spodoptera spp., synanthedon spp., thaumetopoea spp., tortrix spp., trichoplusia ni i yponomeuta spp; acleris spp., adoxophyes spp., agrotis spp., alabama argillaceae, amylois spp., anticarsia gemmatalis, archips spp.. argyrotaenia spp., autographa spp., busseula fusca, cadra cautrlia, carposina nipponensis, chilo spp., choristoneura spp. , clysia ambiguella, cnaphalocrocis spp., cnephasia spp., cochylis spp., colephora spp., crocidolomia binotalis, cryptophlebia leucotreta, cydia spp., diatraea spp., diparopsis castanea, earias spp., ephestia spp., eucosma spp., eupoecilia ambiguella, euproctis spp., euxoa spp., grapholita spp., hedya nubiferana, heliothis spp, hellula undalis, hyphantria cunea, keiferia lycopersicella, leucoptera scitella, lithocollethis spp., lobesia botrana, lymantria spp., lyonetia spp., malacosoma spp. , mamestra brassicae, manduca sexta, operophtera spp., ostrinia nubilalis, pammene spp., pandemis spp., panolis flammea, pectinophora gosszpiella, phthorimaea operculella, pieris rapae, pieris spp., plutella xylostella, prays spp., scirpophaga spp., sesamia spp., sp arganothis spp., spodoptera spp., synanthedon spp., thaumetopoea spp., tortrix spp., trichoplusia ni and yponomeuta spp;
iz reda coleoptera na primjer from the order of coleoptera for example
agriotes spp., anthonomus spp., atomaria linearis, chaetocnema tibialis, cosmopolites spp., curculio spp., dermestes spp., diabrotica spp., epilachna spp., eremnus spp., leptinotarsa decemlineata, lissorhoptrus spp., melolontha spp., orycaephilus spp., otiorhynchus spp., phlyctinus spp., popillia spp., psylliodes spp., rhizopertha spp., scarabeidae, sitophilus spp., sitotroga spp., tenebrio spp., tribolium spp. i trogoderma spp; agriotes spp., anthonomus spp., atomaria linearis, chaetocnema tibialis, cosmopolites spp., curculio spp., dermestes spp., diabrotica spp., epilachna spp., eremnus spp., leptinotarsa decemlineata, lissorhoptrus spp., melolontha spp., orycaephilus spp., otiorhynchus spp., phlyctinus spp., popillia spp., psylliodes spp., rhizopertha spp., scarabeidae, sitophilus spp., sitotroga spp., tenebrio spp., tribolium spp. and trogoderma spp.;
iz reda orthoptera na primjer from the order of Orthoptera, for example
blatta spp., blatella spp., gryllotalpa spp., leucophae maderae, locusta spp., periplaneta spp. i schistocerca ispp.; blatta spp., blatella spp., gryllotalpa spp., leucophae maderae, locusta spp., periplaneta spp. and schistocerca ispp.;
iz reda isoptera na primjer from the order of isopters for example
reticulitermes spp.; reticulitermes spp.;
iz reda psocoptera na primjer from the order of psocopters for example
liposcelis spp.; liposcelis spp.;
iz reda anoplura na primjer from the order Anoplura for example
haematopinus spp., linognathus spp., pediculus spp., pemphigus spp. i phylloxera spp.; haematopinus spp., linognathus spp., pediculus spp., pemphigus spp. and phylloxera spp.;
iz reda mallophaga na primjer from the order mallophaga for example
damalinea spp. i trichodectes spp.; damalinea spp. and trichodectes spp.;
iz reda thysanoptera na primjer from the order thysanoptera for example
frankliniella spp., hercinothrips spp., taeniothrips spp., thrips palmi, thrips tabaci i scirtothrips aurantii; frankliniella spp., hercinothrips spp., taeniothrips spp., thrips palmi, thrips tabaci and scirtothrips aurantii;
iz roda heteroptera na primjer from the genus Heteroptera for example
cimex spp., distantielia theobroma, dysdercus spp., euchistus spp., eurygaster spp., leptocorisa spp., nezara spp., piesma spp., rhodnius spp., sahlbergella singularis, scotinophara spp. i triatoma spp.; cimex spp., distantielia theobroma, dysdercus spp., euchistus spp., eurygaster spp., leptocorisa spp., nezara spp., piesma spp., rhodnius spp., sahlbergella singularis, scotinophara spp. and triatoma spp.;
iz reda homoptera na primjer from the order of homoptera for example
aleurothrixus floccosus, alloyrodes brassicae, aonidiella spp., aphididae, aphis spp., aspidiotus spp., bemisia tabaci, ceroplaster spp., dhrysomphalus aonidium, chrysomphalus dictyospermi, coccus hesperidum, empoasca spp., eriosoma larigerum, erythroneura spp., gascardia spp., laodelphax spp., lecanium corni, lepidosaphes spp., macrosiphus spp., myzus spp., nephotettix spp., nilaparvata spp., paratoria spp., pemphigus spp., planococcus spp., pseudaulacaspis spp., pseudococcus spp., psylla spp., pulvinaria aethiopica, quadraspidiotus spp., thopalosiphum spp., saissetia spp., scaphoideus spp., schizaphis spp., sitobion spp., trialeurodes vaporariorum, trioza erytreae i unaspis citri; aleurothrixus floccosus, alloyrodes brassicae, aonidiella spp., aphididae, aphis spp., aspidiotus spp., bemisia tabaci, ceroplaster spp., dhrysomphalus aonidium, chrysomphalus dictyospermi, coccus hesperidum, empoasca spp., eriosoma larigerum, erythroneura spp., gascardia spp. , laodelphax spp., lecanium corni, lepidosaphes spp., macrosiphus spp., myzus spp., nephotettix spp., nilaparvata spp., paratoria spp., pemphigus spp., planococcus spp., pseudaulacaspis spp., pseudococcus spp., psylla spp. ., pulvinaria aethiopica, quadraspidiotus spp., thopalosiphum spp., saissetia spp., scaphoideus spp., schizaphis spp., sitobion spp., trialeurodes vaporariorum, trioza erytreae and unaspis citri;
iz reda hymenoptera na primjer from the order of hymenoptera for example
acromyrmex, atta spp., cephus spp., diprion spp., diprionidae, gilpinia polytoma, hoplocampa spp., lasius spp., monomnrium pharaonis, neodiprion spp., neodiprion spp., solenopsis spp. i vespa spp.; acromyrmex, atta spp., cephus spp., diprion spp., diprionidae, gilpinia polytoma, hoplocampa spp., lasius spp., monomnrium pharaonis, neodiprion spp., neodiprion spp., solenopsis spp. and vespa spp.;
iz reda diptera na primjer from the Diptera order for example
aedes spp., antherigona soccata, bibio hortulanus, calliphora erythrocephala, ceratitis spp., chrysomyia spp., culex spp., cuterebra spp., dacus spp., drosophila melanogaster, fannia spp., garstrophilus spp., glossina spp., hypoderma spp., hyppobosca spp., liriomyza spp., luculia spp., melanagromyza spp., musca spp., oestrus spp., orseolia spp., oscinella frit, pegomyia hyoscyami, phorbia spp., rhagoletis pomonella, sciara spp., stomoxys spp., tabanus spp., tannia spp. i tipula spp.; aedes spp., antherigona soccata, bibio hortulanus, calliphora erythrocephala, ceratitis spp., chrysomyia spp., culex spp., cuterebra spp., dacus spp., drosophila melanogaster, fannia spp., garstrophilus spp., glossina spp., hypoderma spp. ., hyppobosca spp., liriomyza spp., luculia spp., melanagromyza spp., musca spp., oestrus spp., orseolia spp., oscinella frit, pegomyia hyoscyami, phorbia spp., rhagoletis pomonella, sciara spp., stomoxys spp. , tabanus spp., tannia spp. and onion spp.;
iz reda siphonaptera na primjer from the siphonaptera order for example
ceratophyllus spp. i xenopsylla cheopis; ceratophyllus spp. and xenopsylla cheopis;
iz reda thysanura na primjer from the order thysanura for example
lepisma saccharina; lepisma saccharin;
iz reda acarina na primjer from the order of acarina for example
acarus siro, aceria sheldoni, aculus schlechtendali, amblyomma spp., argas spp., boophilus spp., brevipalpus spp., bryobia praetiosa, calipitrimerus spp.. chorioptes spp., dermanyssus gallinae, eotetranychus carpini, eriophyes spp., hyalomma spp., ixodes spp., olygonychus pratensis, ornithodoros spp., panonychus spp., phyllocoptruta oleivora, polyphagotarsonemus latus, psoroptes spp., rhipicephalus spp., rhizoglyphus spp., sarcoptes spp., tarsonemus spp. i tetranychus spp., te acarus siro, aceria sheldoni, aculus schlechtendali, amblyomma spp., argas spp., boophilus spp., brevipalpus spp., bryobia praetiosa, calipitrimerus spp.. chorioptes spp., dermanyssus gallinae, eotetranychus carpini, eriophyes spp., hyalomma spp., ixodes spp., olygonychus pratensis, ornithodoros spp., panonychus spp., phyllocoptruta oleivora, polyphagotarsonemus latus, psoroptes spp., rhipicephalus spp., rhizoglyphus spp., sarcoptes spp., tarsonemus spp. and tetranychus spp., and
iz klasc; nematoda na primjer from classes; nematodes for example
nametnici na korijenu biljke, npr. roda heterodera spp. i globodera spp. (nematodi koji stvaraju ciste), meloidogyne spp. (nematodi na korijenu biljke), radopholus spp., pratylenchus spp., tylenchulus spp., longidorus spp., tricnodorus spp. i xiphinema spp., plant root pests, e.g. heterodera spp. and globodera spp. (cyst-forming nematodes), meloidogyne spp. (plant root nematodes), radopholus spp., pratylenchus spp., tylenchulus spp., longidorus spp., tricnodorus spp. and xiphinema spp.,
nematodi koji napadaju peteljku, npr. roda ditylenchus spp., nematodes that attack the petiole, e.g. Ditylenchus spp.,
nematodi koji napadaju listove, npr. roda aphelenchoides spp. i nematodes that attack leaves, eg aphelenchoides spp. i
nematodi koji napadaju cvjetove, npr. roda anguina spp.. nematodes that attack flowers, eg anguina spp..
U spomenute fitopatogene gljivice spadaju primjerice: The aforementioned phytopathogenic fungi include, for example:
iz klase fungi imperfecti na primjer from the class fungi imperfecti for example
botrytis spp., pyricularia spp., helminthosporium spp., fusarium spp., septoria spp., cercospora spp. i alternaria spp.; botrytis spp., pyricularia spp., helminthosporium spp., fusarium spp., septoria spp., cercospora spp. and alternaria spp.;
iz klase basidiomycetta na primjer from the class basidiomycetta for example
rhicoctonia spp., hemileia spp. i puccinia spp.; rhicoctonia spp., hemileia spp. and puccinia spp.;
iz klase ascomyceta na primjer from the ascomyceta class for example
venturia spp., erysiphe spp., podosphaera spp., monilinia spp. i uncinula spp. i venturia spp., erysiphe spp., podosphaera spp., monilinia spp. and uncinula spp. and
iz klase oomyceta na primjer from the oomyceta class for example
phytophthora spp., pythium spp. i plasmopara spp.. phytophthora spp., pythium spp. and plasmopara spp..
Sa aktivnim tvarima prema izumu naročito se mogu uništavati odn,. suzbijati štetnici navedenih vrsta na korisnim i ukrasnim biljkama u poljoprivredi, vrtlarstvu i šumarstvu ili dijelovima bilja kao što su plodovi, cvjetovi, krošnji; peteljke, lukovice ili korijen, pri čemu su djelomično i kasnije narasli dijelovi biljaka još zaštićeni od tih štetnika. With the active substances according to the invention, in particular, they can be destroyed or control pests of the above species on useful and ornamental plants in agriculture, horticulture and forestry or parts of plants such as fruits, flowers, crowns; petioles, bulbs or roots, while partially and later grown plant parts are still protected from these pests.
