DK156934B - Fungicide og biocide cyclopropancarboxylsyrer med en polyhalogeneret gruppe - Google Patents
Fungicide og biocide cyclopropancarboxylsyrer med en polyhalogeneret gruppe Download PDFInfo
- Publication number
- DK156934B DK156934B DK414577AA DK414577A DK156934B DK 156934 B DK156934 B DK 156934B DK 414577A A DK414577A A DK 414577AA DK 414577 A DK414577 A DK 414577A DK 156934 B DK156934 B DK 156934B
- Authority
- DK
- Denmark
- Prior art keywords
- cyclopropane
- carboxylic acid
- dimethyl
- ppm
- cis
- Prior art date
Links
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 title claims description 17
- 230000000855 fungicidal effect Effects 0.000 title claims description 14
- 230000003115 biocidal effect Effects 0.000 title claims description 12
- 239000003139 biocide Substances 0.000 title description 4
- 239000000417 fungicide Substances 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 31
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 15
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000004480 active ingredient Substances 0.000 claims description 11
- GKIRPKYJQBWNGO-OCEACIFDSA-N clomifene Chemical compound C1=CC(OCCN(CC)CC)=CC=C1C(\C=1C=CC=CC=1)=C(\Cl)C1=CC=CC=C1 GKIRPKYJQBWNGO-OCEACIFDSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- ZSLSWXUSULSWQT-QRHDOFTISA-N (1r,3r)-3-(1,2-dibromo-2,2-difluoroethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@H](C(Br)C(F)(F)Br)[C@H]1C(O)=O ZSLSWXUSULSWQT-QRHDOFTISA-N 0.000 claims description 2
- VOEOAOWTEZOVCB-QRHDOFTISA-N (1r,3r)-3-(2,2-dibromo-1,2-dichloroethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@H](C(Cl)C(Cl)(Br)Br)[C@H]1C(O)=O VOEOAOWTEZOVCB-QRHDOFTISA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 3
- 125000001153 fluoro group Chemical group F* 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 29
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 28
- 239000002253 acid Substances 0.000 description 20
- 239000000460 chlorine Substances 0.000 description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910052794 bromium Inorganic materials 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 241000786363 Rhampholeon spectrum Species 0.000 description 7
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 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 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 229940126062 Compound A Drugs 0.000 description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- JLNTWVDSQRNWFU-UHFFFAOYSA-N OOOOOOO Chemical compound OOOOOOO JLNTWVDSQRNWFU-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 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 3
- 238000000034 method Methods 0.000 description 3
- 230000000361 pesticidal effect Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NUQSJBAQSZZDJA-OVEKKEMJSA-N (1r,3s)-2,2-dimethyl-3-(1,2,2,2-tetrachloroethyl)cyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@@H](C(Cl)C(Cl)(Cl)Cl)[C@H]1C(O)=O NUQSJBAQSZZDJA-OVEKKEMJSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 241001465180 Botrytis Species 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KUGRPPRAQNPSQD-UHFFFAOYSA-N OOOOO Chemical compound OOOOO KUGRPPRAQNPSQD-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000001408 fungistatic effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229960004029 silicic acid Drugs 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- NUQSJBAQSZZDJA-QRHDOFTISA-N (1r,3r)-2,2-dimethyl-3-(1,2,2,2-tetrachloroethyl)cyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@H](C(Cl)C(Cl)(Cl)Cl)[C@H]1C(O)=O NUQSJBAQSZZDJA-QRHDOFTISA-N 0.000 description 1
- CYCYDSJDZNVSPP-QRHDOFTISA-N (1r,3r)-3-(1,2-dibromo-2,2-dichloroethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@H](C(Br)C(Cl)(Cl)Br)[C@H]1C(O)=O CYCYDSJDZNVSPP-QRHDOFTISA-N 0.000 description 1
- LLMLSUSAKZVFOA-NJGYIYPDSA-N (1r,3r)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@@H](C=C(Cl)Cl)[C@H]1C(O)=O LLMLSUSAKZVFOA-NJGYIYPDSA-N 0.000 description 1
- CYCYDSJDZNVSPP-OVEKKEMJSA-N (1r,3s)-3-(1,2-dibromo-2,2-dichloroethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@@H](C(Br)C(Cl)(Cl)Br)[C@H]1C(O)=O CYCYDSJDZNVSPP-OVEKKEMJSA-N 0.000 description 1
- ZSLSWXUSULSWQT-OVEKKEMJSA-N (1r,3s)-3-(1,2-dibromo-2,2-difluoroethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@@H](C(Br)C(F)(F)Br)[C@H]1C(O)=O ZSLSWXUSULSWQT-OVEKKEMJSA-N 0.000 description 1
- VOEOAOWTEZOVCB-OVEKKEMJSA-N (1r,3s)-3-(2,2-dibromo-1,2-dichloroethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@@H](C(Cl)C(Cl)(Br)Br)[C@H]1C(O)=O VOEOAOWTEZOVCB-OVEKKEMJSA-N 0.000 description 1
- MDIQXIJPQWLFSD-XINAWCOVSA-N (1r,3s)-3-(2,2-dibromoethenyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@H](C=C(Br)Br)[C@H]1C(O)=O MDIQXIJPQWLFSD-XINAWCOVSA-N 0.000 description 1
- LLMLSUSAKZVFOA-XINAWCOVSA-N (1r,3s)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@H]1C(O)=O LLMLSUSAKZVFOA-XINAWCOVSA-N 0.000 description 1
- 101150025032 13 gene Proteins 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- ZSLSWXUSULSWQT-UHFFFAOYSA-N 3-(1,2-dibromo-2,2-difluoroethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(Br)C(F)(F)Br)C1C(O)=O ZSLSWXUSULSWQT-UHFFFAOYSA-N 0.000 description 1
- IRUJOJCSYSMRHD-UHFFFAOYSA-N 3-(1,2-dichloro-2-fluoroethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(Cl)C(F)Cl)C1C(O)=O IRUJOJCSYSMRHD-UHFFFAOYSA-N 0.000 description 1
- DSTFRXBZHUSPOE-UHFFFAOYSA-N 3-(2-chloro-2-fluoroethenyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C=C(F)Cl)C1C(O)=O DSTFRXBZHUSPOE-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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000235390 Absidia glauca Species 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 101100352919 Caenorhabditis elegans ppm-2 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000009849 Cucumis sativus Nutrition 0.000 description 1
- 101100298295 Drosophila melanogaster flfl gene Proteins 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 241000221779 Fusarium sambucinum Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000588915 Klebsiella aerogenes Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000228143 Penicillium Species 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 241001503951 Phoma Species 0.000 description 1
- 241001207509 Phoma sp. Species 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 241000607715 Serratia marcescens Species 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 239000012336 iodinating agent Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- -1 organic base salt Chemical class 0.000 description 1
- 244000045947 parasite Species 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
- C07D209/49—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide and having in the molecule an acyl radical containing a saturated three-membered ring, e.g. chrysanthemumic acid esters
-
- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/15—Saturated compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Environmental Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Communicable Diseases (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Pharmacology & Pharmacy (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oncology (AREA)
- Veterinary Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Indole Compounds (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Fodder In General (AREA)
- Furan Compounds (AREA)
Description
DK 156934 B
- i -
Opfindelsen angâr hidtil ukendte fungicide og biocide cyc-lopropancarboxylsyrer med en polyhalogeneret gruppe i aile deres mulige isomere former og ejendommelige ved den i krav 1 angivne almene formel I.
5
Disse cyclopropancarboxylsyrer har i 1- og 3-stillingen asymmetriske carbonatomer og kan altsâ eksistere i flere stereoisomere former.
10 For en bestemt sterisk konfiguration af de asymmetriske carbonatomer i 1- og 3-stillingen i cyclopropanringen kan der desuden eksistere to diastereoisomere former af disse syrer som folge af eksistensen af det asymmetriske carbon-atom i 1'-stillingen i den substituerede ethylsidekæde, og 15 de kan effektivt karakteriseres ved navnlig deres N.M.R.
spektrum eller deres vandringshastighed ved tyndtlags-chromatografi. Disse isomere kan normalt separeres og iso-leres i ren tilstand, især ved chromatografi. Disse to diastereoisomere skal her og i det folgende betegnes 20 isomer A og isomer B.
, 1 2 3 I det tilfælde, hvor de tre substituenter X , X og X er indbyrdes forskellige, kan der eksistere et yderligere asymmetrisk carbonatom i 2'-stillingen i den polyhalogene-25 rede ethylsidekæde.
Blandt forbindelserne med den almene formel I skal især nævnes sâdanne, som er e jendommelige ved, at X"*" betegner 2 1 fluor, chlor eller brom, X er identisk med X og betegner 3 30 fluor, chlor eller brom, og X har samme betydning som ovenfor, og sâdanne, som er ejendommelige ved, at X^ beteg- 2 1 ner fluor, chlor eller brom, X er forskellig fra X og 3 betegner fluor, chlor eller brom, og X har samme betydning som ovenfor.
