CN87102422A - 农药组合物和方法 - Google Patents
农药组合物和方法 Download PDFInfo
- Publication number
- CN87102422A CN87102422A CN87102422.5A CN87102422A CN87102422A CN 87102422 A CN87102422 A CN 87102422A CN 87102422 A CN87102422 A CN 87102422A CN 87102422 A CN87102422 A CN 87102422A
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- China
- Prior art keywords
- composition
- compound
- phenyl
- pesticide
- alkoxyl
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000000361 pesticidal effect Effects 0.000 title claims description 4
- 231100000419 toxicity Toxicity 0.000 claims abstract description 33
- 230000001988 toxicity Effects 0.000 claims abstract description 33
- 239000000575 pesticide Substances 0.000 claims abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 11
- 241000238631 Hexapoda Species 0.000 claims abstract description 9
- 241000607479 Yersinia pestis Species 0.000 claims abstract 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 36
- 239000003905 agrochemical Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 29
- -1 Octadecyloxy phenyl sulfenyl Chemical group 0.000 claims description 23
- 239000004094 surface-active agent Substances 0.000 claims description 20
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 239000005864 Sulphur Chemical group 0.000 claims description 8
- 238000007046 ethoxylation reaction Methods 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 6
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical class CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
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- 239000002253 acid Substances 0.000 claims description 4
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- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 3
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 3
- 125000003320 C2-C6 alkenyloxy group Chemical group 0.000 claims description 3
- 239000002728 pyrethroid Substances 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
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- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 7