Kao ciljane kulture naročito dolaze u obzir žito kao pšenica, ječam, raž, zob, riža, kukuruz ili šećerni sijerak; repice kao šećerna ili stočna repica; voće kao koštunjavo voće ili bobice, jabuke, kruške, šljive, breskve, bademi, trešnje ili npr. jagode, maline ili kupine; mahunarke kao grah, leća, grašak ili soja; uljarice kao uljena repica, gorušica, mak, masline, suncokret, kokos, ricinus, kakao ili kikiriki; bundeva, krastavci, ili dinje; vlaknasto bilje kao pamuk, lan ili konoplja; agrumi kao naranče, limuni ili mandarine; povrće kao špinat, zelena salata, šparoge, mrkva, luk, paradajz, krumpir ili paprika; lovorike kao avokado, cimetnjak ili kamfor, kao i duhan, orasi, kava, patlidžani, šećerna trska, čaj, papar, vinova loza, hmelj, banane, prirodni kaučuk i ukrasno bilje. As target crops, grains such as wheat, barley, rye, oats, rice, corn or sugar beet are particularly suitable; canola such as sugar canola or canola; fruits such as stone fruits or berries, apples, pears, plums, peaches, almonds, cherries or, for example, strawberries, raspberries or blackberries; legumes such as beans, lentils, peas or soybeans; oilseeds such as rapeseed, mustard, poppy, olive, sunflower, coconut, castor, cocoa or peanut; pumpkin, cucumbers, or melons; fibrous plants such as cotton, flax or hemp; citrus fruits such as oranges, lemons or tangerines; vegetables such as spinach, lettuce, asparagus, carrots, onions, tomatoes, potatoes or peppers; laurels such as avocado, cinnamon or camphor, as well as tobacco, walnuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas, natural rubber and ornamental plants.
Aktivne tvari prema izumu naročito su prikladne za uništavanje insekata, nematoda i reprezentanata reda acarina, naročito insekata koji žderu biljke, kao anthonomus grandi, diabrotica balteata, heliothis virescens-larve, plutella xylostella i spodoptera littoralis-larve, insekti koji sišu sok biljaka kao aphis craviccora i bemisia tabaci, insekti koji napadaju donji dio biljke koji je u zemlji kao diabrotica balteata, zemni nematodi koji napadaju korijen biljke kao meloidogyne incognita i heterodera glycines, te grinje kao tetranychus spp. kod kultura pamuka, voća, kukuruza, soje, repice, agruma i povrća. The active substances according to the invention are particularly suitable for destroying insects, nematodes and representatives of the acarina order, especially insects that eat plants, such as anthonomus grandi, diabrotica balteata, heliothis virescens-larvae, plutella xylostella and spodoptera littoralis-larvae, insects that suck the sap of plants such as aphis craviccora and bemisia tabaci, insects that attack the lower part of the plant that is in the ground such as diabrotica balteata, soil nematodes that attack the plant root such as meloidogyne incognita and heterodera glycines, and mites such as tetranychus spp. in crops of cotton, fruit, corn, soy, canola, citrus fruits and vegetables.
Daljnja područja korištenja aktivnih tvari prema izumu su zaštita zaliha ili skladišta ili materijala u sektoru higijena, naročito zaštita domaćih i korisnih životinja od štetnika spomenute vrste. Further areas of use of active substances according to the invention are the protection of stocks or warehouses or materials in the hygiene sector, especially the protection of domestic and useful animals from pests of the mentioned type.
Stoga se izum odnosi i na sredstva za uništavanje štetnika koja se biraju prema potrebi između emulgirajućih koncentrata, koncentrata suspenzija, otopina koje se direktno raspršuju ili prije apliciranja razjeđuju, pasta za mazanje, razrijeđenih emulzija, prašaka za posipavanje, topivih prašaka, dispergirajućih prašaka, ovlaživih prašaka, sredstava za posipavanja, granulata ili polimernih tvari koje sadrže najmanje jednu od aktivnih tvari prema izumu. Therefore, the invention also refers to agents for destroying pests that can be chosen as needed from emulsifying concentrates, suspension concentrates, solutions that are sprayed directly or diluted before application, spreading pastes, diluted emulsions, dusting powders, soluble powders, dispersing powders, wetting powders, sprinklers, granules or polymeric substances containing at least one of the active substances according to the invention.
Aktivna tvar se u ta sredstva stavlja u čistom obliku, čvrsta tvar kao npr. u posebnoj veličini jezgre ili zajedno sa najmanje jednom od pomoćnih tvari uobičajenoj u tehnici formulacija, kao što su aktivna punila, npr. otapala ili čvrste nosive tvari ili kao što su površinski aktivni spojevi (tenzidi). The active substance is placed in these means in its pure form, a solid substance such as, for example, in a special core size or together with at least one of the auxiliary substances common in the formulation technique, such as active fillers, for example, solvents or solid carrier substances or such as surface active compounds (surfactants).
Kao otapala u obzir npr. dolaze eventualno parcijalno hidri rani aromatski ugljikovodici, poželjno frakcije C8 do C--12 alkilbonzola kao mješavine ksilola, alkilirani naftalini ili tetrahidronaftalin, alifatski ili cikloalifatski ugljikovodici kao parafini ili cikloheksan, alkoholi kao etanol, propanol ili butanol, glikoli kao i njihovi eteri i esteri kao što propilenglikol, eter dipropilenglikola, etilenglikol ili etilenglikolmono-metilni ili -etilni eter, ketoni kao cikloheksanon, izoforon ili diacetonalkohol, jaka polarna otapala kao N-metilpirolid-2-on, dimatilsulfoksid ili N,N-dimetilformamid, voda, eventualno epoksidirana biljna ulja, kao eventualno epoksidirano ulje repice, ricinusa, kokosovog oraha ili soje, te silikonska ulja. Potentially partially hydrogenated aromatic hydrocarbons, preferably fractions of C8 to C-12 alkylbenzols such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols can be used as solvents. as well as their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol mono-methyl or -ethyl ether, ketones such as cyclohexanone, isophorone or diacetone alcohol, strong polar solvents such as N-methylpyrrolid-2-one, dimethylsulfoxide or N,N-dimethylformamide , water, possibly epoxidized vegetable oils, such as possibly epoxidized rape, castor, coconut or soybean oil, and silicone oils.
Kao čvrste nosive tvari, npr. sredstva za prašenje i dispergirajući prašci u pravilu se koriste prirodna kamena brašna kao kalcit, talk, kaolin, montmorilonit ili atapulgit. Za poboljšanje fizikalnih svojstava mogu se dodati i visokodisperzne silicijeve kiseline i visokodisperzni polimerizati sa sposobnošću upijanja. Kao zrnati adsorpcioni nosači granulata u obzir dolaze porozne vrste kao plovućac, lomljena opeka, sepiolit ili bentonit, a kao nesorptivni nosivi materijali kalcit ili pijesak. Osim toga se može koristiti mnoštvo granuliranih materijala anorganske ili organske prirode, naročito dolomit ili usitnjeni ostaci biljaka. As a rule, natural stone flours such as calcite, talc, kaolin, montmorillonite or attapulgite are used as solid carriers, for example dusting agents and dispersing powders. To improve the physical properties, highly dispersed silicic acids and highly dispersed polymers with absorbency can be added. Porous types such as pumice, broken brick, sepiolite or bentonite can be used as granulate adsorption carriers, and calcite or sand as non-sorptive carrier materials. In addition, many granular materials of an inorganic or organic nature can be used, especially dolomite or crushed plant residues.
Kao površinski aktivni spojevi, prema vrsti aktivnih tvari koje se formuliraju, u obzir dolaze kationski i/ili anionski tenzidi ili mješavine tenzida sa dobrim svojstvima emulgiranja, dispergiranja i umrežavanja. U daljnjem tekstu navedeni tenzidi dati su samo kao primjeri; u poznatoj literaturi opisani t.u mnogi prikladni tenzidi koji se koriste u tehnici formulacija. As surface-active compounds, depending on the type of active substances being formulated, cationic and/or anionic surfactants or mixtures of surfactants with good emulsifying, dispersing and cross-linking properties come into consideration. The following surfactants are given only as examples; many suitable surfactants used in the formulation technique are described in the known literature.
Kao neionski tenzidi u prvom redu dolaze u obzir derivati poliglikola alifatskih ili cikloalifatskih alkohola, zasićene i nezasićene masne kiseline i alkilfenoli, koji mogu sadržavati 3 do 30 grupa glikoletera i 8 do 20 atoma ugljika u (alifatskom) ostatku ugljikovodika i 6 do 18 atoma ugljika u alkilnom ostatku alkilfenola. Nadalje su prikladni u vodi topivi adukti polietilenoksida koji na polipropilenglikolu sadrže 20 do 250 grupa etilengikoletera i 10 do 100 grupa propilenglikoletera, etilendiaminopolipropilenglikol i alkilpolipropilenglikol sa 1 do 10 atoma ugljika u alkilnomlancu. Navedeni spojevi sadrže obično po jedinici propilenglikola 1 do 5 jedinica etilenglikola. Kao primjere navodimo nonilfenolpolietoksietanol, poliglikoleter ricinusovog ulja, adukta polipropilen-polietilenoksida, tributilfenoksipolietoksietanol: Nadalje dolaze u obzir esteri masnih kiselina na polioksietilensorbitana kao što je polioksietilensorbitan-trioleat. As nonionic surfactants, derivatives of polyglycols of aliphatic or cycloaliphatic alcohols, saturated and unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycolether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon residue and 6 to 18 carbon atoms, come into consideration as nonionic surfactants. in the alkyl residue of alkylphenol. Water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain are also suitable. These compounds usually contain 1 to 5 units of ethylene glycol per unit of propylene glycol. Examples include nonylphenol polyethoxyethanol, castor oil polyglycol ether, polypropylene-polyethylene oxide adduct, tributylphenoxypolyethoxyethanol: Further, fatty acid esters of polyoxyethylenesorbitan such as polyoxyethylenesorbitan-trioleate come into consideration.
Kod kationskih tenzida u prvom redu se radi o kvarternarnim amonijevim solima, koje kao supstituente imaju na imanje jedan alkilni ostatak sa 8 do 22 C-atoma, a kao daljnje supstituente niske, eventualno halogenirane alkilne, benzilno ili niske hidroksialkilne ostatke. Soli se nalaze uglavnom kao halogenidi, metilsulfati ili etilsulfati. Primjeri su stearil-trimetil-amonijev klorid i benzil-di-(2-kloretil)-etil-amonijev bromid. Cationic surfactants are primarily quaternary ammonium salts, which have as substituents one alkyl residue with 8 to 22 C atoms, and as further substituents low, possibly halogenated alkyl, benzyl or low hydroxyalkyl residues. Salts are found mainly as halides, methylsulfates or ethylsulfates. Examples are stearyl-trimethyl-ammonium chloride and benzyl-di-(2-chloroethyl)-ethyl-ammonium bromide.
Prikladni anionski tenzidi mogu biti kako u vodi topivi sapuni, tako i u vodi topivi sintetski površinski aktivni spojevi, kao sapuni prikladni su alkalne, zemnoalkalne i eventualno supstituirane amonijeve soli viših masnih kiselina (C10-C22) kao natrijeve ili kalijeve soli uljnih ili stearinskih kiselina ili mješavina prirodnih masnih kiselina koje se primierice mogu dobiti iz kokosovog ulja; nadalje spominjemo sol: metil-taurinske masne kiseline. No, češće se koriste sintetski tenzidi, naročito sulfonati masnih kiselina, sulfati masnih kiselina, sulfonirani derivati benzimidazola ili sulfonati alkilarila. Sulfonati i sulfati masnih kiselina uglavnom se nalaze kao analno, zemnoalkalne ili eventualno supstituirane amonijeve soli i uglavnom imaju jedan alkilni ostatak sa 8 do 22 C-atoma, pri čemu alkil obuhvaća i alkilni dio acilnih ostataka; kao primjere navodimo natrijevu ili kalcijevu sol ligninsulfonske kiseline estera dodecil-sumporne kiseline ili mješavine sulfata masnog alkohola koji se dobiva iz prirodnih masnih kiselina. Tu spadaju i soli estera sumporne kiseline, te sulfonske kiseline adukta etilenoksida masnog alkohola. Sulfonirani derivati benzimidazola sadrže 2 grupe sulfonske kiseline i jedan ostatak masne kiseline sa oko u do 22 C-atoma. Alkilarilni sulfonati su na primjer natrijeve, kalcijeve soli ili amonijeve soli trietanolamonija dodecil benzolsulfonske kiseline, dibutilnaftalinsulfonske kiseline ili formaldehidnog kondenzacionog proizvoda naftalinsulfonske kiseline. Nadalje dolaze u obzir odgovarajući fosfati kao što su soli estera fosforne kiselineadukta p-nonilfenol-(4-14)-etilanoksida ili fosfolipidi. Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds, suitable as soaps are alkaline, alkaline earth and possibly substituted ammonium salts of higher fatty acids (C10-C22) such as sodium or potassium salts of oleic or stearic acids or a mixture of natural fatty acids that can be obtained, for example, from coconut oil; we also mention the salt: methyl-taurine fatty acids. However, synthetic surfactants are more often used, especially sulfonates of fatty acids, sulfates of fatty acids, sulfonated benzimidazole derivatives or alkylaryl sulfonates. Fatty acid sulfonates and sulfates are mostly found as anal, alkaline earth or possibly substituted ammonium salts and mostly have one alkyl residue with 8 to 22 C-atoms, whereby alkyl also includes the alkyl part of acyl residues; as examples, we cite the sodium or calcium salt of ligninsulfonic acid of dodecyl-sulfuric acid ester or a mixture of fatty alcohol sulfates obtained from natural fatty acids. This also includes salts of sulfuric acid esters and sulfonic acids of fatty alcohol ethylene oxide adducts. Sulfonated benzimidazole derivatives contain 2 sulfonic acid groups and one fatty acid residue with about u to 22 C-atoms. Alkylaryl sulfonates are, for example, the sodium, calcium or ammonium salts of triethanolammonium dodecyl benzenesulfonic acid, dibutylnaphthalenesulfonic acid or the formaldehyde condensation product of naphthalenesulfonic acid. Furthermore, suitable phosphates such as phosphoric acid ester salts of p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids come into consideration.