35
DK 156934B
- 2 -
Blandt de fungicide og biocide syrer med formlen I ifolge. opfindelsen skal nævnes folgende cyclopropancarboxylsyrer (K) med (lR,cis)- eller (IR,trans)-struktur: 5 - 2,2-dimethyl-3-(21f2'-dibrom-l'r2'-dichlorethyl)-cyclo- propan—1-carboxylsyre, 2.2- dimethyl-3-(1*,2*,2* r2*-tetrachlorethyl)-cyclopropan- 1-carboxylsyre, 2.2- dimethyl-3-(2', 21-difluor-11,2'-dichlorethyl)-cyc- 10 lopropan-l-carboxylsyre, 2.2- dimethyl-3-(2',2'-dichlor-11,2'-dibromethyl)-cyclo-propan-1-carboxylsyre, - 2,2-dimethyl-3-(2',2'-difluor-1',2'-dibromethyl)-cyclo-propan-1-carboxylsyre, 15 - 2,2-dimethyl-3- (1^2^2^21 -tetrabromethyl ) -cyclopro pan-1-carboxyl syre f 2.2- dimethyl-3-(2 *,21-difluor-2',11-diiod-ethyl)-cyclo-propan-1-carboxylsyre, - 2,2-dimethyl-3-(2',2 *-dichlor-2', 11-diiod-ethyl)-cyclo- 20 propan-l-carboxylsyre, 2 ,2-dimethyl-3-( 2 ', 21-dibrom-21,11-diiodethyl)-cyclopro-• ; pan-l-carboxylsyref - 2,2-dimethyl-3- ( 1 ', 2 ', 2 ' -tribromethyl ) -cyclopropan-1-carboxy1syre, 25 - 2,2-dimethyl-3-(1', 2 '-dichlor-2'-bromethyl)-cyclopropan- 1-carboxylsyre, - 2,2-dimethyl-3-(1',2',2'-trichlorethyl)-cyclopropan-1-carboxylsyre, 2.2- dimethyl-3-( 1 ', 21-dibrom-21-chlorethyl)-cyclopropan- 30 1-carboxylsyre, 2.2- dimethyl-3-( 1 ', 2 '-dichlor-2'-fluorethyl)-cyclopropan- 1-carboxylsyr e, 2.2- dimethyl-3-(1r, 21-dibrom-2'-fluorethyl)-cyclopro-pan-1-carboxylsyre, 35 - 2,2-dimethyl-3-(2’-fluor-2',1'-diiodethyl)-cyclopropan- 1-carboxylsyre, - 3 -
DK 156934 B
2.2- dimethyl-3-(21-chlor-2',1'-diiodethyl)-cyclopro-pan-l-carboxylsyre, 2.2- dimethyl-3-(2'-brom-2', 1 '-diiodethyl)-cyclopro-pan-l-carboxylsyre, 5 - 2,2-dimethyl-3-(11,2',2'-trichlor-2'-fluorethyl)-cyclo- propan- 1-carboxy1syre, 2.2- dimethyl-3-(1 ' , 2 '-dibrom-2'-chlor-2'-fluorethyl)--cyclopropan-l-carboxylsyre, 2.2- dimethyl-3- ( 1 ' , 2 1 ,2 ' -trichlor-2 ' -bromethyl ) -cyclo- 10 propan-l-carboxylsyre, 2.2- dimethyl-3- ( 1 ' , 2 ', 2 ' -tribrom-2 1 -chlorethyl ) -cyclopropan-l-carboxylsyre, 2.2- dimethyl-3-(2'-fluor-1',2',2'-tribromethyl)-cyclopropan-l-carboxylsyre, 15 - 2,2-dimethyl-3-(21-brom-2'-fluor-11,21-dichlorethyl)- cyclopropan-l-carboxylsyre, 2.2- dimethyl-3-(2'-fluor-21-chlor-2',1'-diiodethyl)-cyclopropan-l-carboxylsyre, 2.2- dimethyl-3-(21-fluor-2'-brom-21 ,1 '-diiodethyl)- 20 cyclopropan-l-carboxylsyre og 2.2- dimethyl-3-(2'-chlor-2'-brom-21,11-diiodethyl)-cyclopropan-l-carboxylsyre.
Blandt disse syrer skal især nævnes folgende syrer under en 25 vilkârlig af deres isomere former og navnlig i form af iso mer A, isomer B eller en blanding af disse isomere: (IR,cis)-2,2-dimethyl-3-(1*,2',2'r2*-tetrabromethyl)-cyclopropan-l-carboxylsyre, 30 - (lR,trans)-2,2-dimethyl-3-(12221-tetrabromethyl)- cyclopropan-l-carboxylsyre, (lR,trans)-2,2-dimethyl-3-(2',2'-dichlor-1',2'-dibrom-ethyl)-cyclopropan-l-carboxylsyre, (IR,cis)-2,2-dimethyl-3-(2',2'-dibrom-1',2'-dichlor-35 ethyl)-cyclopropan-l-carboxylsyre, (lR,trans)-2,2-dimethyl-3-(2',2'-dibrom-1’,2'-dichlorethyl )-cyclopropan-l-carboxylsyre, - 4 -
DK 156934 B
(lR,trans)-2f2-dimethyl-3-(21,2'-difluor-11,2'-dibrom-ethy1-cyclopropan-1-carboxy1syre, (lR,cis)-2,2-dimethyl-3-(2',2'-dichlor-1',2'-dibrom-ethyl)-cyclopropan-l-carboxylsyre, 5 - (lRrCisî^^-dimethyl-S-^1,2' ,2',11-tetrachlorethyl)- cyclopropan-l-carboxylsyre og (IR,trans)-2,2-dimethy1-3-(212 ', 2 ', 1 '-tetrachlorethyl)-cyclopropan-l-carboxylsyre.
10 De ni ovennævnte produkter betegnes som produkter K.
Ligeledes kan nævnes: (lR,cis)-2,2-dimethy1-3-(2',2'-difluor-2', 1 '-dibrom-ethyl)-cyclopropan-l-carboxylsyre og 15 - (lR,cis)-3-(2'-(RS)-fluor-2'-chlor-1',21-dibromethyl)- cyclopropan-l-carboxylsyre.
De omhandlede forbindelser fremstilles ved, at man omsætter en syre med den almene formel II, 20
1 π VX /CII3 O
x i XX II (II)
= c / c-OH
25 / 2 hvor X og X har samme betydnxng som i krav 1, og hvxlken syre II foreligger i en vilkârlig af sine isomere former, 30 eller et af dens funktionelle derivater med et chlore- rings-, bromerings- eller ioderingsmiddel, som er i stand til at fiksere Cl2, Br2 eller I2til siclekæden i syren II, og at man eventuelt, hvis man har benyttet en syre som udgangsprodukt, omdanner den opnâede syre til funktionelt 35 dérivât.
Som halogeneringsmiddel for esterne II benytter man især chlor, brom eller iod, og halogeneringen af esterne II ud- - 5 -
DK 156934 B
f0res da i et organisk oplosningsmiddel, som ikke reagerer med chlor, brom eller iod, sâsom eddikesyre, carbontetra-chlorid, chloroform eller methylenchlorid.
5 Det funktionelle dérivât af syren II kan især være anhydri- det, et blandet anhydrid, en lavmolekylær alkylester, et metalsalt, et organisk basesalt eller fortrinsvis syrechlo-ridet.
10 Den éventuelle omdannelse til et funktionelt dérivât som defineret ovenfor sker, i det tilfælde, hvor man har benyt-tet en syre med formlen II som udgangsprodukt ved frem-gangsmâden, efter gængse metoder.
15 Cyclopropancarboxylsyrerne (K) ovenfor har fungicide egen- skaber, som gor dem egnede til at benyttes i bekæmpelsen af svampe. De kan især benyttes i kampen mod parasitsvampe pâ omrâder som fx druer, tomater og agurker.
20 Forsog pâ Botrytis, Fusarium, Phoma, Pénicillium, som er beskrevet nedenfor i den eksperimentelle del, pâviser den fungicide virkning af disse syrer.
Opfindelsen angâr ligeledes fungicide midler, der som aktiv 25 bestanddel indeholder i det mindste en af syrerne (K) defi neret som ovenfor.
I disse produkter kan den eller de aktive bestanddele even-telt være tilsat et eller flere andre pesticide midler.
30 Disse produkter kan foreligge i form af pudder, granulat, suspensioner, emulsioner, oplosninger eller andre præpara-ter, som gængs benyttes ved anvendelsen af denne slags for-bindelser.
35 Foruden den aktive bestanddel indeholder disse produkter normalt et bærestof og/eller et ikke-ionisk overfladeaktivt stof, som desuden sikrer en ensartet fordeling af blandin- - 6 -
DK 156934B
gens bestanddele. Det benyttede bærestof kan være en væske sâsom vand, éthanol, carbonhydrider eller andre organiske oplosningsmidler, en mineralolie, en animalsk eller vegeta-bilsk olie eller et pudder sâsom talkum, 1er, silicater og 5 kiselgur.
De fungicide midler indeholder fortrinsvis i tilfælde af pudder til forstovning 25-95 vægtprocent aktivt stof, i tilfælde af pudder til lovpudring 2,5-95 vægtprocent aktivt 10 stof og i tilfælde af pudder eller væske til forstovning pâ jorden 10-30 vægtprocent aktivt stof.