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- 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 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
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- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 3
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 3
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- NAGJZTKCGNOGPW-UHFFFAOYSA-K dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [O-]P([O-])([S-])=S NAGJZTKCGNOGPW-UHFFFAOYSA-K 0.000 description 3
- DOFZAZXDOSGAJZ-UHFFFAOYSA-N disulfoton Chemical compound CCOP(=S)(OCC)SCCSCC DOFZAZXDOSGAJZ-UHFFFAOYSA-N 0.000 description 3
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- SBNFWQZLDJGRLK-RTWAWAEBSA-N (1R)-trans-phenothrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 SBNFWQZLDJGRLK-RTWAWAEBSA-N 0.000 description 2
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 2
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- OKIJSNGRQAOIGZ-UHFFFAOYSA-N Butopyronoxyl Chemical group CCCCOC(=O)C1=CC(=O)CC(C)(C)O1 OKIJSNGRQAOIGZ-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- VEDTXTNSFWUXGQ-UHFFFAOYSA-N Carbophenothion Chemical compound CCOP(=S)(OCC)SCSC1=CC=C(Cl)C=C1 VEDTXTNSFWUXGQ-UHFFFAOYSA-N 0.000 description 2
- 241000254173 Coleoptera Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VBKKVDGJXVOLNE-UHFFFAOYSA-N Dioxation Chemical compound CCOP(=S)(OCC)SC1OCCOC1SP(=S)(OCC)OCC VBKKVDGJXVOLNE-UHFFFAOYSA-N 0.000 description 2
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 description 2
- TZBPRYIIJAJUOY-UHFFFAOYSA-N Pirimiphos-ethyl Chemical group CCOP(=S)(OCC)OC1=CC(C)=NC(N(CC)CC)=N1 TZBPRYIIJAJUOY-UHFFFAOYSA-N 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000037396 body weight Effects 0.000 description 2
- SCKHCCSZFPSHGR-UHFFFAOYSA-N cyanophos Chemical compound COP(=S)(OC)OC1=CC=C(C#N)C=C1 SCKHCCSZFPSHGR-UHFFFAOYSA-N 0.000 description 2
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 description 2
- ZNOLGFHPUIJIMJ-UHFFFAOYSA-N fenitrothion Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C(C)=C1 ZNOLGFHPUIJIMJ-UHFFFAOYSA-N 0.000 description 2