Sredstva u pravilu sadrže 0,1 do 99%, naročito 0,1 do 95 % aktivna tvari i 1 do 99,9%, naročito 5 do 99,9% najmanje jedne čvrste ili tekuće pomoćne tvari, pri čemu u pravilu 0 do 25%, naročitu 0.1 do 20% sredstva mogu biti tenzidi (% uvijek znači težinski postotak). Dok se u slobodnoj prodaji prije mogu dobiti koncentrirana sredstva, krajnji korisnik u pravilu koristi razrijeđena sredstva koja imaju mnogo manje koncentracije aktivne tvari. Najviše korištena sredstva sastoje se od sljedećeg (% = težinski postotak): As a rule, the means contain 0.1 to 99%, especially 0.1 to 95% of active substances and 1 to 99.9%, especially 5 to 99.9% of at least one solid or liquid auxiliary substance, whereby as a rule 0 to 25 %, especially 0.1 to 20% of the agent can be surfactants (% always means percentage by weight). While concentrated means can be obtained over the counter, as a rule, the end user uses diluted means that have a much lower concentration of the active substance. The most used means consist of the following (% = weight percentage):
Emulgirajući koncentrati: Emulsifying concentrates:
aktivna tvar: 1 do 90%, uglavnom 5 do 20% active substance: 1 to 90%, mostly 5 to 20%
tenzid: 1 do 30%, uglavnom 10 do 20% surfactant: 1 to 30%, mostly 10 to 20%
otapalo: 5 do 98%, uglavnom 70 do 85% solvent: 5 to 98%, mostly 70 to 85%
Sredstva za prašenje: Detergents:
aktivna tvar: 0,1 do 10%, uglavnom 0.1 do 1%. active substance: 0.1 to 10%, mostly 0.1 to 1%.
čvrsta nosiva tvar: 99,9 do 90%, uglavnom 99,9 do 99% solid carrier: 99.9 to 90%, mostly 99.9 to 99%
Koncentrati suspenzija: Suspension concentrates:
aktivna tvar: 3 do 75%, uglavnom 10 do 50% active substance: 3 to 75%, mostly 10 to 50%
voda: 94 do 24%, uglavnom 88 do 30% water: 94 to 24%, mostly 88 to 30%
tenzid: 1 do 40%, uglavnom 2 do 30% surfactant: 1 to 40%, mostly 2 to 30%
Ovlaživi prašak: Wetting powder:
aktivna tvar: 0,5 do 90%, uglavnom 1 do 80% active substance: 0.5 to 90%, mostly 1 to 80%
tenzid: 0,5 do 20%, uglavnom 1 do 15% surfactant: 0.5 to 20%, mostly 1 to 15%
čvrsta nosiva tvar: 5 do 99%, uglavnom 15 do 98% solid carrier: 5 to 99%, mostly 15 to 98%
Granulati: Granules:
aktivna tvar: 0,5 do 30%, uglavnom 3 do 15% active substance: 0.5 to 30%, mostly 3 to 15%
čvrsta nosiva tvar: 99,5 do 70%, uglavnom 97 do 85% solid carrier: 99.5 to 70%, mostly 97 to 85%
Djelovanje sredstava prema izumu može se dodatkom ostalih insekticidnih, netotozidnih, akaricidnih i/ili fungicidnih aktivnih tvari uveliko proširiti i prilagoditi datim okolnostima. Kao dodatne aktivne tvari pri tome dolaze u obzir napr. reprezentanti sljedećih klasa aktivnih tvari: organski fosforni spojevi, nitrofenoli i derivati, formamidini, uree, karbamati, piretroidi, klorirani ugljikovodici i preparati bacillus thuringiensis. Sredstva prema izumu mogu sadržavati i daljnje čvrste ili tekuće pomoćne tvari kao stabilizatore, npr. epoksidirana biljna ulja (napr epoksidirano ulje kokosovog oraha, repice ili soje), otpjenjivače, npr. silikonsko ulje, konzervanse, regulatore viskoziteta, veziva i/ili adheziona sredstva, kao i umjetna gnojiva ili druge aktivne tvari za postizavanje posebnih efekata, npr. baktericide, moluskicide ili selektivne herbicide. The action of the agents according to the invention can be greatly expanded and adapted to the given circumstances by the addition of other insecticidal, nettocidal, acaricidal and/or fungicidal active substances. As additional active substances, e.g. representatives of the following classes of active substances: organic phosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and preparations of bacillus thuringiensis. The agents according to the invention may also contain further solid or liquid auxiliary substances as stabilizers, e.g. epoxidized vegetable oils (e.g. epoxidized coconut, canola or soybean oil), release agents, e.g. silicone oil, preservatives, viscosity regulators, binders and/or adhesion agents , as well as artificial fertilizers or other active substances for achieving special effects, eg bactericides, molluscicides or selective herbicides.
Sredstva prema izumu dobivaju se na poznat način, bez pomoćnih tvari npr. mljevenjem i/ili prosijavanjem čvrste aktivne tvari ili mješavine aktivnih tvari, npr. na određenu veličinu zrna, a u prisustvu najmanje jedne pomoćne tvari npr. dobrim miješanjem i/ili mljevenjem aktivne tvari ili mješavine aktivnih tvari sa pomoćnom/pomoćnim tvari/tvarima. Ovaj postupak za proizvodnju sredstava prema izumu i primjena spojeva I za proizvodnju tih sredstava također čine predmet izuma. The agents according to the invention are obtained in a known manner, without excipients, for example by grinding and/or sieving a solid active substance or a mixture of active substances, e.g. to a certain grain size, and in the presence of at least one auxiliary substance, e.g. by mixing and/or grinding the active substance well or mixtures of active substances with auxiliary/auxiliary substance/substances. This process for the production of agents according to the invention and the use of compounds I for the production of these agents also form the subject of the invention.
Postupak primjene sredstava, dakle postupak za uništavanje štetnika spomenute vrste, prema željenim ciljevima i datim okolnostima, a koji može biti prskanje, zamagljivanje, prašenje, prevlačenje, jetkanje, posipavanje ili zalijevanje, te primjena sredstava za uništavanje štetnika navedene vrste daljnji predmet izuma. Tipične koncentracije za primjenu pri tome su u rasponu između 0,1 i 1000 ppm, uglavnom između 0,1 i 500 ppm aktivne tvari. Količine po hektaru iznose općenito 1 do 2000 g aktivne tvari po hektaru, naročito 10 do 1000 g/ha, preporučuje se 20 do 600 g/ha. The method of applying means, i.e. the method for destroying pests of the mentioned species, according to the desired goals and given circumstances, which can be spraying, fogging, dusting, coating, etching, sprinkling or watering, and the application of means for destroying pests of the mentioned species is a further subject of the invention. Typical concentrations for application are in the range between 0.1 and 1000 ppm, mainly between 0.1 and 500 ppm of the active substance. Amounts per hectare are generally 1 to 2000 g of active substance per hectare, especially 10 to 1000 g/ha, 20 to 600 g/ha is recommended.
Postupak primjene koji se preporuča na području zaštite bilja nanošenje na lišće biljke (aplikacija na list), pri čemu se frekvencija aplikacije i potrebna količina može podesiti prema tome, koliko biljke je napadnuto dotičnim štetnikom. Aktivna tvar može dospjeti u biljku i kroz korijen (sistemsko djelovanje), pri čemu se mjesto na kojem biljke rastu natopi tekućim sredstvom ili se aktivna tvar u čvrstom obliku stavi u tlo rasta biljke, npr. u obliku granulata (aplikacija na tlo). Kod kultura riže, takovi granulati mogu se staviti u poplavljeno rižino polje. Uništavanje nematoda vrši se u prvom redu pomoću aplikacije u zemlju odn. tlo. The application procedure that is recommended in the field of plant protection is application to the leaves of the plant (leaf application), whereby the frequency of application and the required amount can be adjusted according to how much of the plant is attacked by the pest in question. The active substance can also reach the plant through the root (systemic effect), whereby the place where the plants grow is soaked with a liquid agent or the active substance is placed in a solid form in the soil where the plant grows, for example in the form of granules (application to the soil). In the case of rice crops, such granules can be placed in a flooded rice field. Destruction of nematodes is done primarily by application to the ground or ground.
Sredstva prema izumu prikladni su i za zaštitu biljnog prirasta npr. voća, lukovica ili zrna ili sadnica, od gljivičnih infekcija i životinjskih štetnika. Biljni prirast može se tretirati sa sredstvom prije nicanja, sjeme se može npr. jetkati prije klijanja. Aktivne tvari prema izumu mogu se nanijeti i na sjemenke (coating), pri čemu se zrna ili natope u tekućem sredstvu ili se na njih nanese sloj čvrstog sredstva. Sredstvo se može aplicirati na mjesto nicanja i kad biljke već niknu, npr. oko biljaka. Postupak obrade biljnog prirasta i tako tretirani biljni prirast su daljnji predmet izuma. The agents according to the invention are also suitable for the protection of plant growth, for example fruit, bulbs or grains or seedlings, against fungal infections and animal pests. Plant growth can be treated with an agent before germination, seeds can be etched before germination, for example. Active substances according to the invention can also be applied to the seeds (coating), whereby the grains are either soaked in a liquid agent or a layer of solid agent is applied to them. The product can be applied to the place of sprouting and when the plants have already sprouted, for example around the plants. The process of processing plant growth and the plant growth treated in this way are a further subject of the invention.
Sljedeći primjeri služe za objašnjenje izuma. Oni ne ograničavaju izum. Temperature su date u stupnjevima Celziusa. The following examples serve to explain the invention. They do not limit the invention. Temperatures are given in degrees Celsius.
Primjeri proizvodnje Production examples
Primjer H1: Example H1:
2-metil-2H-indazol-3-karbonska kiselina 2-methyl-2H-indazole-3-carboxylic acid
a) 2-nitrobenziliden-metilamin. a) 2-nitrobenzylidene-methylamine.