Cyclopropancarboxylsyrerne K ovenfor har ligeledes bakteri-cide egenskaber, som gor dem egnede til at benyttes som in-15 dustrielle biocider.
Forsog anfort nedenfor i den eksperimentelle del og udfort under betingelser analoge med dem, som findes ved bekæmpel-sen af bakterier i industrielt milje, illustrerer den hoje 20 biocide virkning af disse syrer.
Disse forsog er blevet udfort for lim og for industrielle fyldstoffer af typen kaolinopslæmning inficeret med en kom-pleks blanding af bakterier, som normalt udvikler sig i in-25 dustrielle substrater.
De ovennævnte cyclopropancarboxylsyrer K kan altsâ anvendes generelt om industrielle biocider, især til beskyttelse af lim og industrielle fyldstofer samt under anvendelsen af 30 skæreolier. De kan ligeledes benyttes til forebyggelse og eliminering af dannelsen af mikrobielt snavs i kredslob i papirindustrien og til behandling af huder, garvevæsker og læder.
35 - 7 -
DK 156934 B
Opfindelsen angâr ligeledes biocide midler, der som aktiv bestanddel indeholder i det mindste en af syrerne K define-ret som ovenfor.
5 I disse produkter kan den eller de aktive bestanddele til- sættes et eller flere andre pesticide midler. Disse produkter kan foreligge i de samme former som de ovenfor be-skrevne fungicide produkter, dvs. i form af pudder, suspen-sioner, emulsioner eller oplosninger og kan foruden den el-10 1er de aktive bestanddele indeholde et fast eller flydende bærestof og et overfladeaktivt stof.
De biocide produkter indeholder fortrinsvis 20-95 vægtpro-15 cent aktivt stof.
Desuden er cyclopropancarboxylsyrerne med formlen I define-ret som ovenfor egnede mellemprodukter i syntesen af hidtil ukendte estere af disse syrer, hvilke estere har bemærkel-20 sesværdige insekticide, acaricide, nematodicide og fungici de egenskaber. Disse estere samt de forskellige pesticide produkter, som indeholder dem, er beskrevet i DK-ansogning nr. 4144/77 med betegnelsen "Pesticide, især insekticide estere af cyclopropancarboxylsyrer med en polyhalogeneret 25 substituent samt fremgangsmàde til fremstilling deraf".
Fremstillingen af syrerne med formlen I samt visse af deres funktionelle derivater og anvendelsen af syrerne og dériva-terne til fremstilling af nogle insekticide estere er be-30 skrevet nedenfor i den eksperimentelle del.
Nedenstâende eksempler samt undersogelsen af den fungicide og biocide virkning af forbindelserne K illustrerer opfindelsen.
35
DK 156934 B
- 8 -
Eksempel 1 (IR,cis)-2,2-dimethyl-3-(11,2',2',21-tetrabromethyl)-cyclopropan-l-carboxylsyre I 150 ml carbontetrachlorid indf0rer man 19,4 g (lR,cis)-5 2,2-dimethyl-3-(2',2'-dibromvinyl)-cyclopropan-l-carboxyl- syre, og man tilsætter 10,4 g brom oplost i 22 ml carbontetrachlorid, omrorer i 1 time ved 20°C, inddamper til t0rhed ved destination under formindsket tryk og fâr 31,4 g râ-produkt med smp. 145°C. Dette râprodukt omkrystallisérés 10 af 110 ml carbontetrachlorid, og man fâr 22,12 g (lR,cis)- 2,2-dimethyl-3-( 1 ^2^2^21 -tetrabromethyl ) -cyclopropan-l-carboxylsyre med smp. 150°C.
Dette produkt er en blanding af isomer A og isomer B, hvil-15 ket pâvises ved N.M.R.spektrum. N.M.R.spektret gpr det mu- ligt at pâvise en forbindelse (svarende til ca. 2/3 af blandingen) med toppe ved 1,31-1,43 ppm svarende til hydro-genatomerne i tvillingmethylgrupperne og toppe fra 5,33 til 5,66 ppm svarende til hydrogenatomet bundet til det mono-20 bromerede asymmetriske carbonatom samt en anden forbindelse (svarende til ca. 1/3 af blandingen) med toppe ved 1,28 1,48 ppm svarende til hydrogenatomerne i tvillingmethylgrupperne og toppe fra 4,24 til 5,34 ppm svarende til hydrogenatomet bundet til det monobromerede asymmetriske car-25 bonatom.
35 blandingen pâviser man desuden toppe fra 1,67 til 2,17 ppm (hydrogenatomer i 1- og 3-stillingen i cyclopropan) og en top ved ca. 11,25 ppm (mobilt hydrogen i syregruppen).
30
Den opnâede blanding har smp. 150°C og folgende Analyse: CgH^Br^C^ = 457,804 beregnet: C% 20,99 H% 2,20 Br% 69,82 fundet: 20,9 2,2 70,2 - 9 -
DK 156934 B
Eksempel 2 (lR,trans) -2,2-dimethyl-3-(l1,2' ,2' ,2'-tetrabromethyl)--cyclopropan-l-carboxylsyre
Denne forbindelse fâs ved bromering af (lR,trans)-2,2-dime-5 thyl-3-(2',2'-dibromvinyl)-cyclopropan-l-carboxylsyre, blanding af is.omer A og B, pâ den i eksempel 1 beskrevne mâde.
N.M.R.Spektrum: •LO Toppe fra 1,30 til 1,40 ppm (hydrogenatomer i methyl- grupperne i 2-stillingen i cyclopropan), toppe ved 1,65-1,74 og 1,97-2,37 ppm (hydrogenatomer i 1- og 3-stillingen i cyclopropan), toppe ved 4,30-4,47 og ved 4,47-4,65 ppm (hydrogen i 11-stillingen i ethyl), top ]_5 ved 9,63 ppm (hydrogen i carboxylgruppen) .
Eksempel 3 (lR,trans)-2,2-dimethyl-3-(2',21-dichlor-1*,21-dibromethyl) -cyclopropan-l-carboxylsyre 20 Ved indvirkning af brom pâ (lR,trans)-2,2-dimethyl-3-(2,f- 2'-dichlorvinyl)-cyclopropan-l-carboxylsyre fâr man (IR,trans)-2,2-dimethy1-3-(2',2'-dichlor-1',2'-dibromethyl) -cyclopropan-l-carboxylsyre, blanding af isomer A og B.
25 N.M.R.spektrum:
Toppe ved 1,17-1,37 ppm (hydrogenatomer i methylgrup-perne i 2-stillingen i cyclopropan), toppe fra 1,65-1,73 ppm, ved 1,93-2,03 ppm (hydrogenatomer i 1-stil-lingen i cyclopropan), toppe ved 4,23-4,45 og 4,45-30 4,62 ppm (hydrogen i 11-stillingen i ethyl i 3-stil lingen i cyclopropan).
Eksempel 4 (lR,cis)-2,2-dimethyl-3-(2',21-dibrom-11,2'-dichlorethyl)-35 cyclopropan-l-carboxylsyre I 30 ml carbontetrachlorid indforer man ved gennembobling ved -15°C 11,8 g chlor, og derpâ tilsætter man langsomt ved
DK 156934 B
- 10 - -10°C 24 g af en oplosning af (1Κ,σΪ3)-2,2-ά^β^γ1-3-(2', 2'-dibroiiivinyl)-cyclopropan-l-carboxylsyre i 37 ml methy-lenchlorid, omrorer 1 time 30 minutter ved 0°C og 2 timer ved 25°C, inddamper under formindsket tryk, renser ved 5 krystallisation af carbontetrachlorid og fâr 7,4 g (lR,cis) -2,2-dimethyl-3-(21,2T-dibrom-11,2'-dichlorethyl)-cyclopro-pan-l-carboxylsyre med smp. 134°C, blanding af isomer A og B.
10 N.M.R.spektrum:
Toppe ved 1,32-1,44 og ved 1,28-1,48 ppm (hydrogenato-mer i methylgrupperne i 2-stillingen i cyclopropan), toppe ved 5,08-5,45 og ved 4,67-5,0 ppm (hydrogen i 11-stillingen i ethylkæden i 3-stillingen i cyclopro-15 pan), top ved 10,1 ppm (hydrogen i carboxylgruppen).
Eksempel 5 (lR,trans)-2,2-dimethyl-3-(2l,21-dibrom-11^'-dichlorethyl) -cyclopropan-l-carboxylsyre 20 I en blanding af 20 ml carbontetrachlorid og 20 ml methy- lenchlorid indforer man 24 g (lR,trans)-2,2-dimethyl-3-(2', 21-dibromvinyl)-cyclopropan-l-carboxylsyre, afkoler til -10°C, mætter oplosningen med chlor, anbringer en opadsti-gende koler pâ reaktionsbeholderen og med tilforsel af et 25 fluidum ved -60°C (methanol og kulsyreis) til undgâelse af tab af chlor, omrorer i 2 timer 30 minutter ved -10°C og derefter i 1 time 30 minutter ved 10°C, lader overskuddet af chlor dampe af, eliminerer opl0sningsmidlerne ved de-stillation under formindsket tryk, renser resten (35,5 g) 30 ved chromatografi pâ silicagel under eluering med en blan ding af cyclohexan, ethylacetat og eddikesyre (75:25:1) og derefter med en blanding af samme oplesningsmidler i for-holdet 80:20:1 og fâr 16,3 g (lR,trans)-2,2-dimethyl-3-(2', 21-dibrom-1',2'-dichlorethyl)-cyclopropan-l-carboxylsyre.