- XDNBJTQLKCIJBV-UHFFFAOYSA-N fensulfothion Chemical compound CCOP(=S)(OCC)OC1=CC=C(S(C)=O)C=C1 XDNBJTQLKCIJBV-UHFFFAOYSA-N 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- ATROHALUCMTWTB-OWBHPGMISA-N phoxim Chemical compound CCOP(=S)(OCC)O\N=C(\C#N)C1=CC=CC=C1 ATROHALUCMTWTB-OWBHPGMISA-N 0.000 description 2
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- XIUROWKZWPIAIB-UHFFFAOYSA-N sulfotep Chemical compound CCOP(=S)(OCC)OP(=S)(OCC)OCC XIUROWKZWPIAIB-UHFFFAOYSA-N 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
- WWJZWCUNLNYYAU-UHFFFAOYSA-N temephos Chemical compound C1=CC(OP(=S)(OC)OC)=CC=C1SC1=CC=C(OP(=S)(OC)OC)C=C1 WWJZWCUNLNYYAU-UHFFFAOYSA-N 0.000 description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- OPASCBHCTNRLRM-UHFFFAOYSA-N thiometon Chemical compound CCSCCSP(=S)(OC)OC OPASCBHCTNRLRM-UHFFFAOYSA-N 0.000 description 2
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- OUCCVXVYGFBXSV-UHFFFAOYSA-N (4-chlorophenyl)sulfanylmethylsulfanyl-dimethoxy-sulfanylidene-$l^{5}-phosphane Chemical compound COP(=S)(OC)SCSC1=CC=C(Cl)C=C1 OUCCVXVYGFBXSV-UHFFFAOYSA-N 0.000 description 1
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- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 description 1
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- VXSIXFKKSNGRRO-MXOVTSAMSA-N [(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate;[(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-3-[(e)-3-methoxy-2-methyl-3-oxoprop-1-enyl Chemical class CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1.CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VXSIXFKKSNGRRO-MXOVTSAMSA-N 0.000 description 1
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- 231100000636 lethal dose Toxicity 0.000 description 1