[image] [image]
110.5 g 2-nitrobenzaldehida rastvori se u 850 ml benzola. U tu otopinu stavi se 24.8 g metilamina i reakcijska mješavina kuha se na uređaju za izlučivanje vode, dok se ne odvoji 17 ml vode. Reakcijska mješavina se ohladi, zgusne i sirovi proizvod se suši u visokom vakuumu. Tako se dobije 2-nitrobenziliden-metilamin sa talištem od 30°C. 110.5 g of 2-nitrobenzaldehyde is dissolved in 850 ml of benzene. 24.8 g of methylamine is added to this solution and the reaction mixture is boiled on a water separator until 17 ml of water is separated. The reaction mixture is cooled, concentrated and the crude product is dried under high vacuum. Thus, 2-nitrobenzylidene-methylamine with a melting point of 30°C is obtained.
b) 3-cijano-2-metil-2H-indazol-1-oksid b) 3-cyano-2-methyl-2H-indazole-1-oxide
[image] [image]
U otopinu od 120 g 2-nitrobenziliden-metilamina u 600 ml metanola koja je ohlađena na temperaturi između +5ºC i +10ºC, doda se 17.9 g kalijevog cijanida. Na kraju se polako ukapa 44,1 g ledene octene kiseline. Za vrijeme egzotermne reakcije mješavina se hlađenjem ledom drži na temperaturi od oko +10ºC. Nakon što je dodata polovina određene količine ledene octene kiseline, proizvod se iskristalizira. Reakcijskoj mješavini se doda daljnjih 200 ml metanola, i ukapa se preostala ledena octena kiselina. Frakcijska mješavina se 0.5 sati miješa na sobno temperaturi, a potom se ohladi na +10°C. Nataloženi proizvod se filtrira. Proizvod se ispere sa malo etanola, potom sa haksanom, a onda se ohladi. Tako se dobije 3-cijano-2-metil-2H-indazol-1-oksid sa talištem od 156-158°C. 17.9 g of potassium cyanide is added to a solution of 120 g of 2-nitrobenzylidene-methylamine in 600 ml of methanol that has been cooled to a temperature between +5ºC and +10ºC. Finally, 44.1 g of glacial acetic acid is slowly added. During the exothermic reaction, the mixture is kept at a temperature of around +10ºC by cooling with ice. After half of the specified amount of glacial acetic acid has been added, the product crystallizes. A further 200 ml of methanol was added to the reaction mixture, and the remaining glacial acetic acid was added dropwise. The fractional mixture is stirred for 0.5 hours at room temperature, and then cooled to +10°C. The precipitated product is filtered. The product is washed with a little ethanol, then with hexane, and then cooled. Thus, 3-cyano-2-methyl-2H-indazole-1-oxide with a melting point of 156-158°C is obtained.
c) 3-cijano-2-metil-2H-indazol c) 3-cyano-2-methyl-2H-indazole
[image] [image]
Otopini od 64.7 g 3-cijano-2-metil-2H-indazol-1-oksida u 500 ml kloroforma polagano se doda 120 g fosfortriklorida. Temperatura reakcije pri tome se uz hlađenje ledom drži na +40ºC. Po završenom dodavanju reakcijska mješavina se 1 sat kuha na refluksu, ohladi se i izlije na 1 i ledene vode. Doda se 30-postotna otopina kaustične sode, dok otopina ne postane alkalna. Triput se ekstrahira sa po 200 ml kloroforma. Kombinirani kloroform ekstrakti isperu se dvaput sa vodom i jednom sa zasićenom otopinom kuhinjske soli, suše iznad natrijevog sulfata, filtriraju i zgusnu. Sirovi proizvod prekristalizira se iz estera octene kiseline/heksana. Tako se dobije 3-cijano-2 metil-2H-indazol sa talištem od 98-100ºC. 120 g of phosphorus trichloride was slowly added to a solution of 64.7 g of 3-cyano-2-methyl-2H-indazole-1-oxide in 500 ml of chloroform. The reaction temperature is kept at +40ºC with ice cooling. After the addition is complete, the reaction mixture is refluxed for 1 hour, cooled and poured into 1 liter of ice water. A 30 percent solution of caustic soda is added until the solution becomes alkaline. It is extracted three times with 200 ml of chloroform. The combined chloroform extracts are washed twice with water and once with a saturated solution of table salt, dried over sodium sulfate, filtered and concentrated. The crude product is recrystallized from acetic acid ester/hexane. Thus, 3-cyano-2 methyl-2H-indazole with a melting point of 98-100ºC is obtained.
d) 2-metil-2H-indazol-3-karbonska kiselina d) 2-methyl-2H-indazole-3-carboxylic acid
[image] [image]
Mješavina od 70 g 3-cijano-2-metil-2H-indazola i 1,75-postotne sumporne kiseline 2.5 sata se miješa na +110ºC (Temperatura kupke) Na kraju se reakcijska mješavina ohladi i izlije na 2 kg leda, te ekstrahira sa esterom octene kiseline. Faza estera octene kiseline se odvoji, jednom se ispere sa vodom, jednom sa zasićenom otopinom kuhinjske soli, suši preko natrijevog sulfata, filtrira i upari na rotacionom isparivaču. Ostatak se razmulji u ne jako hladnom esteru octene kiseline, filtrira i suši u vakuumu. Tako se dobije 2-metil-2H-indazol-3-karbonska kiselina sa talištem od 233-235ºC (razlaganje). A mixture of 70 g of 3-cyano-2-methyl-2H-indazole and 1.75% sulfuric acid is stirred for 2.5 hours at +110ºC (bath temperature). Finally, the reaction mixture is cooled and poured onto 2 kg of ice, and extracted with acetic acid ester. The acetic acid ester phase is separated, washed once with water, once with a saturated solution of table salt, dried over sodium sulfate, filtered and evaporated on a rotary evaporator. The residue is slurried in not very cold acetic acid ester, filtered and dried in a vacuum. This gives 2-methyl-2H-indazole-3-carboxylic acid with a melting point of 233-235ºC (decomposition).
Na analogan način dobiva se iz In an analogous way, it is obtained from
-5-klor-2-nitrobenzaldehida i metilamina 5-klor-2-metil-2H-indazol-3-karbonska kiselina sa talištem na 247-248ºC; -5-chloro-2-nitrobenzaldehyde and methylamine 5-chloro-2-methyl-2H-indazole-3-carboxylic acid with a melting point of 247-248ºC;
-5-metil-2-nitrobenzaldehid i metilamina 2,5-dimetil-2H-indazol-3-karbonska kiselina sa talištem od 240-241°C; -5-methyl-2-nitrobenzaldehyde and methylamine 2,5-dimethyl-2H-indazole-3-carboxylic acid with a melting point of 240-241°C;
-3-metil-2-nitrobenzaldehida i metilamina 2,7-dimetil-2H-indazol-3-karbonska kiselina sa talištem 224-225ºC; -3-methyl-2-nitrobenzaldehyde and methylamine 2,7-dimethyl-2H-indazole-3-carboxylic acid with a melting point of 224-225ºC;
-2-nitrobenzaldehida i ciklopropilamina 2-ciklopropil-2H-indazol-3-karbonska kiselina, sa talištem od 187-189ºC. -2-nitrobenzaldehyde and cyclopropylamine 2-cyclopropyl-2H-indazole-3-carboxylic acid, with a melting point of 187-189ºC.
Primjer H2: Example H2:
2-metil-2H-indazol-3-karbonska kiselina-(3-(4-fluorfenoksi)-benzil)-amid 2-methyl-2H-indazole-3-carboxylic acid-(3-(4-fluorophenoxy)-benzyl)-amide
[image] [image]
Otopini od 4 g 2-metil-2H-indazol-3-karbonske kiseline u 50 ml tetrahidrofurana doda se 3.2 g oksalilklorida i 5 kapi dimetilformamida i reakcijska mješavina se 0.5 sati miješa na sobnoj temperaturi. Na kraju se reakcijska mješavina zgusne, a ostatak se rastvori u 50 ml toluola. U ovu otopinu koja je ohlađena na temperaturi između 0ºC i +5ºC ukapa se otopina od 4.9 g 3-(4-fluorfenoksi)-benzilamina i 2.0 g piridina u 10 ml toluola. Po završenom dodavanju reakcijska mmješavina se 1 sat miješa na sobnoj temperaturi i razrijedi sa esterom octene kiseline. Ta mješavina se dvaput; ispere sa vodom, jednom sa zasićenom otopinom kuhinjske soli, suši preko natrijevog sulfata, filtrira i upari na rotacionom isparivaču. Sirovi proizvod se pročisti stupnom kromatografijom preko silika gela sa esterom octene kiseline/heksanom (1:1). Tako se dobije amid 2-metil-2H-indazol-3-karbonska kiselina-(3-(4-fluorfenoksi)-benzila) sa talištem od 91-93°C. 3.2 g of oxalyl chloride and 5 drops of dimethylformamide were added to a solution of 4 g of 2-methyl-2H-indazole-3-carboxylic acid in 50 ml of tetrahydrofuran, and the reaction mixture was stirred for 0.5 hours at room temperature. At the end, the reaction mixture is thickened, and the residue is dissolved in 50 ml of toluene. A solution of 4.9 g of 3-(4-fluorophenoxy)-benzylamine and 2.0 g of pyridine in 10 ml of toluene is added dropwise to this solution, which has been cooled to a temperature between 0ºC and +5ºC. After the addition is complete, the reaction mixture is stirred for 1 hour at room temperature and diluted with acetic acid ester. That mixture is twice; washed with water, once with a saturated solution of table salt, dried over sodium sulfate, filtered and evaporated on a rotary evaporator. The crude product is purified by column chromatography over silica gel with acetic acid ester/hexane (1:1). Thus, the amide 2-methyl-2H-indazole-3-carboxylic acid-(3-(4-fluorophenoxy)-benzyl) with a melting point of 91-93°C is obtained.
Primjer H3: Example H3:
amid N-acetil-2-metil-2H-indazol-3-karbonska kiselina-(4-(4-trifluormetilfenoksil)-benzila) amide N-acetyl-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxyl)-benzyl)
[image] [image]
Suspenziji od 0,5 g natrijevog hidrida (55% u ulju) u 40 ml dimetoksietana ukapa se na sobnoj temperaturi 5,0 g amida 2-metil-2H-indazol-3-karbonska kiselina-(4-trifluormetilfenoksi)-benzila) rastvorenog u 20 ml dimetoksietana. Mješavina se miješa još daljnjih 15 minuta. Potom se na sobnoj temperaturi ukapa 1,0 g acetilklorida u 10 ml dimetoksietana. Na kraju se jedan sat miješa. Mješavina se zgusne na rotacionom isparivaču, a ostatak se razrijedi sa etilnim esterom octene kiseline. Mješavina se dvaput ispere sa vodom i jednom sa zasićenom otopinom kuhinjske soli, suši preko natrijevog sulfata, filtrira i upari na rotacionom isparivaču. Ostatak se pročisti stupnom kromatografijom preko silika-gela sa esterom octene kiseline/heksanom (1:1). Tako se dobije amid N-acetil-2-metil-2H-indazol-3-karbonska kiselina-(4-(4-trifluorometil-fenoksi)-benzila) sa talištem od 89-91°C. To a suspension of 0.5 g of sodium hydride (55% in oil) in 40 ml of dimethoxyethane, 5.0 g of amide 2-methyl-2H-indazole-3-carboxylic acid-(4-trifluoromethylphenoxy)-benzyl) dissolved in 20 ml of dimethoxyethane. The mixture is stirred for another 15 minutes. Then, at room temperature, 1.0 g of acetyl chloride is added dropwise to 10 ml of dimethoxyethane. At the end, it is stirred for one hour. The mixture is concentrated on a rotary evaporator, and the residue is diluted with ethyl acetate. The mixture is washed twice with water and once with a saturated solution of table salt, dried over sodium sulfate, filtered and evaporated on a rotary evaporator. The residue is purified by column chromatography over silica gel with acetic acid ester/hexane (1:1). This gives the amide N-acetyl-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethyl-phenoxy)-benzyl) with a melting point of 89-91°C.
Na analogan način dobiva se Iz amida 2-metil-2H-indazol-3-karbonska kiselina-(4-(4-trifluormetilfenoksi)-benzila) i amida 2-klorid etilkapronske kiseline N-(2-etilenheksanoil)-2-metil-2H-indazol-3-karbonska kiselina-(4-(4-trifluormetilfenoksi)-benzila; sa talištem od 97-98°C. In an analogous way, amide 2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxy)-benzyl) and amide 2-chloride of ethylcaproic acid N-(2-ethylenehexanoyl)-2-methyl- 2H-Indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxy)-benzyl; with a melting point of 97-98°C.
Primjer H4 Example H4
amid N-(tert.butoksioksalil)-2-metil-2H-indazol-3-karbonska kiselina-(4-(4-trifluormetilfenoksil)-benzila) amide N-(tert.butoxyoxalyl)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxyl)-benzyl)
[image] [image]
dimetoksietana ukapa se na sobnoj temperaturi 5,0 g amida 2-metil-2H-indazol-3-karbonska kiselina-(4-(4-trifluormetilfenoksi)-benzila), rastvorenog u 20 ml dimetoksietana. Mješavina se miješa još daljnjih 15 minuta. Potom se na sobnoj temperaturi ukapa 2,0 g tert.-butoksioksalilklorida rastvorenog u 10 ml dimetoksietana. Potom se jedan sat miješa. Reakcijska mješavina se filtrira preko dijatomejske zemlje i filtrat se upari na rotacionom isparivaču. Dobiveni sirovi proizvod se kao tekuće sredstvo pročišćava stupnom kromatografijom preko silika-gela sa esterom octene kiseline/heksanom (1:3). Tako se dobije amid N-(tert.butoksioksalil)-2-metil-2H-indazol-3-karbonska kiselina-(4-(4-trifluormetilfenoksil)-benzila), talište 107-108°C. of dimethoxyethane, 5.0 g of amide 2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxy)-benzyl), dissolved in 20 ml of dimethoxyethane, is added dropwise at room temperature. The mixture is stirred for another 15 minutes. Then 2.0 g of tert.-butoxyoxalyl chloride dissolved in 10 ml of dimethoxyethane is added dropwise at room temperature. Then it is mixed for one hour. The reaction mixture is filtered through diatomaceous earth and the filtrate is evaporated on a rotary evaporator. The obtained crude product is purified as a liquid agent by column chromatography over silica gel with acetic acid ester/hexane (1:3). This gives the amide N-(tert.butoxyoxalyl)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxyl)-benzyl), melting point 107-108°C.