N.M.R.spektrum (deuterochloroform):
Toppe ved 1,33-1,56 ppm, karakteristiske for hydrogen- 35
DK 156934 B
- Il - atomerne i tvillingmethylgrupperne i 2-stillingen i cyclopropyl, toppe ved 1,70-2,25 ppm, karakteristiske for hydrogenatomerne i 1- og 3-stillingen i cyclopropyl, toppe ved 4,10-4,38 ppm, karakteristiske for hy-5 drogenet i 1'-stillingen i den substituerede ethyl- sidekæde, top ved 10,9 ppm, karakteristisk for hydro-genatomet i carboxylgruppen.
Eksempel 6 10 (lR,trans)-2,2-dimethyl-3-(2',21-difluor-11,2'-dibromethyl) -cyclopropan-l-carboxylsyre I analogi med det ovenfor anforte vil man ved indvirkning af brom pâ (lRitransi^^-dimethyl-S-^1,21-difluorvinyl)-cyclopropan-l-carboxylsyre, men idet man arbejder ved 15 -60°C, fâ (lR,trans)-2,2-dimethyl-3-(2',2'-difluor-1',2'- dibromethyl)-cyclopropan-l-carboxylsyre med smp. 122°C, blanding af isomer A og B.
N.M.R.spektrum: 20 Toppe fra 1,33 til 1,66 ppm (hydrogenatomer i methyl- grupperne i 3'-stillingen i cyclopropan), toppe fra 1,60 til 2,23 ppm (hydrogenatomer i 1- og 3-stillingen i cyclopropan), toppe fra 3,75 til 4,37 ppm (hydrogen i 1'-stillingen i ethylkæden i 3-stillingen i cyclo-25 propan), top ved 10,96 ppm (hydrogen i carboxylgrup pen) .
Eksempel 7 (IR,cis)-2,2-dimethyl-3-(2',21-dichlor-1', 2 1-dibromethyl)-30 -cyclopropan-l-carboxylsyre
Ved indvirkning af brom pâ (IR,cis)-2,2-dimethyl-3-(2',2'--dichlorvinyl)-cyclopropan-l-carboxylsyre fâr man (lR,cis)--2,2-dimethyl-3-(2',21-dichlor-11,21-dibromethyl)-cyclopropan-l-carboxylsyre, blanding af isomer A og B.
35 - 12 -
DK 156934 B
N.M.R.spektrum:
Toppe ved 1,26-1,30 og ved 1,41-1,42 ppm (hydrogenato-mer i methylgrupperne i 3-stillingen i cyclopropan), toppe ved 1,83-2,17 ppm (hydrogen i 1- og 3-stillingen 5 i cyclopropan), toppe fra 4,83 til 5,58 ppm (hydrogen i 1'-stillingen i ethylgruppen i 3-stillingen i cyclopropan), top ved 8,17 ppm (hydrogen i carboxylgrup-pen).
10 Eksempel 8 (IR,cis)-2,2-dimethyl-3-(2' <-2' ,2' ,1'-tetrachlorethyl)--cyclopropan-l-carboxylsyre I 30 ml carbontetrachlorid lader man chlor boble indtil mætning (man oploser 11,8 g chlor), og man indforer i l0bet 15 af ca. 30 minutter en oplosning af 16,7 g (lR,cis)-2,2-di- methyl-3-(21,2'-dichlorvinyl)-cyclopropan-l-carboxylsyre i 40 ml methylenchlorid ved en temperatur under 0°C, omrorer i 24 timer ved 0°C, bringer reaktionsblandingens temperatur pâ 25°C, omrorer i 3 timer ved denne temperatur, eliminerer 20 overskuddet af chlor ved gennembobling af nitrogen, inddam- per til torhed ved destination under formindsket tryk, renser resten ved chromatografi pâ silicagel under eluering med en blanding af cyclohexan og ethylacetat (8:2), kry-stalliserer af petroleumsether (kp. 35-75°C) og fâr 3,14 g 25 (IR,cis)-2,2-dimethyl-3-(2',2',2',1'-tetrachlorethyl)-cyc - lopropan-l-carboxylsyre med smp. 144°C.
Analyse: C8H10^4^2 = ^79,98 beregnet: C% 34,3 H% 3,6 Cl% 50,6 30 fundet: 34,4 3,7 50,3 N.M.R.spektrum (deuterochloroform):
Toppe ved 1,26-1,42 ppm og 1,30-1,42 ppm, karakteri-stiske for hydrogenatomerne i tvillingmethylgrupper-35 ne, toppe fra 4,67 til 5,17 ppm og fra 5,08 til 5,43 ppm, karakteristiske for hydrogenatomet i l'-stillin-
DK 156934 B
- 13 - gen i den substituerede ethylsidekæde, top ved 10,2 ppm, karakteristisk for hydrogsnet i carboxylgruppen, top fra 1,67 til 2,0 ppm, karakteristisk for hydrogen-atomerne i cyclopropyl.
5
Eksempel 9 (IR,trans)-2,2-dimethy1-3-(21,21,21,11-tetrachlorethyl)--cyclopropan-l-carboxylsyre I 30 ml carbontetrachlorid oploser man ved -10°C 13,25 g 10 chlor, og man tilsætter i lobet af ca. 15 minutter 18,8 g (IR,trans)-2,2-dimethy1-3-(2',2'-dichlorvinyl)-cyclopropan-l-carboxylsyre opiost i 30 ml methylenchlorid, idet der over reaktionsbeholderen er anbragt en koler, hvori der cirkulerer en vaeske ved -60°C til kondensation af uomsat 15 chlor, og man omrorer i 1 time 30 minutter ved -10°C og derefter 1 time 30 minutter ved 0°C, hvorefter man elimine-rer overskuddet af chlor ved 20°C ved gennembobling af nitrogen, hvorefter man inddamper til torhed under formind-sket tryk og renser resten ved chromatografi pâ silicagel 20 under eluering med en blanding af cyclohexan og ethylacetat (7:3) og fâr 23 g(IR,trans)-2,2-dimethyl-3-(2',2',2',1'-tetrachlorethyl )-cyclopropan-l-carboxylsyre.
N.M.R.spektrum (deuterochloroform): 25 Toppe ved 1,25-1,53 ppm, karakteristiske for hydrogen- atomerne i methylgrupperne i 2-stillingen i cyclopropyl, toppe ved 1,68-2,21 ppm, karakteristiske for hy-drogenatomerne i 1- og 3-stillingen i cyclopropyl, toppe ved 4,12-4,21 ppm, karakteristiske for hydrogen-30 atomet i 1'-stillingen i den substituerede ethylside- kæde, top ved 11,3 ppm, karakteristisk for hydrogen-atomet i carboxylgruppen.
35 - 14 -
DK 156934 B
Eksempel 10 (lR,cis)-2 ,2-dimethyl-3-(2',2 ' -difluor-11 ,2'-dibromethyl)--cyclopropan-l-carboxylsyre I 120 ml methylenchlorid indf0rer man 17 g (lR,cis)-2,2-5 -dimethyl-3-(21,2'-difluorvinyl)-cyclopropan-l-carboxylsy- re, og man indf0rer ved -65°C i l0bet af ca. 2 timer 15,2 g brom opl0st i 40 ml carbontetrachlorid, omr0rer i 2 timer 30 minutter ved -65°C, lader temperaturen stige til 20°C, inddamper til t0rhed ved destination under formindsket 10 tryk, oploser resten i varmen i 50 ml carbontetrachlorid, afkoler til 0°C, omrorer ved denne temperatur i 45 minutter, eliminerer det uoploselige materiale ved filtrering, inddamper filtratet til torhed ved destination under formindsket tryk, oploser resten i 40 ml carbontetrachlorid, 15 omrorer i 30 minutter ved -10°C, eliminerer det uoploselige materiale ved filtrering, inddamper filtratet til torhed ved destination under formindsket tryk, renser resten ved chromatografi pâ silicagel under eluering med en blanding af cyclohexan og ethylacetat (75:25), krystalliserer af pe-20 troleumsether (kp. 35-75°C) og fâr 1,465 g (lR,cis)-2,2-di-methyl-3-(2',2'-difluor-11,21-dibromethyl)-cyclopropan-l-carboxylsyre med smp. 124°C.
N.M.R.spektrum (deuterochloroform): 25 Toppe ved 1,28-1,38 ppm, karakteristiske for hydrogen- atomerne i tvillingmethylgrupperne, toppe ved 1,67-2,0 ppm, karakteristiske for hydrogenatomerne i cyc-lopropyl, toppe ved 4,67-5,33 ppm, karakteristiske for hydrogenatomet i den substituerede ethylsidekæde.