- 231100000225 lethality Toxicity 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229960000453 malathion Drugs 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- QHOQHJPRIBSPCY-UHFFFAOYSA-N pirimiphos-methyl Chemical group CCN(CC)C1=NC(C)=CC(OP(=S)(OC)OC)=N1 QHOQHJPRIBSPCY-UHFFFAOYSA-N 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 244000062645 predators Species 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- 229940070846 pyrethrins Drugs 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000003128 rodenticide Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 235000011888 snacks Nutrition 0.000 description 1
- 239000006283 soil fumigant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 208000011117 substance-related disease Diseases 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- ZOKXUAHZSKEQSS-UHFFFAOYSA-N tribufos Chemical compound CCCCSP(=O)(SCCCC)SCCCC ZOKXUAHZSKEQSS-UHFFFAOYSA-N 0.000 description 1
- KLAPGAOQRZTCBI-UHFFFAOYSA-N tris(butylsulfanyl)phosphane Chemical compound CCCCSP(SCCCC)SCCCC KLAPGAOQRZTCBI-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
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- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic radicals
Landscapes
- Life Sciences & Earth Sciences (AREA)
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- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明提供了低经皮毒性的农药,特别是低经皮毒性的农药组合物。该组合物由一种亲脂农药,一种非离子型表面活性剂和一种干燥的惰性填料组成。提供了减轻亲脂农药,特别是农药组合物的经皮毒性的方法,以及施用该组合物防治昆虫虫害的方法。
Description
本发明涉及一种由农药和干燥的惰性填料组成的经皮毒性农药组合物,经加入一种HLB值(亲水-亲脂平衡)为大约17到大约20的非离子型表面活性剂后,增加了处理时的安全性。
通常,有许多农药用于农艺和园艺。“农药”一词系指在农田或任需要防治生物的地点能显示生物活性的任何化合物或组合物。这里所说的生物活性或防治包括所有形式的生长发育的变更,从调节,延缓直至杀死;也包括农业环境中害虫生活周期的某些时期的所有植物和动物生命形态。本发明中的农药包括除臭剂、植物生长调节剂、土壤熏蒸剂、杀软体动物剂、杀虫剂、除草剂、杀菌剂、杀鼠剂、杀线虫剂、杀藻剂、食肉动物防治剂以及昆虫和动物驱除剂。组合物中除主要成份外,还可以有辅助的生物活性化合物,如增效剂、解毒剂、肥料、土壤活力增强剂(soillife extenders)、以及辅助农药。
文中采用的术语“生物有效量”系指以任何规范的方法施用于农业现场引起上述一种或多种生物效果的任何量农药或农药组合物。正如本说明书后面将要进一步解释的那样,施用于指定位域的农药量取决于农药本身,也取决于该农药固有的生物活性的类型及其要求达到的程度。
如何选用恰当的施用量,并不超过熟悉该技术的人员的专业知识范围。
某些农药,如氯代烃氨基甲酸酯杀虫剂和膦酸酯、有机磷酸酯、有机硫代磷酸酯这样的有机磷农药,对处理它们的工作人员存在着经皮毒性的问题。
如果粗心地、不正确地或无视用法说明来处理这类农药,那么,根据其毒性,有可能对那些为销售进行包装,为装运而处理,为现场使用进行混合或在现场使用的人们带来危害。这种农药的毒性与许多因素有关,包括在生物作用现场该农药物质的内在毒性。这种农药的各种物理性质比如它的亲水-亲脂平衡会影响到它吸附到处理它的人员的各种机体组织上或影响到处理它的人员的各机体战组织对它的吸收,这样,就影响了它对处理人员的毒性。
因而,需要为这些农药化合物开发各种制剂以便减轻对处理它们的人员的经皮毒性,而仍然保持它们在施用于害虫或可能发现害虫的地点时的杀虫效力。