Na analogan način dobiva se iz amida 2-metil-2H-indazol-3-karbonska kiselina-(4-(4-trifluormetilfenoksi)-benzila) i amida N,N-dipropil-N'-metil-N'-sulfonilkloriduree N-(3,3-dipropil-1-metilureido-1-sulfenil)-2-metil-2H-indazol-3-karbonska kiselina-(4-(4-trifluormetil-fenoksi)-benzila) sa talištem od 110-111ºC. 2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxy)-benzyl) and amide N,N-dipropyl-N'-methyl-N'-sulfonylchloridurea N- (3,3-dipropyl-1-methylureido-1-sulphenyl)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethyl-phenoxy)-benzyl) with a melting point of 110-111ºC.
Primjer H5: Example H5:
Na analogan način mogu se dobiti i spojevi tabela 1 do 7, In an analogous way, the compounds of tables 1 to 7 can be obtained,
Tabela 1 Table 1
[image] [image]
[image] [image] [image] [image] [image] [image]
Tabela 2 Table 2
[image] [image]
[image] [image] [image] [image] [image] [image]
Tabela 3 Table 3
[image] [image]
[image] [image]
Tabela 4 Table 4
[image] [image]
[image] [image] [image] [image]
Tabela 5 Table 5
[image] [image]
[image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image]
Tabela 6 Table 6
[image] [image]
[image] [image] [image] [image] [image] [image]
Tabela 7 Table 7
[image] [image]
[image] [image]
Primjeri formulacije (% = težinski postotak) Formulation examples (% = weight percentage)
Primjer F1: Example F1:
emulzioni koncentrati a) b) c) emulsion concentrates a) b) c)
Aktivna tvar br. 5.117 25% 40% 50% Active substance no. 5,117 25% 40% 50%
Ca-dodecilbenzosulfonat 5% 8% 6% Ca-dodecylbenzosulfonate 5% 8% 6%
Polietilenglikoleter ricinusovog ulja (36 mol AEO) 5% - - Polyethylene glycol ether of castor oil (36 mol AEO) 5% - -
Tributilfenolpolietilenglikoleter (30 mol AEO) - 12% 4% Tributylphenol polyethylene glycol ether (30 mol AEO) - 12% 4%
Cikloheksanon - 15% 20% Cyclohexanone - 15% 20%
Mješavina 65% 25% 20% Mixture 65% 25% 20%
Iz takovih koncentrata mogu se razrjeđivanjem s vodom dobiti emulzije svake željene koncentracije. Emulsions of any desired concentration can be obtained from such concentrates by diluting them with water.
Primjer F2: Example F2:
Otopine a) b) c) d) Solutions a) b) c) d)
Aktivna tvar br. 3.20 80% 10% 5% 95% Active substance no. 3.20 80% 10% 5% 95%
Etilenglikolmonometileter 20% - - - Ethylene glycol monomethyl ether 20% - - -
Polietilenglikol MG 400 - 70% - - Polyethylene glycol MG 400 - 70% - -
N-metil-2-pirolidon - 20% - - N-methyl-2-pyrrolidone - 20% - -
Epoksidirano ulje kokosovog oraha - - 1% 5% Epoxidized coconut oil - - 1% 5%
Benzin (granice ključanja 160-190ºC) - - 94% - Gasoline (boiling point 160-190ºC) - - 94% -
Otopine su prikladne za primjenu u obliku najmanjih kapljica. Solutions are suitable for application in the form of the smallest droplets.
Primjer F3: Example F3:
Granulati a) b) c) d) Granules a) b) c) d)
Aktivna tvar br. 4.27 5% 10% 8% 21% Active substance no. 4.27 5% 10% 8% 21%
Kaolin 94% - 79% 54% Kaolin 94% - 79% 54%
Visokodisperzna silicijeva kiselina 1% - 13% 7% Highly dispersed silicic acid 1% - 13% 7%
Atapulgit - 90% - 18% Attapulgite - 90% - 18%
Aktivna tvar rastvori se u diklormetanu, otopina se rasprši na nosač i otapalo se na kraju upari u vakuumu. The active substance is dissolved in dichloromethane, the solution is sprayed onto the carrier and the solvent is finally evaporated in a vacuum.
Primjer F4: Example F4:
Sredstvo za prašenje a) b) Dusting agent a) b)
Aktivna tvar br. 5.117 2% 5% Active substance no. 5,117 2% 5%
Visokodisperzna silicijeva kiselina 1% 5% Highly dispersed silicic acid 1% 5%
Talk 97% - Talc 97% -
Kaolin - 90% Kaolin - 90%
Dobrim miješanjem nosivih tvari sa aktivnom tvari, dobiva se sredstvo za prašenje gotovo za upotrebu. By mixing the carrier substances well with the active substance, a ready-to-use dusting agent is obtained.
Primjer F5: Example F5:
prašak za prskanje a) b) c) spray powder a) b) c)
Aktivna tvar br. 2.05 25% 50% 75% Active substance no. 2.05 25% 50% 75%
Na-lignmsultonat 5% 5% - Na-lignmsultonate 5% 5% -
Na-laurilsulfonat 3% - 5% Na-lauryl sulfonate 3% - 5%
Na-diizobutilinaftalinsulfonat - 6% 10% Na-diisobutylene naphthalene sulfonate - 6% 10%
Oktilfenolpolietilenglikoleter (7 - 8 mol AeO) - 2% - Octylphenol polyethylene glycol ether (7 - 8 mol AeO) - 2% -
Visokodisperzna silicijeva kiselina 5% 10% 10% Highly dispersed silicic acid 5% 10% 10%
Kaolin 62% 27% - Kaolin 62% 27% -
Aktivna tvar pomiješa se sa dodatnim tvarima i mješavina se dobro samelje u prikladnom mlinu. Dobiva se prašak za prskanje, koji se sa vodom može razrijediti u suspenzije svake željene koncentracije. The active substance is mixed with additional substances and the mixture is ground well in a suitable mill. A spray powder is obtained, which can be diluted with water into suspensions of any desired concentration.
Primjer F6: Example F6:
emulzioni koncentrat: emulsion concentrate:
Aktivna tvar br. 2.113 10% Active substance no. 2,113 10%
Oktilfenolpolietilenglikoleter (4-5 mol Aeu) 3% Octylphenol polyethylene glycol ether (4-5 mol Aeu) 3%
Ca-dodecilbenzolsulfonat 3% Ca-dodecylbenzenesulfonate 3%
Poliglikoleter ricinusovog ulja (36 mol AeO) 4% Castor oil polyglycol ether (36 mol AeO) 4%
Cikloheksanon 30% Cyclohexanone 30%
Mješavina ksilola 50% Xylene mixture 50%
Iz ovog koncentrata mogu se razrjeđivanjem sa vodom dobiti emulzije svake željene koncentracije. Emulsions of any desired concentration can be obtained from this concentrate by diluting it with water.
Primjer F7: Example F7:
sredstvo za prašenje a) b) detergent a) b)
Aktivna tvar br. 2.08 5% 8% Active substance no. 2.08 5% 8%
Talk 95% - Talc 95% -
Kaolin - 92% Kaolin - 92%
Sredstva za prašenje gotova za upotrebu dobivaju se tako, da se aktivna, tvar pomiješa sa nosačem i mješavina se samelje u prikladnom mlinu. Ready-to-use dusting agents are obtained by mixing the active substance with the carrier and grinding the mixture in a suitable mill.
Primjer F8: Example F8:
Ekstruder granulat Extruder granulate
Aktivna tvar br. 4.19 10% Active substance no. 4.19 10%
Na-ligninsulfonat 2% Na-ligninsulfonate 2%
Karboksimetilceluloza 1% Carboxymethylcellulose 1%
Kaolin 87% Kaolin 87%
Aktivna tvar pomiješa se s dodatnim tvarima, mješavina se samelje i ovlaži sa vodom. Vlažna mješavina se ekstrudira i granulira, a dobiveni granulat se na kraju suši u struji zraka. The active substance is mixed with additional substances, the mixture is ground and moistened with water. The wet mixture is extruded and granulated, and the resulting granulate is finally dried in a stream of air.
Primjer F9: Example F9:
ovojni granu1at envelope granu1at
Aktivna tvar br. 1.02 3% Active substance no. 1.02 3%
Polietilenglikol (MG 200) 3% Polyethylene glycol (MG 200) 3%
Kaolin 94% Kaolin 94%
Fino samljevena aktivna tvar se u mješalici jednakomjerno nanese na kaolin navlažen sa polietilenglikolom. Na taj način dobiva se ovojni granulat bez prašine. The finely ground active substance is evenly applied to kaolin moistened with polyethylene glycol in a mixer. In this way, dust-free coating granulate is obtained.
Primjer F10: Example F10:
koncentrat suspenzije suspension concentrate
Aktivna tvar br. 2.95 40% Active substance no. 2.95 40%
Etilenglikol 10% Ethylene glycol 10%
Nonilfenolpolietilenglikoleter (15 mol AeO) 6% Nonylphenol polyethylene glycol ether (15 mol AeO) 6%
Na-ligninsulfonat 10% Na-ligninsulfonate 10%
Karboksimetilceluloza 1% Carboxymethylcellulose 1%
Silikonsko ulje u obliku 75-postotne vodene emulzije 1% Silicone oil in the form of a 75% aqueous emulsion 1%
Voda 32% Water 32%
Fino mljevena aktivna tvar dobro se izmiješa sa dodatnim tvarima. Tako se dobije koncentrat suspenzije, iz kojeg se razrjeđivanjem sa vodom mogu dobiti suspenzije bilo koje željene koncentracije. The finely ground active substance is well mixed with additional substances. In this way, a suspension concentrate is obtained, from which, by diluting with water, suspensions of any desired concentration can be obtained.
Biološki primjeri Biological examples
Primjer B1 Example B1
Djelovanje protiv nilaparvata lugens Action against nilaparvata lugens
Biljke riže tretiraju se sa vodenom emulzijom za prskanje, koja sadrži 400 ppm aktivne tvari: nakon sušenja prskane naslage, na biljke riže stave se ličinke cvrčka 2. i 3. stadija. Nakon 21 dana vrši se numeričko izračunavanje. Iz usporedbe broja preživjelih cvrčaka na tretiranim biljkama sa onima na netretiranima, određuje se procentualna redukcija populacije (% djelovanja). The rice plants are treated with an aqueous emulsion for spraying, which contains 400 ppm of the active substance: after drying the sprayed layer, 2nd and 3rd stage cricket larvae are placed on the rice plants. After 21 days, a numerical calculation is performed. From the comparison of the number of surviving crickets on treated plants with those on untreated ones, the percentage reduction of the population (% effect) is determined.
Spojevi tabela 1 do 7 pokazuju u ovom testu dobro djelovanje protiv nilaparvata lugens. Naročito spojevi 1.02, 2.05, 5.153 i 5.706 pokazuju djelovanje iznad 80%. The compounds of Tables 1 to 7 show good activity against Nilaparvata lugens in this test. Especially the compounds 1.02, 2.05, 5.153 and 5.706 show activity above 80%.
Primjer B2 Example B2
Ovo/larvicidno djelovanje na heliothis virescens This/larvicidal action on heliothis virescens
Na pamuku odložena jajašca heliothis virescens, poprskaju se sa vodenom emulzijom koja sadrži 400 ppm aktivne tvari. Nakon 8 dana vrši se numeričko izračunavanje procentualnog izlijeganja jajašaca i rata preživljavanja gusjenica usporedbom sa netretiranim kontrolnim jajašcima (% redukcije populacije). Heliothis virescens eggs deposited on cotton are sprayed with an aqueous emulsion containing 400 ppm of the active substance. After 8 days, a numerical calculation of the percent hatching of the eggs and the survival rate of the caterpillars is performed in comparison with untreated control eggs (% population reduction).