30
Eksempel 11 (IR,cis)-2,2-dimethyl-3-(21-(RS)-fluor-21-chlor-11,2'-dibromethyl )-cyclopropan-l-carboxylsyre I 100 ml carbontetrachlorid oplaser man 8,9 g (lR,cis)-2,2-35 dimethyl-3-(2'-chlor-2'-fluorvinyl)-cyclopropan-l-carboxylsyre (blanding af isomer E og Z), og man tilsætter ved -10°C i lobet af ca. 30 minutter 2,4 ml brom oplost i 20 - 15 -
DK 156934 B
ml carbontetrachlorid, omrorer i 4 timer ved 10°C, inddam-per til torhed ved destination umder formindsket tryk, chromatograferer restèn pâ silicagel under eluering med ethylacetat og fâr 13,7 g (lR,cis)-2,2-dimethyl-3-(21-(RS)-5 fluor-21-chlor-1',21-dibromethyl)-cyclopropan-l-carboxylsy- re.
I.R.spektrum (chloroform):
Absorption ved 1710 cm L, karakteristisk for C=0, 10 absorption ved 3510 cm \ karakteristisk for OH.
N.M.R.spektrum (deuterochloroform) :
Toppe ved 1,30-1,32-1,42 ppm, karakteristiske for hy-drogenatomerne i tvillingmethylgrupperne, toppe ved 15 1,75-2,08 ppm, karakteristiske for hydrogenatomerne i cyclopropyl, toppe ved 4,67-5,50 ppm, karakteristiske for hydrogenatomet i 11-stillingen i den mættede ethylsidekæde, top ved 10,75 ppm, karakteristisk for hydrogenatomet i carboxylgruppen.
20
Eksempel 12 Fungicidt middel
Man fremstiller et vasdbart pudder, hvis sammensætning er som folger: 25 ( IR, cis ) -2,2-dimethyl-3- (2^2^2^11 -tetrachlorethyl ) -cyclopropan-l-carboxylsyre (forbindelse E) 20 g
Ekapersol "S" (1) (indreg. varemærke) 15 g - Brecolane NVA (2) (indreg. varemærke) 0,5 g 30 - Zeosil 39L (3) (indreg. varemærke) 32,5 g - Vercoryl (S) (4) (indreg. varemærke) 25 g (1) Kondensationsprodukt af natriumnaphthalensulfonat.
(2) Natriumalkylnaphthalensulfonat.
(3) Syntetisk hydratiseret silicagel fremstillet ved fæld- 35 ning.
(4) Kolloidalt kaolin.
- 16 -
DK 156934 B
Eksempel 13 Funqicidt middel
Man fremstiller en oplosning indeholdende: ( IR, cis ) -2,2-dimethyl-3- (2',2^2^11 -tetrachlorethyl ) -5 cyclopropan-l-carboxylsyre (forbindelse E) 25 g/liter
Emcol H 300 B * (indreg. varemærke) 80 g/liter - Xylen 895 g/liter * Calciumsalt af alkylbenzensulfonater (anionisk del) blandet med polyoxyethylenerede ethere (ikke-ionisk 10 del).
Eksempel 14 Biocidt præparat
Man fremstiller et vædbart pudder med f0lgende sammensæt-15 ning: ( IR,trans)-2,2-dimethyl-3-(2 *,2',2',1',tetra-bromethyl)-cyclopropan-l-carboxylsyre 25 g - Ekapersol "S" (1) (indreg. varemærke) 15 g 20 - Brecolane NVA (2) (indreg. varemærke) 0,5 g
Zeosil 39 (3) (indreg. varemærke) 34,5 g - Vercoryl (S) (4) (indreg. varemærke) 25 g (1) Kondensationsprodukt af natriumnaphthalensulfonat.
25 (2) Natriumalkylnaphthalensulfonat.
(2) Syntetisk hydratiseret silicagel fremstillet ved fæld-ning.
(4) Kolloidalt kaolin.
30 Eksempel 15
Biocidt præparat
Man benytter en oplosning med folgende sammensætning: (IR,trans)-2,2-dimethyl-3-(21,2',2',l'-tetra-35 bromethyl)-cyclopropan-l-carboxylsyre 25 g éthanol 75 g - 17 -
DK 156934 B
Eksempel 16
Undersogelse af fungicid virkninq (IR,cis)-2,2-dimethyl-3-(2',2'-dibrom-1',21-dichlor-ethyl)-cyclopropan-l-carboxylsyre (forbindelse A) 5 - (lR,trans)-2,2-dimethyl-3-(2',21-difluor-11,2'-dibrom- ethyl)-cyclopropan-l-carboxylsyre (forbindelse B) (lR,cis)-2,2-dimethyl-3-(21,21-dichlor-1',2'-dibrom-ethyl)-cyclopropan-l-carboxylsyre (forbindelse C) ( IR,trans ) -2,2-dimethyl-3- (2^2^2^11 -tetrabromme-10 thyl)-cyclopropan-l-carboxylsyre (forbindelse D) (lR,cis)-2,2-dimethyl-3-(2',2',2',1'-tetrachlorethyl)-cyclopropan-l-carboxylsyre (forbindelse E) (lR,cis)-2/2-dimethyl-3-(2',2',2',1'-tetrabromethyl)-cyclopropan-l-carboxylsyre (forbindelse F) 15 - (lR,trans)-2,2-dimethyl-3-(2',2'-dichlor-1',2'-dibrom- ethyl)-cyclopropan-l-carboxylsyre (forbindelse G).
Man undersoger den fungistatiske effektivitet af den forbindelse, som skal undersoges, idet man indforer 0,5 ml op-20 losning af forbindelsen og 0,5 ml af en suspension af spo- rer af den svamp, som skal bekæmpes, indstillet til ca.
100.000 sporer pr. ml i 4 ml Staron's næringsmilje.
Aflæsningen foretages efter 7 dages inkubation ved visuel 25 kontrol af udviklingen af svampen eller fravær af udvikling (0% eller 100%'s effektivitet).
Staron's næringsmiljo har folgende sammensætning: - Glucose 20 g 3 f) pepton 6 g gærekstrakt 1 g majsstobevæske 4 g natriumchlorid 0,50 g monokaliumphosphat 1 g
λ S
- magnesiumsulfat 0,5 g ferrosulfat 10 mg - vand ad 1 liter - 18 -
DK 156934 B
Under anvendelse af samme protokol sorti ovenfor finder man folgende fungistatiske tærskelværdier: 1) Forsog pâ Botrytis sinerea 5 Forbindelse A: 150-200 ppm forbindelse E: 75-100 ppm 2 ) Forsog pâ Fusarium roseum Forbindelse A: 100-150 ppm forbindelse C: 100-150 ppm forbindelse D: 75-100 ppm forbindelse E: 50- 75 ppm forbindelse G: 100-150 ppm 15 3) Forsog pâ Phoma sp.
Forbindelse A: 50- 75 ppm forbindelse B: 100-150 ppm forbindelse C: 150-200 ppm forbindelse D: 100-150 ppm 20 forbindelse E: 50- 75 ppm forbindelse F: 50- 75 ppm forbindelse G: 100-150 ppm 25 4) Forsog pâ Pénicillium roqueforti
Forbindelse A: 50- 75 ppm forbindelse B: 100-150 ppm forbindelse C: 150-200 ppm forbindelse D: 100-150 ppm 30 forbindelse E: 50- 75 ppm forbindelse F: 250-500 ppm forbindelse G: 100-150 ppm 5) Forsoq pâ Aspergillus niger
Forbindelse F: 250-500 ppm 1
Forsoq pâ Absidia glauca
Fn-rVi-i nr1f=l sp F; 2^0-^00 rmm
DK 156934 B
- 19 -
Konklusion:
Forbindelse A, B, C, D, E, F og G har en intéressant fungi-cid aktivitet.
5 Eksempel 17
Underspgelse af den biocide virkning af forbindelse A, B, C, D, E, F oq G Forsoq pâ lim
Man benytter en oplpsning af 3 g carboxymethylstivelse i 91 10 g vand. Man inkorporerer forbindelsen, som skal unders0- ges, i 1 ml acetoneopl0sning, tilsætter 5 ml af et podema-teriale, som udgores af en blanding af sporer af Aerobacter aerogenes, Pseudomonas aeruginosa, Escherichia coli, Serra-tia marcescens, Bacillus subtilis og Staphylococcus aureus.
15 Man bringer denne blanding pâ 37°C i varmeskab i 48 timer og derefter ved 20°C i 6 dage.
Man foretager kontrollen af bakteriepopulationen 48 timer og 8 dage efter behandling og inficering ved metoden med 20 fortyndinger i sérum og inkorporering i gelose bouillon.