我们已经发现了一种农药组合物,它既保持了施用于现场对害虫有高的生物效力,同时又减轻了对人的经皮毒性。这类组合物包括一种生物有效量的经皮毒性农药、一种HLB值大约17到大约20的非离子型表面活性剂和一种干燥而惰性的填料。
说得更具体些,这类组合物包括下述组成:
(a)一种生物有效量的经皮毒性农药;
(b)乙氧基化二壬基苯酚表面活性剂;和
(c)一种颗粒状的干燥的惰性粘土填料。
经皮毒性包括动物或人体由于皮肤与毒性物质接触一定时间而产生的内吸毒性。经皮毒性可以由暴露于有毒物质24小时的LD-50(致死中量)来定义。
本文公布的农药组合物包括经皮毒性的有机磷、拟除虫菊酯、磷酸酯和硫代磷酸酯化合物。下面是这些化合物的例子,括号中是它们的通用名。
S-(叔丁基硫甲基)-O,O-二乙基二硫代磷酸酯(terbufos,特丁三九一一)
O,O-二乙基-O-(4-甲亚硫酰苯基)硫代磷酸酯(fensulfothion,砜线磷)
O,O-二乙基-O-(2-异丙基-6-甲基-4-嘧啶基)硫代磷酸酯(diazinon,地亚农)
O,O-二乙基-S-(2-乙硫乙基)二硫代磷酸酯(disulfoton,乙拌磷)
S-氯甲基-O,O-二乙基二硫代磷酸酯(chlormephos,氯甲硫磷)
O-乙基-S,S-二丙基二硫代磷酸酯(ethoprophos,丙线磷)
O,O-二乙基-S-(乙硫甲基)二硫代磷酸酯(phorate,三九一-)
O-(4-溴-2-氯苯基)-O-乙基-S-丙基二硫代磷酸酯(prophenofos)
S-[1,2-二(乙氧羰基)乙基]-O,O-二甲基二硫代磷酸酯(malathio,马拉硫磷)
O,O,O′,O′-四乙基-S,S′-亚甲基双(二硫代磷酸酯)(ethion,乙硫磷)
O-(4-溴-2,5-二氯苯基)-O,O-二乙基硫代磷酸酯(bromophsethyl,乙基溴硫磷)
S-[(4-氯苯基)硫甲基]-O,O-二乙基二硫代磷酸酯(carbophenothion,三硫磷)
[2-氯-1-(2,4-二氯苯基)乙烯基]二乙基磷酸酯
(chlorphenvinphos,毒虫畏)
O-(2,5-二氯-4-甲硫基苯基)-O,O-二乙基硫代磷酸酯(chlorthiophos,氯甲硫磷)
O-(4-氰基苯基)-O,O-二甲基硫代磷酸酯(cyanophos,杀螟腈)
O,O-二甲基-O-(2-甲硫乙基)硫代磷酸酯(demiphion-O,异田乐硫磷)
O,O-二乙基-O-(2-乙硫乙基)硫代磷酸酯基(demeton-o,异-0五九)
O-(2,4-二氯苯基)-O,O-二乙基硫代磷酸酯(dichlorofenthion,氯线磷)
O-(2,4-二氯苯基)-O-乙基苯基硫代磷酸酯(EPBP,伊比硫磷)
O,O-二乙基-O-(5-苯基异噁唑-3-基硫代磷酸酯(isoxathion,异噁唑硫磷)
[1,3-二(甲氧羰基)-1-丙烯-2-基]二甲基磷酸酯
S,S-1,4-二恶烷-2,3-双(O,O-二乙基二硫代磷酸酯(dioxathion,二噁硫磷)
O,O-二甲基-O-(4-硝基-间-甲苯基)硫代磷酸酯(fenitrothion,杀螟松)
O,O-二甲基-O-(4-甲硫基-间-甲苯基)硫代磷酸酯(fenthion,倍硫磷)
O-(5-氯-1-异丙基-1,2,4-三唑-3-基)-O,O-二乙基硫代磷酸酯(isazophos,异丙三唑硫磷)
S-(2-异丙硫乙基)-O,O-二甲基二硫代磷酸酯(isothioate,甲丙乙拌磷)
(4-甲硫苯基)二丙基磷酸酯基(propaphos,丙虫磷)
(1,2-二溴-2,2-二氯乙基)二甲基磷酸酯(naled,二溴磷)
O,O-二乙基[(α-氰基苄叉)氨基氧代]硫代磷酸酯(phoxim,肟硫磷)
O,O-二乙基-O-(4-硝基苯基)硫代磷酸酯(parathion,一六0五)
O-(2-二乙氨基-6-甲基嘧啶-4-基)-O,O-二乙基硫代磷酸酯(pirimiphos-ethyl,嘧啶硫磷)
O-(2-二乙氨基-6-甲基嘧啶-4-基)-O,O-二甲基硫代磷酸酯(pirimiphos-methyl,甲基嘧啶硫磷)
O,O,O′,O′-四乙基二硫代焦磷酸酯(sulfotep,硫特普)
O,O,O′,O′-四甲基-O,O′-(硫代二-对苯撑)双硫代磷酸酯(temephos,双硫磷)
S-(2-乙硫乙基)-O,O-二甲二硫代磷酸酯(thiometon,甲基乙拌磷)
O,O-二乙基-O-(1-苯基-1,2,4-三唑-3-基)硫代磷酸酯(triazophos,三唑硫磷)
O-乙基-O-(2,4,5-三氯苯基)乙基硫代磷酸酯(trichloronate,壤虫硫磷)
(±)-3-烯丙基-2-甲基-4-氧代环戊-2-烯基(±)-顺,反-菊酸酯(allenthrin,丙烯菊酯)
(±)-3-烯丙基-2-甲基-4-氧代环戊-2-烯基(±)-反-菊酸酯(bioallenthrin,右旋反丙烯菊酯)