Spojevi prema tabelama 1-7 u ovom testu pokazuju dobro djelovanje protiv heliothis virescens. Naročito spojevi 1.02, 1.20, 2.05 i 5.706 pokazuju djelovanje više od 80%. The compounds according to Tables 1-7 in this test show good activity against Heliothis virescens. Especially the compounds 1.02, 1.20, 2.05 and 5.706 show an activity of more than 80%.
Primjer 83: Example 83:
Djelovanje protiv heliothis virescens gusjenica Action against Heliothis virescens caterpillars
Mlade biljke soje poprskaju se sa vodenom emulzijom, koja sadrži 400 ppm aktivne tvari. Nakon što se naslaga osuši, na biljke soje stavi se 10 gusjenica prvog stadija heliothis virescens i odloži se u plastičnu posudu. Nakon 6 dana vrši se numeričko izračunavanje. Iz usporedbe broja gusjenica i šteta od grizotina na tretiranim sa onim biljkama koje nisu tretirane, određuje se procentualna redukcija populacije odn. procentualna redukcija šteta od grizotina (% djelovanja). Young soybean plants are sprayed with an aqueous emulsion containing 400 ppm of the active substance. After the deposit dries, 10 caterpillars of the first stage of heliothis virescens are placed on the soybean plants and placed in a plastic container. After 6 days, a numerical calculation is performed. The percentage reduction of the population or percentage reduction of bite damage (% effect).
Spojevi tabela 1 do 7 pokazuju u ovom testu dobro djelovanje protiv heliothis virescens. Naročito spojevi 1.02, 1.20, 2.05 i 5.155 pokazuju djelovanje veće od 80%. The compounds of tables 1 to 7 show good activity against heliothis virescens in this test. Especially the compounds 1.02, 1.20, 2.05 and 5.155 show an activity greater than 80%.
Primjer 84: Example 84:
Djelovanje protiv spodoptera littoralis gusjenica Action against Spodoptera littoralis caterpillars
Mlade biljke soje poprskaju se sa vodenom emulzijom koja sadrži 400 ppm aktivne tvari. Nakon što se naslaga osuši, na biljke soje stavi se 10 gusjenica trećeg stadija spodoptera littoralis i sve se stavi u plastičnu posudu. Nakon tri dana vrši se numeričko izračunavanje. Iz usporedbe broja mrtvih gusjenica i šteta od grizotina na tretiranim biljkamasa onim netretiranim, određuje se procentualna redukcija populacije onda procentualna redukcija šteta od grizotina (% djelovanja). Young soybean plants are sprayed with an aqueous emulsion containing 400 ppm of the active substance. After the deposit dries, 10 caterpillars of the third stage of spodoptera littoralis are placed on soybean plants and everything is placed in a plastic container. After three days, a numerical calculation is performed. From the comparison of the number of dead caterpillars and the damage caused by gnats on the treated plant mass and the untreated ones, the percentage reduction of the population is determined, then the percentage reduction of the damage caused by gnats (% effect).
Spojevi tabela 1 do 7 u ovom testu pokazuju dobro djelovanje protiv spodoptera littoralis. Naročito spojevi 2.05 i 5.155 pokazuju dobro djelovanje veće od 80%. The compounds of tables 1 to 7 in this test show good activity against Spodoptera littoralis. Especially the compounds 2.05 and 5.155 show a good effect of more than 80%.
Primjer B5 Example B5
Djelovanje protiv aphis craccivora Action against aphis craccivora
Klice graška inficiraju se sa aphis craccivora, poprskaju sa emulzijom koja sadrži 400 ppm aktivne tvari i inkubira se na 20ºC. Nakon 3 i 6 dana vrši se numeričko izračunavanje. Iz usporedbe broja mrtvih lisnih uši na tretiranimsa onima na netretiranim biljkama, određuje se procentualna redukcija populacije (% djelovanja). Pea sprouts are infected with aphis craccivora, sprayed with an emulsion containing 400 ppm of the active substance and incubated at 20ºC. After 3 and 6 days, a numerical calculation is performed. From the comparison of the number of dead aphids on treated with those on untreated plants, the percentage reduction of the population (% effect) is determined.
Spojevi tabela 1 do 7 u ovom testu pokazuju dobro djelovanje protiv aphis craccivora. Naročito spojevi 2.05, 4.04 i 5.706 pokazuju dobro djelovanje iznad 80%. The compounds of tables 1 to 7 in this test show good activity against aphis craccivora. Especially compounds 2.05, 4.04 and 5.706 show a good activity above 80%.
Primjer B6 Example B6
Djelovanje protiv crocidolomia binotalis gusjenica Action against crocidolomia binotalis caterpillars
Mlade biljke kelja poprskaju se sa vodenom emulzijom koja sadrži 400 ppm aktivne tvari. Nakon što se naslaga osušila, na biljke kelja stavi se 10 gusjenica trećeg stadija crocidolomia binotalis i sve se stavi u plastičnu posudu. Nakon tri dana vrši se numeričko izračunavanje. Iz usporedbe broja mrtvih gusjenica i šteta od grizotina na tretiranim sa onima netretiranim biljkama, određuje se procentualna redukcija populacije odn. procentualna redukcija šteta od grizotina (% djelovanja). Young kale plants are sprayed with an aqueous emulsion containing 400 ppm of the active substance. After the deposit has dried, 10 caterpillars of the third stage of crocidolomia binotalis are placed on the kale plants and everything is placed in a plastic container. After three days, a numerical calculation is performed. The percentage reduction of the population or percentage reduction of bite damage (% effect).
Spojevi tabela 1 do 7 pokazujuu ovom testu dobro djelovanje protiv crocidolomia binotalis, iznad 80%. Naročito spojevi 1.02 i 1.20 pokazuju djelovanje iznad 80%. The compounds of tables 1 to 7 show good activity against crocidolomia binotalis in this test, above 80%. Especially the compounds 1.02 and 1.20 show activity above 80%.
Primjer B7 Example B7
Djelovanje protiv tetranychus urticae Action against tetranychus urticae
Na mlade biljke graha stavi se miješana populacija tetranychus urticae i 1 dan kasnije poprska se sa vodenom emulzijom koja sadrži 400 ppm aktivne tvari. Biljke se 6 dana inkubiraju na 25ºC, a potom se vrši numeričko izračunavanje. Iz usporedbe broja mrtvih jajašca, ličinka i adulta na tretiranim sa onima na netretiranim biljkama, određuje se procentualna redukcija populacije (% djelovanja). A mixed population of tetranychus urticae is placed on the young bean plants and 1 day later they are sprayed with an aqueous emulsion containing 400 ppm of the active substance. The plants are incubated for 6 days at 25ºC, and then a numerical calculation is made. From the comparison of the number of dead eggs, larvae and adults on treated with those on untreated plants, the percentage reduction of the population (% effect) is determined.
Spojevi tabela 1 do 7 pokazuju u ovom testu djelovanje Iznad 80% protiv tetranychus urticae. The compounds of tables 1 to 7 show in this test an activity of Above 80% against tetranychus urticae.
Primjer B8: Example B8:
Ovicidno djelovanje na heliothis vilescens Ovicidal effect on heliothis vilescens
Jajašca heliothis virescens odložena na filtar papiru na kratko se umoče u acetonsku-vodenu ispitnu otopinu koja sadrži 400 ppm aktivne tvari. Nakon što se ispitna otopina osušila, jajašca se inkubiraju u Petrijevoj posudi. Nakon 6 dana vrši se izračunavanje procentualnog izlijeganja jajašca u usporedbi sa netretiranim kontrolnim skupinama (% redukcije izlijeganja). Spojevi prema tabelama 1 do 7 u ovom testu pokazuju dobro djelovanje protiv heliothis virescens. Naročito spojevi 1.02, 1.20, 2.05, 5.155 i 5.706 pokazuju djelovanje iznad 80%. Eggs of Heliothis virescens deposited on filter paper are briefly dipped in an acetone-water test solution containing 400 ppm of the active substance. After the test solution has dried, the eggs are incubated in a Petri dish. After 6 days, the percentage hatching of eggs is calculated in comparison with untreated control groups (% hatching reduction). The compounds according to tables 1 to 7 in this test show good activity against heliothis virescens. Especially the compounds 1.02, 1.20, 2.05, 5.155 and 5.706 show activity above 80%.
Primjer B9: Example B9:
Djelovanje protiv bemisia tabaci Action against Bemisia tabaci
Biljke grmolikih mahunarki stave se u kaveze od gaze i na njih se stave adulti bemisia tabaci (bijela muha). Nakon odlaganja jajašca svi adulti se odstrane i 10 dana kasnije se biljke na kojima se nalaze čahure, tretiraju sa vodenom emulzijom koja sadrži aktivne tvari koje se ispituju (koncentracija 400 ppm). Numeričko izračunavanje %-izlijeganja vrši se 14 dana nakon aplikacije aktivne tvari usporedbom sa netretiranim kontrolnim grupama. Bush leguminous plants are placed in gauze cages and adult bemisia tabaci (whitefly) are placed on them. After laying the eggs, all adults are removed and 10 days later the plants on which the cocoons are located are treated with an aqueous emulsion containing the active substances being tested (concentration 400 ppm). Numerical calculation of % hatching is performed 14 days after the application of the active substance by comparison with untreated control groups.
Spojevi prema tabelama 1 do 7 pokazuju u ovom testu dobro djelovanje protiv bemisia tabaci. Naročito spojevi 1.02 i 1.20 pokazuju djelovanje iznad 80%. The compounds according to tables 1 to 7 show good activity against bemisia tabaci in this test. Especially the compounds 1.02 and 1.20 show activity above 80%.
Primjer B10: Example B10:
Djelovanje protiv ličinka diabrotica balteata Action against the larvae of diabrotica balteata
Klice kukuruza poprskaju se sa vodenom emulzijom koja sadrži 400 ppm aktivne tvari. Nakon što se naslaga emulzije osušila, na klice kukuruza stavi se 10 ličinka drugog stadija diabrotica balteata i sve se stavi u plastičnu posudu. Nakon 6 dana vrši se numeričko izračunavanje. Iz usporedbe broja mrtvih ličinka na tretiranim sa onima na netretiranim biljkama, određuje se procentualna redukcija populacije (% djelovanja). Spojevi tabela 1 do 7 pokazuju u ovom testu dobro djelovanje protiv diabrotica balteata. Naročito spojevi 1.02, 1.20, 2.05, 4.01, 4.03, 5.155 i 5.706 pokazuju djelovanje iznad 80%. Corn sprouts are sprayed with an aqueous emulsion containing 400 ppm of the active substance. After the emulsion layer has dried, 10 larvae of the second stage of diabrotica balteata are placed on the corn sprouts and everything is placed in a plastic container. After 6 days, a numerical calculation is performed. From the comparison of the number of dead larvae on treated with those on untreated plants, the percentage reduction of the population (% action) is determined. The compounds of tables 1 to 7 show good activity against diabrotica balteate in this test. Especially the compounds 1.02, 1.20, 2.05, 4.01, 4.03, 5.155 and 5.706 show activity above 80%.
Primjer B11: Example B11:
Djelovanje protiv gusjenica plutella xylostella Action against Plutella xylostella caterpillars
Mlade biljke kelja poprskaju se sa vodenom emulzijom koja sadrži 400 ppm aktivne tvari. Nakon što se naslaga osušila, na biljke kelja stavi se 10 gusjenica trećeg stadija plutella xylostella i sve se stavi u plastičnu posudu. Nakon 3 dana vrši se numeričko izračunavanje. Iz usporedbe broja mrtvih gusjenica i šteta od grizotina na tretiranim sa onima na netretiranim biljkama, određuje se procentualna redukcija populacije odn. procentualna redukcija šteta od grizotina (% dlelovanja). Young kale plants are sprayed with an aqueous emulsion containing 400 ppm of the active substance. After the deposit has dried, 10 caterpillars of the third stage of plutella xylostella are placed on the kale plants and everything is placed in a plastic container. After 3 days, a numerical calculation is performed. The percentage reduction of the population or percentage reduction of bite damage (% chipping).
Spojevi tabela 1 do 7 pokazuju u ovom testu dobro djelovanje protiv plutella xylostella. Naročito spojevi 1.02 i 1.20 pokazuju djelovanje iznad 80%. The compounds of tables 1 to 7 show good activity against Plutella xylostella in this test. Especially the compounds 1.02 and 1.20 show activity above 80%.