Idet man benytter denne arbejdsprotokol, fâr man folgende resultater: 25 30 35
DK 156934 B
- 20 -
Φ "SR LO Cn Ό H IA LA
p C LA O- O ' IA CT\ <f* (A LA
H O CM H O O Cn CTi CM LA
φ -p O — i—1 — — — — —
H- H 0Ί C7\ CM H LA
φ O Cn <Ti Cn (Tv IN Cn
H
O 0) fl bC 0} -p d ’iR en
rj >d la Ο Ο Ο Ο Ο (Τι O
O O OOOOO-'-O
,Χ 00 - HpHiHiHHCT\fH
o en
H •H -P
faO -ïR N- G\ (N <Τ CM ·
'OC! LTi <f- O 00 O fA eQ A
h h fl cm en ο n- ο n n en s O fl 0 O - H *· H - * ? p ο -p - oo en en co A ο H O in en en co en ο ή ω *
Ή ‘H ^ -P
i a en ω
•H H oR CT
co m ο ο ο ο o en ο h fcû <f O OOOOO “ o >
d Ο «· HHHHHCnrS H
Φ · O en -P
Λ bfl - -¾ feo S 10 •H ·Η .
H H I ό
Φ p p N- în N eo N vo vo *H
•de: ic ooooooo o S d O d 0 H H H H H H H °ν· dil ,X p P X X X X X X X ·η
Φ p φ φ .:=. Ι> [N [S- tN IA <t P
^R P -H PH H H H H H IN LA ’ Ή Λ a •>s vû la eo. ko ko cû a a o o ooo 0 Φ CM H HOHHH 0 •p ο χοχκηχχχ 0 bû H - m Ό MO CM H H fl
Cj 0 O H H H CM A 0 H £ ^ fl Φ fl
H 0 b£ oR H
S o d a o PO O O O O O IN O fl fl «H ‘ CM 0
0 fl CO O
•H Ή fl fl cd O taû I · Ά HO P CD v£) vû LO Ό Ό Ό
O I fl OOOOOOO O
P faO 0 d 0 H H H H H H H
ϋΛΌ XXXXXXX W)
•H p00t>-[>-INA[NA<f· O
SH fl *H P H LT\ (A 1Λ IN IA 00 <t" OP 0 P4 j_j j-j _«_3
Bd«H^RVD ΙΑ ΙΑ «i
«aj p φ lA O O OOO H
P 0 CM H H i—1 i—-î r-H
op P o X . O X O X X X * (1, - CM CM O IN N Ω
OflOOO H H IA C0 C
A 0 " P o «H oR o
φ A OOOOOOO
O A PQ
° < 00 000 .00 «.0 κιωωωωωΜ flw
HHHHHHH OH
ΦΦΦ00ΦΦ H 0 -d P P P P P P WP· fl fl fl fl fl fl · fl _ 2 fl
•H < -HW -HO ·Η Ω H H* H fa HO H H
PPPPPPP PP
flflflflflflfl flfl
OOOOOOO OO
Cu Cü fa fa fa fa fa X 1¾
Claims (9)
1. Cyclopropancarboxylsyrer med fungicid og biocid virk-ning i aile deres mulige isomere former og med den almene 5 formel I x\ H II.Cv /CH. 2\ i ^ i X —C---Cs s , /2’ 1'|, \ xT 2 /0-011 (I) ^ 1 J,3 ___iV 10. x ' \
11 II hvor X^" betegner et fluoratom, et chloratom eller et brom- 2. atom, X , som er identisk med eller forskellig fra X , be- 3 X5 tegner et fluoratom, chloratom eller bromatom, og X beteg ner et chloratom eller et bromatom.
2. Cyclopropancarboxylsyrer ifolge krav 1 i form af isomer A, isomer B eller en blanding af disse isomere og med fol- 20 gende navn: ( IR, trans ) -2,2-dimethyl-3- ( 1^2^2^21 -tetrabromethyl ) -cyclopropan-l-carboxylsyre, (IR,trans)-2,2-dimethyl-3-(21,21-dichlor-11,21-dibrom-ethyl)-cyclopropan-l-carboxylsyre, 25 - (IR,cis)-2,2-dimethy1-3-(21,2'-dibrom-1',21-dichlor- ethyl)-cyclopropan-l-carboxylsyre, (IR,trans)-2,2-dimethyl-3-(2^21-dibrom-1',2'-dichlor-ethyl)-cyclopropan-l-carboxylsyre eller (lR,trans)-2,2-dimethyl-3-(2',2'-difluor-1',2'-dibrom-30 ethyl)-cyclopropan-l-carboxylsyre.
3. Cyclopropancarboxylsyrer ifolge krav 1 i form af isomer A, isomer B eller en blanding af disse isomere af ( IR, cis ) -2,2-dimethyl-3- ( 1^2^2^21 -tetrabromethyl ) -35 cyclopropan-l-carboxylsyre. DK 156934B - 22 -
4. Cyclopropancarboxylsyrer ifolge krav 1 i form af isomer A, isomer B eller en blanding af disse isomere af (IR,cis)-2,2-dimethyl-3-(21,2'-dichlor-11,21-dibrom-ethyl)-cyclopropan-l-carboxylsyre. 5
5. Cyclopropancarboxylsyre ifolge krav 1 i form af isomer A, isomer B eller en blanding af disse isomere af ( IR, cis ) -2,2-dimethyl-3- ( 2^2^2^11 -tetrachlorethyl ) -cyclopropan-l-carboxylsyre, 10 - (lR,trans)-2,2-dimethy1-3-(2',2',2',1'-tetrachlorethyl)- cyclopropan-l-carboxylsyre.
6. Cyclopropancarboxylsyrer ifolge krav 1 i form af isomer A, isomer B eller en blanding af disse isomere af 15 - (IR,cis)-2,2-dimethyl-3-(2',21-difluor-21,11-dibrom- ethyl)-cyclopropan-l-carboxylsyre eller (IR,cis)-3-(2'-(RS)-fluor-2'-chlor-1',21-dibromethyl)-cyclopropan-l-carboxylsyre.
7. Fungicide præparater, der som aktiv bestanddel indehol- der i det mindste en af forbindelserne ifolge krav 2-4.
8. Fungicide præparater, der som aktiv bestanddel indehol-der i det mindste en af forbindelserne ifolge krav 5. 25
9. Biocide præparater indeholdende som aktiv bestanddel i det mindste en af forbindelserne ifolge krav 2-4. 1 35 Biocide præparater indeholdende som aktiv bestanddel i 30 det mindste en af forbindelserne ifolge krav 5.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7628279 | 1976-09-21 | ||
| FR7628279A FR2364884A1 (fr) | 1976-09-21 | 1976-09-21 | Nouveaux esters d'acides cyclopropane, carboxyliques comportant un substituant polyhalogene, procedes de preparation et compositions insecticides les renfermant |
| FR7722078 | 1977-07-19 | ||
| FR7722078A FR2398041A2 (fr) | 1977-07-19 | 1977-07-19 | Esters d'acides cyclopropane carboxylique comportant un substituant polyhalogene, procede de preparation et leur application comme insecticides, acaricides, nematicides et comme medicaments veterinaires |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK414577A DK414577A (da) | 1978-03-22 |
| DK156934B true DK156934B (da) | 1989-10-23 |
| DK156934C DK156934C (da) | 1990-03-26 |
Family
ID=26219635
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK414477A DK157970C (da) | 1976-09-21 | 1977-09-20 | Pesticide, isaer insekticide estere af cyclopropancarboxylsyrer med en polyhalogeneret substituent samt praeparater indeholdende mindst en af disse |
| DK414577A DK156934C (da) | 1976-09-21 | 1977-09-20 | Fungicide og biocide cyclopropancarboxylsyrer med en polyhalogeneret gruppe |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK414477A DK157970C (da) | 1976-09-21 | 1977-09-20 | Pesticide, isaer insekticide estere af cyclopropancarboxylsyrer med en polyhalogeneret substituent samt praeparater indeholdende mindst en af disse |
Country Status (31)
| Country | Link |
|---|---|
| US (3) | US4179575A (da) |
| JP (2) | JPS5340744A (da) |
| AR (1) | AR230423A1 (da) |
| AT (1) | AT363280B (da) |
| AU (2) | AU514599B2 (da) |
| BR (2) | BR7706314A (da) |
| CA (2) | CA1242733A (da) |
| CH (2) | CH630884A5 (da) |
| DD (2) | DD135899A5 (da) |
| DE (2) | DE2742547A1 (da) |
| DK (2) | DK157970C (da) |
| ES (2) | ES462475A1 (da) |
| FI (2) | FI71723C (da) |
| GB (2) | GB1561470A (da) |
| GR (1) | GR70299B (da) |
| HU (2) | HU179756B (da) |
| IE (2) | IE45595B1 (da) |
| IL (2) | IL52981A0 (da) |
| IT (2) | IT1090232B (da) |
| LU (2) | LU78156A1 (da) |
| MX (1) | MX5332E (da) |
| NL (2) | NL180899C (da) |
| NO (1) | NO148184C (da) |
| NZ (1) | NZ185226A (da) |
| OA (1) | OA05761A (da) |
| PH (1) | PH15593A (da) |
| PL (1) | PL119266B1 (da) |
| PT (1) | PT67062B (da) |
| SE (2) | SE446527B (da) |
| SU (1) | SU1316553A3 (da) |
| YU (2) | YU40818B (da) |
Families Citing this family (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2419932A2 (fr) * | 1978-03-17 | 1979-10-12 | Roussel Uclaf | Nouveaux esters d'acides cyclopropane carboxyliques comportant un substituant polyhalogene, procede de preparation et compositions insecticides les renfermant |