3-苯氧苄基(±)-顺,反-菊酸酯(phenothrin,苯醚菊酯)
除虫菊酯
2-(2-丁氧乙氧基)乙基硫氰酸酯
异冰片基硫代氰酸乙酸酯(萜品基硫代氰酸乙酸酯)
二硫化碳
2-(4-叔丁基苯氧基)环己基丙-2-炔基亚硫酸酯(propargite,克螨特)
4,6-二硝基-2-辛基苯基丁烯酸酯(dinocap,消螨普)
4,4′-二氯二苯乙醇酸乙酯(chlorobenzilate)
S,S,S-三丁基三硫代磷酸酯
S,S,S-三丁基三硫代亚磷酸酯(merphos,脱叶亚磷)
环烷酸铜
5-乙氧基-3-三氯甲基-1,2,4-噻二唑(etridiazole,氯唑灵)
O-乙基-S,S-二苯基二硫代磷酸酯(edifenphos,克瘟散)
6-丁氧基羰基-2,3-二氢-2,2-二甲基吡喃-4-酮(but opyronoxyl,避蚊酮)
N,N-二乙基-间-甲苯酰胺(deet,避蚊胺)
邻苯二甲酸二丁酯
丁二酸二丁酯
1,5a,6,9,9a,9b-六氢4a(4H)-二苯并呋喃-甲酸酯
吡啶-2,5-二羧酸二丙酯
用于本发明的组合物中的农药有许多不同类型,某些种类更为可取。有机磷化合物是较好的一类,特别是下式所代表的一类化合物
式中,X是氧或硫;R,R1和R2各自选自C1-C6烷基,C1-C6烷氧基,C1-C6烷硫基,C2-C6链烯基,C2-C6链烯氧基,C2-C6链烯硫基,苯基,苯氧基,苯硫基,C7-C9苯基烷基,C7-C9苯基烷氧基,和C7-C9苯基烷硫基;而这些基团又可以被囟素,C1-C4烷基,C1-C4烷氧基,氰基和硝基中最多三个取代基任意取代。
术语“烷基”,“烷氧基”等,既包括直链基团也包括支链基团,并且可以包括所有碳原子范围。而更可取的有机磷化合物是那些X为硫,R、R1和R2分别是C1-C4烷氧基或苯氧基的化合物,且该苯环可任意被C1-C3烷基,硝基,氰基和囟素中最多三个取代基取代。最可取的化合物是X为硫,R为C1-C4烷氧基,R1为C1-C4烷氧基,而R2为苯氧基的化合物,且该苯环可被选自C1-C3烷基和硝基的最多三个取代基取代。
较好的农药化合物是S-叔丁硫甲基-O,O-二乙基二硫代磷酸酯和O,O-二乙基-S-乙硫甲基二硫代磷酸酯。
最好的化合物具有下述通式:
式中R3和R4选自甲基和乙基,Y是氢或最多4个碳原子的烷基。
在本发明的组合物中作为活性组份的最好的农药化合物是在美国专利2,988,474中提到的那些化合物,而最为可取的化合物是O-乙基-S-苯基乙基二硫代磷酸酯(stauffer化学公司以商品名Dyfonate出售此化合物)。
适于在组合物中使用的表面活性剂是非离子型的,其HLB值大约17到大约20。
最可取的表面活性剂是150mole乙氧基化二壬基苯酚(HLB值为19.0,GAF公司以商品名Igepa DM970制造该化合物,其它各公司都有不同的商品名)。
在这种制剂中非离子型表面活性剂在化学上起稳定粘土粒上有机磷或其它活性农药化合物的作用,同时也有降低有机磷/粘土粒制剂的经皮毒性的作用。
一般组合物中的其它适宜的表面活性剂,举例有烷基和二烷基苯氧基聚(亚乙基氧)乙醇。具有前述HLB值范围的适宜的表面活性剂例如下述结构式代表的表面活性剂
式中n等于1或2。
在本发明中,适宜的表面活性剂的其它例子列于表Ⅰ中。
表Ⅰ
HLB 商品名 结构
17.9 Myrj 53 聚氧乙烯(50)硬脂酸酯
18.0 Etocas 100 乙氧基化(100)蓖麻油
18.0 Lantrol AWS 烷氧基化羊毛脂油
18.0 Veronic L167 乙氧基化椰子单甘油酯
18.1 Alcasurf CO200 乙氧基化蓖麻油
18.1 Chemmax CO-200/50 乙氧基化蓖麻油
18.1 Pegosperse CO 200聚氧乙烯200,蓖麻油
18.1 Veronic Li48 乙氧基化单和二甘油酯
18.0 Tergitol 15-s-50 仲醇聚乙二醇醚
18.3 Kessco PEG400 聚乙二醇单油酸酯
18.8 Brig 700 聚乙烯(100)十八碳醚
18.8 Kessco PEG酯 聚乙二醇单硬脂酸酯
18.5 Pluronic L-35
17.0 Pluronic P-65
本发明的组合物中用作惰性填料的较好的粘土有活性白土类和蒙脱土类。活性白土的主型分子式为Mg5Si8O(OH)28H2O而蒙脱土的主型分子式为Al2(Si4O16)(OH)2。
活性白土用作本发明的组合物中的惰性填料是非常有效的。
这两种粘土对于熟悉该技术的人员是熟知的,而且在Handbook of Insecticide Dust Diluents and Carries一书(T.C.Watkins and L.B.Norton,Dorland Books,Caldwell,New Jersey(1955)中已作了描述。
也可以采用其它传统的填料,但是,粘土是最可取的。