Primjer B12: Example B12:
Djelovanje protiv adulta anthonomus grandis Action against adult anthonomus grandis
Mlade biljke pamuka poprskaju se sa vodenom emulzijom koja sadrži 4 00 ppm aktivne tvari. Nakon što se naslaga osuši, na biljke pamuka stavi se 10 adulta anthonomus grandis i sve se stavi u plastičnu posudu. 3 dana kasnije vrši se numeričko izračunavanje. Iz usporedbe broja mrtvih kornjaša i šteta od grizotina na tretiranim sa onima na netretiranim biljkama određuje se procentualna redukcija populacije odn,. procentualna redukcija šteta od grizotina (% djelovanja). Young cotton plants are sprayed with an aqueous emulsion containing 400 ppm of the active substance. After the layer has dried, 10 adult anthonomus grandis are placed on the cotton plants and everything is placed in a plastic container. 3 days later the numerical calculation is done. The percentage reduction of the population or. percentage reduction of bite damage (% effect).
Spojevi tabela 1 do 7 pokazuju u ovom testu dobro djelovanje protiv anthonomus grandis. Naročito spojevi 1.02, 1.20, 2.05, 5.155 i 5.706 pokazuju djelovanje iznad 80%. The compounds of tables 1 to 7 show good activity against anthonomus grandis in this test. Especially the compounds 1.02, 1.20, 2.05, 5.155 and 5.706 show activity above 80%.
Primjer B13: Example B13:
Djelovanje protiv puccinia graminis na pšenici Action against puccinia graminis on wheat
a) rezidualno zaštitno djelovanje: a) residual protective effect:
Biljke pšenice se sedam dana nakon klijanja poprskaju sa emulzijom dobivenom iz praška aktivne tvari (0,02% aktivne supstance). Nakon 24 sata tretirane biljke se inficiraju sa suspenzijom koja sadrži uredospore gljivica. Nakon inkubacije u trajanju od 48 sati kod 95-100% relativne vlage i na temperaturi oko 20ºC, inficirane biljke se stave u staklenik sa temperaturom od oko 22ºC. Procjena razvoja pikaca rdje vrši se 12 dana nakon infekcije. Seven days after germination, wheat plants are sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance). After 24 hours, the treated plants are infected with a suspension containing uredospores of the fungus. After incubation for 48 hours at 95-100% relative humidity and at a temperature of about 20ºC, the infected plants are placed in a greenhouse with a temperature of about 22ºC. The assessment of the development of rust spots is made 12 days after infection.
b) Sistemsko djelovanje: b) Systemic action:
Biljke pšenice se 5 dana nakon klijanja poliju sa emulzijom dobivenom iz praška za prskanje (0,006% aktivne supstance u odnosu na volumen tla). Nakon 48 sati tretirane biljke se inficiraju sa suspenzijom uredospora gljivice. Nakon inkubacije u trajanju od 48 sati kod 96-100% relativne vlage zraka i na oko 20ºC, inficirane biljke stave se u staklenik sa temperaturom od oko 22ºC. Procjena razvoja pikaca rdje vrši se 12 dana nakon infekcije. 5 days after germination, the wheat plants are sprinkled with an emulsion obtained from the spray powder (0.006% of the active substance in relation to the soil volume). After 48 hours, the treated plants are infected with a suspension of uredospores of the fungus. After incubation for 48 hours at 96-100% relative air humidity and at about 20ºC, the infected plants are placed in a greenhouse with a temperature of about 22ºC. The assessment of the development of rust spots is made 12 days after infection.
Spojevi iz tabela 1 do 7 pokazuju dobro djelovanje protiv puccinia gljivica. Naročito spoj 1.02 pokazuje djelovanje više od 80%. Netretirane, no inficirane kontrolne biljke okužene su sa puccinia 100%. The compounds from tables 1 to 7 show good activity against puccinia fungi. Especially the compound 1.02 shows an activity of more than 80%. Untreated but infected control plants were infected with puccinia 100%.
Primjer B14: Example B14:
Djelovanje protiv phythophthora infestans na paradajz Action against Phythophthora infestans on tomatoes
a) rezidualno zaštitno djelovanje: a) residual protective effect:
Nakon trotjednog priploda biljke paradajza poprskaju se sa emulzijom koja se dobila iz praška aktivne tvari (0,02% aktivne supstance). Nakon 24 sata tretirane biljke se inficiraju sa suspenzijom sporangija gljivica. Ocjenjivanje okuženosti gljivicama vršilo se nakon inkubacije inficiranih biljaka u trajanju od 5 dana kod 90-100% relativne vlage zraka i na 20ºC. After three weeks of breeding, the tomato plants are sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance). After 24 hours, the treated plants are infected with a suspension of fungal sporangia. Evaluation of fungal infection was performed after incubation of infected plants for 5 days at 90-100% relative air humidity and at 20ºC.
b) sistemsko djelovanje: b) systemic action:
Nakon trotjednog priploda, biljke paradajza polivene su sa emulzijom dobivenom iz praška aktivne tvari (0,006% aktivne supstance u odnosu na volumen zemlje). Pri tome se pazi, da emulzija ne dođe u kontakt sa dijelovima biljke iznad zemlje. Nakon 48 sati tretirane biljke su inficirane sa suspenzijom sporangija gljivica. Ocjena okuženosti gljivicama vrši se nakon inkubacije inficiranih biljaka u trajanju od 5 dana kod 90-100% relativne vlage zraka i na 20ºC. After three weeks of breeding, the tomato plants were watered with an emulsion obtained from the powder of the active substance (0.006% of the active substance in relation to the volume of the soil). In doing so, care must be taken that the emulsion does not come into contact with the parts of the plant above the ground. After 48 hours, the treated plants were infected with a suspension of fungal sporangia. Assessment of fungal infection is performed after incubation of infected plants for 5 days at 90-100% relative humidity and at 20ºC.
Spojevi iz tabela 1 do 7 pokazuju dobro zaštitno djelovanje protiv phytophthora gljivice. Naročito spojevi 1.02, 1.20, 1.164, 4.04 i 4.06 pokazuju dobro djelovanje iznad 80%. Netretirane, no inficirane kontrolne biljke bile su 100% okužene phytophthorom. The compounds from tables 1 to 7 show good protective activity against the fungus phytophthora. Especially compounds 1.02, 1.20, 1.164, 4.04 and 4.06 show a good activity above 80%. Untreated but infected control plants were 100% infected with phytophthora.
Primjer B15: Example B15:
Djelovanje protiv cercospora arachidicola na biljke zemnog oraha Action against cercospora arachidicola on peanut plants
10-15 cm visoke biljke zemnog oraha poprskaju se sa emulzijom dobivenom iz praška aktivne supstance (0,02% aktivne supstance) i 48 sati kasnije inficira se sa suspenzijom konidija gljivica. Inficirane biljke 72 sata se inkubiraju na oko 21ºC i na velikoj vlazi zraka i nakon pojave tipičnih mrlja na listovima, stavi se u staklenik. Ocjena fugicidnog djelovanja vrši se 12 dana nakon infekcije, temeljeno na broju i veličini mrlja. U usporedbi sa netretiranim, no inficiranim kontrolnim biljkama (broj i veličina mrlja = 100%), biljke zemnog oraha koje su bile tretirane sa aktivnim tvarima iz tabele 1 do 7, pokazuju reduciranu okuženost cercosporom. Naročito spoj 4.01 pokazuje djelovanje veće od 80%. 10-15 cm tall peanut plants are sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance) and 48 hours later they are infected with a suspension of fungal conidia. Infected plants are incubated for 72 hours at around 21ºC and with high air humidity, and after the appearance of typical spots on the leaves, they are placed in a greenhouse. The evaluation of the fugicidal action is performed 12 days after infection, based on the number and size of spots. Compared to untreated but infected control plants (number and size of spots = 100%), peanut plants that were treated with the active substances from Tables 1 to 7 show reduced cercospora infection. In particular, compound 4.01 shows an activity greater than 80%.
Primjer B16: Example B16:
Djelovanje protiv plasmopara viticola na lozi Action against Plasmopara viticola on vines
a) rezidualno – zaštitno djelovanje: a) residual - protective effect:
U stadiju sa 4 - 5 listova, iz sjemena iznikla loza poprska se sa emulzijom dobivenom od praška aktivne tvari (0,02% aktivne supstance). nakon 24 sata tretirane biljke se inficiraju sa suspenzijom sporangija gljivice. Nakon inkubacije od 6 dana kod 95-100% relativne vlage zraka i na 20ºC, procjenjuje se okuženost sa gljivicom. At the stage with 4 - 5 leaves, the vine grown from the seed is sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance). after 24 hours, the treated plants are infected with a suspension of fungal sporangia. After incubation for 6 days at 95-100% relative air humidity and at 20ºC, infection with the fungus is assessed.
b) kurativno djelovanje: b) curative effect:
Iz sjemena iznikla loza u stadiju sa 4-t listova inficira se sa suspenzijom sporangija gljivica. Nakon Inkubacije od 24 sata u vlažnoj komori kod 95-100% relativne vlage zraka i na 20ºC,, inficirane biljke poprskaju se sa emulzijom dobivenom od praška aktivne tvari (0,02% aktivne supstance). Nakon što se naslaga osuši, tretirane biljke se opet stave u vlažnu komoru. Ocjena okuženja gljivicama vrši se 6 dana nakon infekcije. The vines grown from the seeds in the stage with 4 leaves are infected with a suspension of fungal sporangia. After incubation for 24 hours in a humid chamber at 95-100% relative air humidity and at 20ºC, the infected plants are sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance). After the deposit has dried, the treated plants are again placed in the humid chamber. Assessment of fungal infection is performed 6 days after infection.
Spojevi iz tabela 1 do 7 pokazuju protiv plasmopara viticola dobro djelovanje. Naročito spoj 1.02 pokazuje djelovanje iznad 80%. Netretirane, no inficirane kontrolne biljke imale su naprotiv 100-postotno okuženje plasmoparom. The compounds from tables 1 to 7 show good activity against Plasmopara viticola. Especially the compound 1.02 shows activity above 80%. Untreated but infected control plants, on the other hand, had 100 percent contamination with plasmopara.
Primjer B17: Example B17:
Djelovanje protiv pyricularia oryzae na biljkama riže Action against pyricularia oryzae on rice plants
a) rezidualno zaštitno djelovanje a) residual protective action
Nakon dvotjednog priploda, biljke riže se poprskaju sa emulzijom dobivenom iz praška aktivne tvari (0,02% aktivne supstance). Nakon 48 sati tretirane biljke se inficiraju sa suspenzijom konidija gljivice. Nakon 5 dana inkubacije kod 96-100% relativne vlage zraka i na oko 22º'C ocjenjuje se okuženje gljivicama. After two weeks of breeding, the rice plants are sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance). After 48 hours, the treated plants are infected with a suspension of fungal conidia. After 5 days of incubation at 96-100% relative air humidity and at about 22º'C, fungal infection is evaluated.
b) sistemsko djelovanje b) systemic action
2 tjedna stare biljke riže zaliju se sa emulzijom dobivenom iz praška aktivne tvari (0,006% aktivne supstanco u odnosu na volumen zemlje). Potom se lonci toliko napune vodom, da najdonji dijelovi peteljka biljaka riže stoje u vodi. Nakon 96 sati se tretirane biljke inficiraju sa suspenzijom konidija gljivice. Nakon inkubacije inficiranih biljaka od 5 dana kod 95-100% relativne vlage zraka i na oko 24ºC ocjenjuje se okuženje gljivicama. 2-week-old rice plants are watered with an emulsion obtained from the powder of the active substance (0.006% of the active substance in relation to the volume of the soil). Then the pots are filled with water so much that the bottom parts of the stalks of the rice plants stand in the water. After 96 hours, the treated plants are infected with a suspension of fungal conidia. After incubation of infected plants for 5 days at 95-100% relative air humidity and at about 24ºC, fungal infection is assessed.
Biljke riže koje se tretiraju sa emulzijom na bazi aktivnih supstanca tabela 1 do 7, pokazuju u usporedbi sa netretiranim kontrolnim biljkama samo malo okuženje gljivicama. Naročito spoj 1.02 pokazuje djelovanje iznad 80%. Rice plants that are treated with an emulsion based on the active substances of Tables 1 to 7 show only a small fungal infection compared to untreated control plants. Especially the compound 1.02 shows activity above 80%.