| EP0001795B1 (de) * | 1977-11-01 | 1981-01-07 | Ciba-Geigy Ag | Cyclopropankarbonsäure-phenoxy-alpha-vinyl-benzylester, Verfahren zu ihrer Herstellung und ihre Verwendung in der Schädlingsbekämpfung |
| US4221812A (en) | 1978-02-09 | 1980-09-09 | Ciba-Geigy Corporation | Pesticidal spiropentanecarboxylates |
| JPS5511576A (en) * | 1978-07-11 | 1980-01-26 | Kuraray Co Ltd | Substituted cyclopropanecarboxylic ester and insecticide containing the same as effective component |
| EP0012722B1 (de) * | 1978-12-15 | 1981-12-09 | Ciba-Geigy Ag | Verfahren zur Herstellung von optisch aktiven, in 3-Stellung substituierten 2-(2',2'-Dihalogenvinyl)-cyclopropan-1-carbonsäuren und deren Derivaten; 4-(2',2',2'-Trihalogenäthyl)-cyclobutan-1-sulfonsäuresalze und deren Herstellung |
| JPS55167256A (en) * | 1979-06-12 | 1980-12-26 | Kuraray Co Ltd | 3-(4-chlorophenoxy)benzyl 2,2-dimethyl-3-(2,2-dichlorovinyl) cyclopropane-carboxylate and insecticide comprising it as active constituent |
| FR2484256B1 (fr) * | 1979-06-29 | 1986-10-24 | Roussel Uclaf | Procede de lutte contre les parasites des animaux a sang chaud |
| US4402973A (en) * | 1980-10-02 | 1983-09-06 | Fmc Corporation | Insecticidal (1,1'-biphenyl)-3-ylmethyl esters |
| BE886160A (nl) * | 1979-11-27 | 1981-05-14 | Shell Int Research | Cyclopropaan-carbonzure ester-derivaten |
| DE3004092A1 (de) * | 1980-02-05 | 1981-08-13 | Bayer Ag, 5090 Leverkusen | Substituierte 3-(1,2-dibrom-alkyl)- 2,2-dimethyl-cyclopropan-1-carbonsaeureester, verfahren sowie zwischenprodukte zu ihrer herstellung und ihre verwendung in schaedlingsbekaempfungsmitteln |
| HU182802B (en) * | 1980-02-26 | 1984-03-28 | Biogal Gyogyszergyar | Fotostabil delousing (insecticide) composition containing synthetic piretroides |
| US4331682A (en) | 1980-03-14 | 1982-05-25 | Ciba-Geigy Corporation | Cyclopropanecarboxylic acid-α-haloethynyl-m-phenoxybenzyl esters and their use for combating insect pests |
| US4459305A (en) * | 1980-04-10 | 1984-07-10 | Dainippon Sochugiku Kabushiki Kaisha | Cyclopropanecarboxylic acid ester derivatives, a method of manufacturing them, and their uses |
| FR2498201A2 (fr) * | 1980-06-11 | 1982-07-23 | Roussel Uclaf | Compositions stables a la lumiere contenant des composes pyrethrinoides et des colorants |
| US4492687A (en) * | 1980-06-11 | 1985-01-08 | Roussel Uclaf | Light-stable pesticidal compositions |
| US4376785A (en) * | 1980-06-19 | 1983-03-15 | Sumitomo Chemical Company, Limited | Cyclopropanecarboxylates and a low fish toxic insecticide and/or acaricide containing them |
| IT1150963B (it) * | 1980-07-29 | 1986-12-17 | Montedison Spa | Piretroidi |
| JPS5879909A (ja) * | 1981-11-07 | 1983-05-13 | Yoshio Katsuta | 低魚毒性殺虫・殺ダニ剤及びその製造法 |
| EP0095047B1 (de) * | 1982-05-05 | 1985-11-27 | Bayer Ag | Verfahren zur Herstellung von 3-vinylsubstituierten 2,2-Dimethylcyclopropan-1-carbonsäuren bzw. ihren Estern und neue Zwischenprodukte dafür |
| US4493844A (en) * | 1982-08-19 | 1985-01-15 | Fmc Corporation | Insecticidal 2,2'-bridged(1,1'-biphenyl)-3-ylmethyl carboxamides |
| US4487778A (en) * | 1983-01-27 | 1984-12-11 | Fmc Corporation | Insecticidal esters derived from benzocycloalkane-thiophenemethyl compounds |
| US4605748A (en) * | 1983-01-27 | 1986-08-12 | Fmc Corporation | Benzocycloalkane-thiophenemethyl compounds as intermediates |
| DE3623532A1 (de) * | 1986-07-12 | 1988-01-21 | Bayer Ag | Verwendung von thiadiazinonen zur bekaempfung von endoparasiten |
| DE19953775A1 (de) | 1999-11-09 | 2001-05-10 | Bayer Ag | Wirkstoffkombinationen mit insektiziden und akariziden Eigenschaften |
| DE10007411A1 (de) * | 2000-02-18 | 2001-08-23 | Bayer Ag | Wirkstoffkombinationen mit insektiziden und akariziden Eigenschaften |
| AR029677A1 (es) | 2000-06-29 | 2003-07-10 | Bayer Ag | Combinaciones de compuestos activos con propiedades insecticidas y acaricidas |
| DE102004001271A1 (de) * | 2004-01-08 | 2005-08-04 | Bayer Cropscience Ag | Wirkstoffkombinationen mit insektiziden Eigenschaften |
| DE102004006324A1 (de) * | 2004-02-10 | 2005-08-25 | Bayer Cropscience Ag | Wirkstoffkombinationen mit insektiziden Eigenschaften |
| US20090281157A1 (en) * | 2006-07-11 | 2009-11-12 | Bayer Cropscience Ag | Active Ingredient Combinations With Insecticidal and Acaricidal Properties |
| DE102006046688B3 (de) * | 2006-09-29 | 2008-01-24 | Siemens Ag | Kälteanlage mit einem warmen und einem kalten Verbindungselement und einem mit den Verbindungselementen verbundenen Wärmerohr |
| US20100099717A1 (en) * | 2006-09-30 | 2010-04-22 | Bayer Cropscience Aktiengesellschaft | Suspension concentrates for improving the root absorption of agrochemical active ingredients |
| EP2039248A1 (de) * | 2007-09-21 | 2009-03-25 | Bayer CropScience AG | Wirkstoffkombinationen mit insektiziden und akariziden Eigenschaften |
| DE102007045953B4 (de) | 2007-09-26 | 2018-07-05 | Bayer Intellectual Property Gmbh | Wirkstoffkombinationen mit insektiziden und akariziden Eigenschaften |
| NZ589018A (en) * | 2008-05-07 | 2012-07-27 | Bayer Cropscience Ag | Synergistic active ingredient combinations |
| EP2127522A1 (de) | 2008-05-29 | 2009-12-02 | Bayer CropScience AG | Wirkstoffkombinationen mit insektiziden und akariziden Eigenschaften |
| CN102448304B (zh) | 2009-03-25 | 2015-03-11 | 拜尔农作物科学股份公司 | 具有杀昆虫和杀螨特性的活性成分结合物 |
| DE102009028001A1 (de) | 2009-07-24 | 2011-01-27 | Bayer Cropscience Ag | Wirkstoffkombinationen mit insektiziden und akariziden Eigenschaften |
| EP2382865A1 (de) | 2010-04-28 | 2011-11-02 | Bayer CropScience AG | Synergistische Wirkstoffkombinationen |
| CN109485564B (zh) * | 2018-11-28 | 2021-08-27 | 赵学迅 | 一种制备联苯菊酯的新方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3320121A (en) * | 1963-11-21 | 1967-05-16 | Sun Oil Co | 2-(2',2'-dihalocyclopropyl)-1,1-dihalocyclopropane and 2,2-dihalocyclopropyl carboxylic acid as antibacterial agents |
| US3856976A (en) * | 1971-04-23 | 1974-12-24 | Shell Oil Co | Cyclopropane derivative fungicides |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1168797A (en) * | 1965-12-09 | 1969-10-29 | Nat Res Dev | Cyclopropane Carboxylic Acid Derivatives and their use as Insecticides |
| US3702333A (en) * | 1967-08-11 | 1972-11-07 | Yoshitomi Pharmaceutical | Cyclopropanecarboxylic acid esters possessing pesticidal properties |
| US3666789A (en) * | 1969-05-21 | 1972-05-30 | Sumitomo Chemical Co | Cyclopropanecarboxylic acid esters |
| JPS4821487B1 (da) * | 1970-08-04 | 1973-06-29 | ||
| GB1413491A (en) * | 1972-05-25 | 1975-11-12 | Nat Res Dev | 3-substituted-2,2-dimethyl-cyclopropane carboxylic acid esters their preparation and their use in pesticidal compositions |
| JPS50895B2 (da) * | 1972-05-31 | 1975-01-13 | ||
| JPS5521008B2 (da) * | 1972-11-29 | 1980-06-06 | ||
| JPS5542045B2 (da) * | 1973-04-20 | 1980-10-28 | ||