将活性组份(农药和表面活性剂)喷洒在粘土上并进行调和,从而得到活性组份均匀分布在整个体系中的制剂。粒度范围在10-60目,特别是18-48目(美国筛号)的本发明的粒状组合物是非常实用的。
因此,本发明的令人满意的组合物包括下述组成:
(a)大约1-45%(重量)生物活性量的有机磷化合物,该化合物具有下述通式:
式中R3和R4各自为甲基或乙基,Y可以是氢或最多4个碳的烷基。
(b)大约0.1-10%(重量)的150mole乙氧基化二壬基苯酚。
(c)大约50-98%(重量)的粘土粒。
上面规定的制剂是通过有机磷化合物来描述的,就象美国专利2,988,474所叙述的那样,可以预料,其它疏水性农药-粘土粒制剂,通过采用这里叙述的表面活性剂可以具有经皮安全性。
本发明描述的制剂类型如下。
活性白土粒 80% 活性白土粒 75%
Igepal DM970 5% Igepal DM970 5%
- -
100% 100%
*=S-叔丁基硫甲基-O,O-二乙基二硫代磷酸酯
**=O,O-二乙基-S-乙硫基甲基二硫磷酸酯
活性白土粒 80% 活性白土粒 75%
Igepal DM 970 5% Igepal DM 970 5%
- -
100% 100%
Igepal DM 970的结构式如下
农药制剂通常如下制备:取一定量的Dyfonate随即与需要量的Igepal DM970混合,然后将此混合物喷洒在粘土粒上,并彻底混合。典型方法如下。
例1
将15.82克Dyfonate
(工业纯,活性组份含量95%)于水浴上加热至55-75℃,然后溶入5克Igepal DM970,随即将此溶液用吸液管转移至装有79.18克粘土粒的旋转烧杯中。此后,旋转将近一小时,以使各组份充分混合。
本发明的农药组合物可有各种含量的农药,表面活性剂和干燥的惰性填料
农药化合物在粒状组合物中的量取决于惰性载体的吸收能力和喷洒设备的喷洒功效。一般说来,农药在组合物中的比例可占到1%到大约45%,以15%为最好(以重量为准)。
以重量百分数表示,表面活性剂在组合物中所占的比例与它的确切组成有关,可以占到大约0.1%到大约10%,较好的范围是1%到6%,而最理想的范围是2%到5%。
干燥的惰性填料在农药组合物中的量可以占到50%到大约98%,最好是大约80%。
可以通过下述例子对本发明更好的了解,这仅仅是典型的,而且是非限制性的。
下述例子证明了采用本发明的组合物减少了经皮毒性。
在例Ⅱ中进行经皮毒性试验时,在两种制剂之间进行了比较:其中一种含有Igepal DM 970非离子型表面活性剂,而另一种含有传统的化学稳定剂,二丙二醇。经皮毒性按照下述方法进行测定。
例Ⅱ
经皮毒性
按照美国环境保护局对于在美国注册农药提出的标准测定经皮毒性;公害平均:人类和家畜,联邦政府注册(Fed.Reg.)43卷163号,37336-37402(1978年8月22日)。
白化体兔(加尼福尼亚州,Soguel,菲利普养兔场,Stauffland白种)被豢养在控温的畜圈里(65-70°F),每个悬挂的钢笼里(24寸×16.5寸×14寸)放入两只兔。投喂随意量的饲料(加尼福尼亚州,摩根山,冈特兄弟公司,特制混合饲料)和水。
处理前,随机地对这些兔子进行选择,并用耳签进行编号。处理前一天将要处理的皮肤区域齐根剪去毛且禁食过夜,仅喂以水。
试验的第一次剂量是501毫克/公斤(10只兔,5雄5雌)。此后,选择的剂量呈对数变化。选择的标准至少使三个试验组的死亡率在10%和90%之间,以便进行雄体和雌体的LD50(伤皮和/或未伤皮)的计算,且置信度为95%而差异为20%或更小。至少要进行三个剂量水平和对照的试验。
每个剂量标准用四雄四雌八只兔子。在某些试验中,在每一个剂量水平上有一半的兔子作了进一步的处理,即用针在完全暴露的地方交叉划伤。划伤要深得进入角质层,但却未进入真皮。组合物被均匀地施用于受药点。通过一个非吸收性绷带使组合物与皮肤接触。为确保绷带的完好不动,外面再裹以纱布。24小时后,除去包裹层,擦净和/或洗涤皮肤以除去残余的试验物质。然后将它们用新纱布裹住并放置在原处72小时。
四只兔子(雄雌各两只)用同样的方式包裹进行了假处理。
施药后要对这些兔子进行至少14天的观察或直到未死兔子的所有可逆毒性信号消失为止。
临床症状的观察和死亡数的记录通常是在第一个白天和此后的一早一晚进行。周末和假期每天观察一次。所有的临床症状都用开始,持续和严重来记录。兔子化第零天(处理前),7天,14天或死亡时都称重,并计算这些天数的平均体重。
实验表明,受试动物的皮肤先行擦伤并不影响急性经皮毒性。这些试验的结果列于表Ⅱ中。
表Ⅱ
按照Litchfield和Wilcoxon方法测定LD50
路线:经皮 品种:兔子 性别:雌雄
制剂 经皮LD50
5%二丙二醇
80%活性白土粒
100%
5% Igepal DM 970
80%活性白土粒
-
100%
*括号中的值是95%置信界线。