Primjer B18: Example B18:
rezidualno-zaštitno djelovanje protiv venturia inaegualis na izdancima jabuka residual protective effect against venturia inaegualis on apple shoots
Sadnice jabuka sa 10-20 cm dugačkim svježim izdancima poprskaju se sa emulzijom dobivenom iz praška aktivne tvari (0,02% aktivne supstance). Nakon 24 sata se tretirane biljke inficiraju sa suspenzijom konidija gljivica. Biljke se 5 dana inkubiraju kod 90-100% relativne vlage zraka, nakon čega se 10 dana stave u staklenik sa temperaturom od 20-24ºC. Okuženje gljivicom ocjenjuje se 15 dana nakon infekcije. Apple seedlings with 10-20 cm long fresh shoots are sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance). After 24 hours, the treated plants are infected with a suspension of fungal conidia. The plants are incubated for 5 days at 90-100% relative air humidity, after which they are placed in a greenhouse with a temperature of 20-24ºC for 10 days. Infection with the fungus is assessed 15 days after infection.
Spojevi iz tabela 1 do 7 pokazuju dobro zaštitno djelovanje protiv venturia. Naročito spoj 1.02 pokazuje djelovanje veće od 80%. The compounds from Tables 1 to 7 show good protective action against venturi. In particular, compound 1.02 shows an activity greater than 80%.
Primjer B19: Example B19:
Djelovanje protiv erysiphe graminis na ječmu Action against erysipha graminis on barley
a) rezidualno-zaštitno djelovanje a) residual protective action
Oko 8 cm visoke biljke ječma poprskaju se sa emulzijom dobivenom od praška aktivne tvari (0,02 % aktivne supstance). Nakon 3-4 sata tretirane biljke se popraše sa konidijima gljivice. Inficirane biljke ječma stave se u staklenik sa temperaturom od oko 22ºC i okuženost gljivicama ocjenjuje se nakon 10 dana. About 8 cm tall barley plants are sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance). After 3-4 hours, the treated plants are dusted with fungal conidia. Infected barley plants are placed in a greenhouse with a temperature of about 22ºC and fungal infection is evaluated after 10 days.
b) sistemsko djelovanje b) systemic action
Oko 8 cm visoke biljke ječma zaliju se sa emulzijom dobivenom iz praška aktivne tvari (0,002% aktivne supstance u odnosu na volumen zemlje). Pri tome se pazilo, da emulzija ne dođe u kontakt sa nadzemnim dijelovima biljke. Nakon 48 sati tretirane biljke poprašene su sa konidijama gljivica. Inficirane biljke ječma stavljene su u staklenik sa temperaturom od oko 22ºC, a okuženost gljivicama ocijenjena je nakon 10 dana. About 8 cm tall barley plants are watered with an emulsion obtained from the powder of the active substance (0.002% of the active substance in relation to the volume of the soil). Care was taken to ensure that the emulsion did not come into contact with the above-ground parts of the plant. After 48 hours, the treated plants were dusted with fungal conidia. Infected barley plants were placed in a greenhouse with a temperature of about 22ºC, and fungal infection was evaluated after 10 days.
Spojevi Formula iz tabela 1 do 7pokazuju dobro djelovanje protiv erysiphe gljivica. Netretirane, no inficirane kontrolne biljke pokazuju okuženost gljivicama od 100%. Naročito spoj 11.02 pokazuje djelovanje više od 80%. Compounds Formulas from Tables 1 to 7 show good activity against erysipelas fungi. Untreated but infected control plants show 100% fungal infection. Especially the compound 11.02 shows an activity of more than 80%.
Primjer B20: Example B20:
Djelovanje protiv meloidogyne incognita na paradajzu Action against Meloidogyne incognita on tomatoes
Jajašca meloidogyne incognita umiješaju se u pijesak. Ta mješavina stavi se u glinene lonce od 200 ml (5000 jajašca po loncu). Istoga dana se posadi u svaki lonac po jedna 3 tjedna stara biljka paradajza i formulirana aktivna tvar stavi se u lonce pomoću "drench "-aplikacije (0,0006% aktivne supstance u odnosu na volumen tla). Biljke u loncima stave se u staklenik na temperaturi od 26 ±1ºC 1 relativnoj vlagi zraka od 60%, Nakon 4 tjedna vrši se evaluiranje pregledom biljaka na stvaranje kvržica na korijenima prema tzv. indeksu kvržica na korijenima ("Root-Knot Index"). Na netretiranim inficiranim kontrolnim biljkama stvorilo se mnogo kvržica na korijenima (=100%). Nasuprot tome, spojevi iz tabela 1 do 7 pokazuju dobro djelovanje (manje od 20% je kuženo). Meloidogyne incognita eggs are mixed into the sand. This mixture is placed in clay pots of 200 ml (5000 eggs per pot). On the same day, one 3-week-old tomato plant is planted in each pot and the formulated active substance is placed in the pots using a "drench" application (0.0006% of the active substance in relation to the soil volume). Potted plants are placed in a greenhouse at a temperature of 26 ±1ºC 1 relative humidity of 60%. After 4 weeks, the plants are evaluated by examining the formation of nodules on the roots according to the so-called root knot index ("Root-Knot Index"). Many root nodules were formed on untreated infected control plants (=100%). In contrast, compounds from Tables 1 to 7 show good activity (less than 20% infected).
Primjer B21: Example B21:
Djelovanje protiv heterodera glycines na soji Action against heterodera glycines on soybean
Pješčana zemlja infestira se sa jajašcima heterodera glycines, oko 6000 jajašca po loncu. Na kraju se supstance koje se trebaju ispitati, izmiješaju u odgovarajuće koncentracije. Tretirana i infestirana zemlja stavi se u lonce (180 ccm) i u svaki se posiju po tri zrna soje (cv. Maple Arrow). Svako tretiranje se tri puta ponovi. Lonci se na 27ºC četiri do pet tjedana inkubiraju u stakleniku. Potom se biljke pažljivo izvade iz lonaca, korijeni se operu i odredi se broj cista. Sandy soil is infested with heterodera glycines eggs, about 6000 eggs per pot. Finally, the substances to be tested are mixed in appropriate concentrations. Treated and infested soil is placed in pots (180 cc) and three soybeans (cv. Maple Arrow) are sown in each pot. Each treatment is repeated three times. The pots are incubated at 27ºC for four to five weeks in a greenhouse. Then the plants are carefully removed from the pots, the roots are washed and the number of cysts is determined.
Spojevi iz tabela 1 do 7 pokazuju dobro djelovanje protiv heterodera glycines, što se vidi u gotovo potpunoj redukciji stvaranja cista. The compounds from Tables 1 to 7 show good activity against heterodera glycines, which can be seen in the almost complete reduction of cyst formation.
Claims (35)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH267492 | 1992-08-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
HRP931151A2 true HRP931151A2 (en) | 1996-06-30 |
Family
ID=4239036
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
HR931151A HRP931151A2 (en) | 1992-08-28 | 1993-08-27 | Indazole derivatives |
Country Status (8)
Country | Link |
---|---|
CN (1) | CN1091426A (en) |
AU (1) | AU4949293A (en) |
HR (1) | HRP931151A2 (en) |
IL (1) | IL106735A0 (en) |
MX (1) | MX9305171A (en) |
TR (1) | TR27142A (en) |
WO (1) | WO1994005642A1 (en) |
ZA (1) | ZA936305B (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08277287A (en) * | 1995-02-09 | 1996-10-22 | Mitsubishi Chem Corp | Indazoles and their use |
WO2002083647A1 (en) * | 2001-04-06 | 2002-10-24 | Nihon Nohyaku Co., Ltd. | Pyrazolecarboxamide derivative, intermediate therefor, and pest control agent containing the same as active ingredient |
MXPA04012704A (en) * | 2002-06-19 | 2005-03-23 | Schering Corp | Cannabinoid receptor agonists. |
FR2845382A1 (en) | 2002-10-02 | 2004-04-09 | Sanofi Synthelabo | INDAZOLECARBOXAMIDE DERIVATIVES, THEIR PREPARATION AND THEIR USE IN THERAPEUTICS |
FR2867778B1 (en) | 2004-03-16 | 2006-06-09 | Sanofi Synthelabo | USE OF INDAZOLECARBOXAMIDE DERIVATIVES FOR THE PREPARATION OF A MEDICAMENT FOR THE TREATMENT AND PREVENTION OF MALARIA |
ITMI20062230A1 (en) | 2006-11-22 | 2008-05-23 | Acraf | 2-ALCHIL-INDAZOLIC COMPOUND PROCEDURE FOR PREPARATION AND PHARMACEUTICAL COMPOSITION THAT INCLUDES IT |
UA100291C2 (en) * | 2008-08-01 | 2012-12-10 | Байєр Кропсайнс Аг | Fungicide n-cycloalkyl-n-biphenylmethyl-carboxamide derivatives |
CN102464618B (en) | 2010-11-03 | 2014-07-23 | 中国中化股份有限公司 | Pyrazolecarboxamide compound and application thereof |
KR101373185B1 (en) | 2010-12-17 | 2014-03-13 | 주식회사경농 | Indazole derivatives and insecticide composition comprising same |
WO2018108156A1 (en) * | 2016-12-16 | 2018-06-21 | 成都先导药物开发有限公司 | Rock inhibitor and application thereof |
CN112514904B (en) * | 2021-01-26 | 2021-10-26 | 青岛农业大学 | Application of benzydamine hydrochloride in preparation of bactericide for preventing and treating plant diseases caused by plant pathogenic bacteria |
CN113372276B (en) * | 2021-05-25 | 2022-04-22 | 三峡大学 | Indazole derivative and application thereof |
CN115536586B (en) * | 2021-06-30 | 2024-08-09 | 华东理工大学 | Pyrazole amide compound as well as preparation method and application thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6425763A (en) * | 1987-04-24 | 1989-01-27 | Mitsubishi Chem Ind | Pyrazoles and insecticide and acaricide containing said pyrazoles as active ingredient |
US4861777A (en) * | 1987-09-11 | 1989-08-29 | Mitsubishi Kasei Corporation | Pyrazole derivative and insecticidal and miticidal composition containing the derivative as active ingredient |
AU626402B2 (en) * | 1989-04-19 | 1992-07-30 | Sumitomo Chemical Company, Limited | An amide compound and its production and use |
-
1993
- 1993-08-18 WO PCT/EP1993/002203 patent/WO1994005642A1/en active Application Filing
- 1993-08-18 AU AU49492/93A patent/AU4949293A/en not_active Abandoned
- 1993-08-19 IL IL106735A patent/IL106735A0/en unknown
- 1993-08-26 TR TR00728/93A patent/TR27142A/en unknown
- 1993-08-26 MX MX9305171A patent/MX9305171A/en unknown
- 1993-08-27 ZA ZA936305A patent/ZA936305B/en unknown
- 1993-08-27 CN CN93116911A patent/CN1091426A/en active Pending
- 1993-08-27 HR HR931151A patent/HRP931151A2/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
WO1994005642A1 (en) | 1994-03-17 |
MX9305171A (en) | 1994-02-28 |
AU4949293A (en) | 1994-03-29 |
TR27142A (en) | 1994-11-09 |
CN1091426A (en) | 1994-08-31 |
IL106735A0 (en) | 1993-12-08 |
ZA936305B (en) | 1994-02-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2240738C (en) | Pesticidal composition containing thiamethoxam and fungicides | |
AU664846B2 (en) | Cyanophenylpyrroles | |
US5985921A (en) | 2-Phenyl-2-methoxyimino acetic acid esters | |
HRP931151A2 (en) | Indazole derivatives | |
US5763481A (en) | Vinylcarboxylic acid derivatives | |
US5358957A (en) | Butyric acid derivatives | |
AU721427B2 (en) | Pesticidal compositions | |
WO1998006710A1 (en) | Substituted 4-nitroimino-perhydro-1,3,5-oxadiazine derivatives, their use as pesticides and intermediates for their preparation | |
ES2294789T3 (en) | DERIVATIVES OF INDAZOL PESTICIDES. | |
US6048824A (en) | 2-nitromethylidene/2-cyanimino/2-nitro-imino-pyrrolidines and piperidines, intermediates, and their use as pesticides | |
WO1994005633A1 (en) | 3-cyano-4-halogeno-2-(subst.phenyl)-pyrroles as pesticides and fungicides | |
NZ270235A (en) | Substituted sulphonyloxy benzophenone hydrazone derivatives; pesticides | |
JPH06184084A (en) | Carbamic acid derivative | |
JP4015788B2 (en) | Pest control agent | |
WO1995029889A1 (en) | Perhaloalkoxybenzenophenone hydrazones and their use as pesticides |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A1OB | Publication of a patent application | ||
OBST | Application withdrawn |