| JPS5212697B2 (da) * | 1973-08-23 | 1977-04-08 | ||
| JPS6059221B2 (ja) * | 1975-02-12 | 1985-12-24 | 住友化学工業株式会社 | アルキルシクロプロピルケトン誘導体の製造方法 |
| JPS5195043A (en) * | 1975-02-12 | 1976-08-20 | beeta jiharogenoetenirushikuropuropanjudotaino seizohoho | |
| GB1519052A (en) * | 1975-05-16 | 1978-07-26 | Ici Ltd | Process for preparing branched carboxylic acids |
| GB1581340A (en) * | 1976-07-26 | 1980-12-10 | Shell Int Research | Preparation of esters |
| TR20016A (tr) * | 1977-02-11 | 1980-06-16 | Ciba Geigy Ag | Yeni isterler |
-
1977
- 1977-08-31 SE SE7709800A patent/SE446527B/xx not_active IP Right Cessation
- 1977-08-31 SE SE7709801A patent/SE441179B/xx not_active IP Right Cessation
- 1977-09-05 OA OA56275A patent/OA05761A/xx unknown
- 1977-09-15 HU HU77RO941A patent/HU179756B/hu not_active IP Right Cessation
- 1977-09-15 HU HU77RO942A patent/HU178710B/hu not_active IP Right Cessation
- 1977-09-19 GR GR54381A patent/GR70299B/el unknown
- 1977-09-19 US US05/834,573 patent/US4179575A/en not_active Expired - Lifetime
- 1977-09-19 FI FI772745A patent/FI71723C/fi not_active IP Right Cessation
- 1977-09-20 GB GB39149/77A patent/GB1561470A/en not_active Expired
- 1977-09-20 LU LU78156A patent/LU78156A1/xx unknown
- 1977-09-20 DK DK414477A patent/DK157970C/da not_active IP Right Cessation
- 1977-09-20 NL NLAANVRAGE7710327,A patent/NL180899C/xx not_active IP Right Cessation
- 1977-09-20 MX MX776200U patent/MX5332E/es unknown
- 1977-09-20 NO NO773224A patent/NO148184C/no unknown
- 1977-09-20 IT IT51088/77A patent/IT1090232B/it active
- 1977-09-20 DD DD77201117A patent/DD135899A5/xx not_active IP Right Cessation
- 1977-09-20 DK DK414577A patent/DK156934C/da not_active IP Right Cessation
- 1977-09-20 ES ES462475A patent/ES462475A1/es not_active Expired
- 1977-09-20 PT PT197767062A patent/PT67062B/pt unknown
- 1977-09-20 IE IE1920/77A patent/IE45595B1/en not_active IP Right Cessation
- 1977-09-20 LU LU78155A patent/LU78155A1/xx unknown
- 1977-09-20 ES ES462473A patent/ES462473A1/es not_active Expired
- 1977-09-20 IT IT51087/77A patent/IT1090231B/it active Protection Beyond IP Right Term
- 1977-09-20 GB GB39148/77A patent/GB1561469A/en not_active Expired
- 1977-09-20 NL NLAANVRAGE7710328,A patent/NL182561C/xx not_active IP Right Cessation
- 1977-09-20 AR AR269268A patent/AR230423A1/es active
- 1977-09-20 IE IE1919/77A patent/IE45594B1/en not_active IP Right Cessation
- 1977-09-20 YU YU2219/77A patent/YU40818B/xx unknown
- 1977-09-20 PL PL1977200963A patent/PL119266B1/pl not_active IP Right Cessation
- 1977-09-21 IL IL52981A patent/IL52981A0/xx not_active IP Right Cessation
- 1977-09-21 BR BR7706314A patent/BR7706314A/pt unknown
- 1977-09-21 JP JP11274777A patent/JPS5340744A/ja active Granted
- 1977-09-21 CH CH1156677A patent/CH630884A5/fr not_active IP Right Cessation
- 1977-09-21 CA CA000287177A patent/CA1242733A/fr not_active Expired
- 1977-09-21 NZ NZ185226A patent/NZ185226A/xx unknown
- 1977-09-21 JP JP52112746A patent/JPS6011689B2/ja not_active Expired
- 1977-09-21 BR BR7706313A patent/BR7706313A/pt unknown
- 1977-09-21 AU AU28990/77A patent/AU514599B2/en not_active Expired
- 1977-09-21 DD DD77201145A patent/DD135152A5/xx unknown
- 1977-09-21 CA CA000287204A patent/CA1140589A/fr not_active Expired
- 1977-09-21 IL IL52980A patent/IL52980A0/xx not_active IP Right Cessation
- 1977-09-21 DE DE19772742547 patent/DE2742547A1/de active Granted
- 1977-09-21 DE DE2742546A patent/DE2742546C2/de not_active Expired
- 1977-09-21 AU AU28989/77A patent/AU512280B2/en not_active Expired
- 1977-09-21 CH CH1156777A patent/CH627431A5/fr not_active IP Right Cessation
-
1979
- 1979-02-26 AT AT0147279A patent/AT363280B/de not_active IP Right Cessation
- 1979-03-07 US US06/018,166 patent/US4224227A/en not_active Expired - Lifetime
- 1979-06-19 PH PH22669A patent/PH15593A/en unknown
- 1979-06-25 US US06/051,348 patent/US4257978A/en not_active Expired - Lifetime
-
1981
- 1981-03-12 SU SU813254447A patent/SU1316553A3/ru active
-
1983
- 1983-07-05 YU YU1450/83A patent/YU43317B/xx unknown
-
1984
- 1984-02-17 FI FI840658A patent/FI73966C/fi not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3320121A (en) * | 1963-11-21 | 1967-05-16 | Sun Oil Co | 2-(2',2'-dihalocyclopropyl)-1,1-dihalocyclopropane and 2,2-dihalocyclopropyl carboxylic acid as antibacterial agents |
| US3856976A (en) * | 1971-04-23 | 1974-12-24 | Shell Oil Co | Cyclopropane derivative fungicides |
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DK156934B (da) | Fungicide og biocide cyclopropancarboxylsyrer med en polyhalogeneret gruppe | |
| Melʹnikov | Chemistry of pesticides | |
| DE2737297C2 (da) | ||
| JPS64363B2 (da) | ||
| DE3028290A1 (de) | 2,2-dimethyl-3-(2',2'-dihalogenvinyl)cyclopropancarbonsaeure-2-methyl-3-(2'-propinyl)-cyclopent-2-en-4-on-l-ylester, verfahren zu ihrer herstellung und ihre verwendung bei der bekaempfung von schadinsekten | |
| DE1816685A1 (de) | Cyanofluorpyridine und fungicide Mittel sowie Verfahren zu deren Herstellung | |
| DD142281A5 (de) | Verfahren zur bekaempfung von insekten und acaren | |
| US4150144A (en) | 3-Phenyl-oxazolidine-2,4-dione microbicides | |
| DD140456A5 (de) | Verfahren zur herstellung von 3-(n-acyl-n-arylamino)-gamma-butyrolactonen und-gamma-butyrothiolactonen | |
| US2835625A (en) | Isopropoxycarbonyl dimethyldithio-carbamate | |
| CH630601A5 (en) | Cyclopropanecarboxylic acids containing a polyhalogenated group | |
| US3459534A (en) | Methods of controlling bacteria,fungi,nematodes and weed pests with tetrahalohydroxybenzamides | |
| DE2241560A1 (de) | Pflanzenwuchsregelnde mittel, benzophenonderivate, verfahren zu ihrer herstellung und ihre verwendung als pflanzenwuchsregler | |
| DE2335347C3 (de) | Substituierte Essigsäureester, Verfahren zu ihrer Herstellung und ihre Verwendung als Pestizide | |
| US4459308A (en) | Pyrethroids | |
| US2776239A (en) | Piperonylidene tetrahydrofuranone | |
| US3719765A (en) | Substituted trimesonitriles for regulating pests on plants | |
| US2776921A (en) | Unsaturated alkylphenone insecticides for soft-bodied insects | |
| SU648050A3 (ru) | Инсектицидное средство | |
| GB2102408A (en) | 3-phenoxybenzyl cyclopropanecarboxylate esters and their use as pesticides | |
| DE3038083A1 (de) | 5-(2'-chlor-4'-trifluormethylphenoxy)-2-nitrostyrolderivate, verfahren zu ihrer herstellung und diese verbindungen enthaltende herbizide mittel | |
| DE2333264A1 (de) | Phenyl-n-alkylcarbamate oder -thiocarbamate und pesticide mittel | |
| KR820000008B1 (ko) | 프탈 이미도메틸 시클로프로판 카복실산 에스테르의 제조방법 | |
| DE2603864A1 (de) | Cyclohexadienderivate | |
| DE2533172B2 (de) | Herbizides Mittel auf Basis von Nitrophenolätherderivaten |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PBP | Patent lapsed |