LD50按每公斤体重组合物的毫克数进行测定。
例Ⅲ
例Ⅲ
按照Litchfield和Wilcoxon方法测定LD50
路线:经皮 品种:兔子 性别:雌雄
制剂 经皮LD50
5%二丙二醇
75%活性白土
-
100%
2.20%Thinet
231(208-258)*
5%Igepal DM 970
75%活性白土粒
-
100%
5%二丙二醇
80%活性白土
-
100%
5% Igepal DM 970
80%活性白土
-
100%
*括号中的值是95%置信界线。
LD50系按每公斤体重组合物的毫克数来测定。
这就再一次看到,表面活性剂Igepal DM970代替二丙二醇之后,制剂的经皮毒性大约减小了一半。
杀虫效力
组合物的杀虫效力用下述方法进行试验:
含有大约7000个卵的1立方厘米(毫升)黄瓜甲虫幼虫(Diabrotica undercimpunctata)被稀释到最终浓度为250个卵/毫升,方法是将0.5毫升未稀释的卵悬浮于14毫升含有0.2%达可粘(Diamond碱公司)的水中。在5℃下,卵在这种悬浮液中可以保存5天而无明显的失活。
10克潮湿的“上层土壤”(加尼福尼亚州,旧金山,Wonderline,Rod Mclellan公司)放于一个一盎司的清洁塑料杯(得克萨斯州,El Faso,Thnnderbird容器公司)中。将试验物质溶解在丙酮或其它适当的溶剂中。再将已稀释到所需浓度的0.05毫升等分试样加到土壤中。盖上盖,在Vari-Whirl混合器上将土壤混合大约15秒钟。在土壤表面压一个坑,加入0.2毫升卵悬浮液。用土将卵盖住并在室温(大约70°F)下保存。四天以后放入直立莴苣叶的一个切片。一周后观察杯中活着的幼虫。
试验浓度以10ppm直到发生大约50%死亡数的浓度。
用了两个试验组合物来比较本发明的组合物的杀虫效力。按本发明组合物的配制的第一个组合物(1)含15% Dyfonate
,5%Igepal DM970和80%活性白土,第二个组合物(2)含20% Dyfonate
,5%二丙二醇和75%活性白土。试验结果列于表Ⅳ。
表Ⅳ
黄瓜甲虫的LC50值(ppm)
组合物(1) 0.4
组合物(2) 0.4
以上述结果可以看出,本发明的组合物对黄瓜甲虫的LC50值与含有传统化学稳定剂-二丙二醇的类似组合物是一致的。这就表明,用Igepal DM 970代替二丙二醇对于活性组份的生物效力并无不利的影响。
熟悉该技术领域的人员显然可以看出,本发明的组合物显著地减小了经皮毒性而对于组合物中所用农药化合物的生物效力没有降低。
Claims (10)
1、一种农药组合物包括以下组成:
(a)一种经皮毒性农药化合物;
(b)一种HLB值为大约17到20的非离子型表面活性剂;和
(c)一种干燥的惰性填料。
2、权利要求1的农药组合物,其中所说的经皮毒性农药是一种有机磷农药。
3、权利要求2的农药组合物,其中所说的有机磷农药化合物可以是磷酸酯,硫代磷酸酯和拟除虫菊酯。
5、权利要求3的农药组合物,其中所说的有机磷农药化合物包括下式所示的化合物,
式中,R3和R4是甲基或乙基,Y是氢或最多4个碳原子的烷基。
6、权利要求1的组合物,其中所说的表面活性剂是150mole乙氧基化二壬基苯酚。
7、减轻经皮毒性农药化合物对哺乳动物经皮毒性的方法,该方法包括,向所说的经皮毒性化合物加入一定量HLB值为大约17到大约20的非离子型表面活性剂,这就足以减小所说经皮毒性化合物的经皮毒性。
8、权利要求7的方法,其中所说的经皮毒性化合物是O-乙基-S-苯基-乙基二硫代磷酸酯。
9、防治昆虫虫害的方法,该方法包括向发现了昆虫虫害的地域,于害虫生活周期的某时期施用杀虫有效量的杀虫组合物。该组合物包括以下组成:
(a)由下式所代表的有机磷化合物:
式中,X是氧或硫;R,R1和R2各自为C1-C6烷基,C1-C6烷氧基,C1-C6烷硫基,C2-C6链烯基,C2-C6链烯氧基,C2-C6链烯硫基,苯基,苯氧基,苯硫基,C7-C9苯基烷基,C7-C9苯基烷氧基,和C7-C9苯基烷硫基,每一个基团又可任意被囟素,C1-C4烷基,C1-C4烷氧基,氰基和硝基中最多三个取代基任意取代。
(b)一种HLB值为大约17到大约20的乙氧基化二壬基苯酚表面活性剂。
(c)一种干燥的惰性填料。
10、权利要求9的方法,其中所说的有机磷化合物是O-乙基-S-苯基-乙基二硫代磷酸酯。
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US6646011B2 (en) | 1998-06-03 | 2003-11-11 | Johnson & Johnson Consumer Companies, Inc. | Insect repellant compositions |
US9206381B2 (en) | 2011-09-21 | 2015-12-08 | Ecolab Usa Inc. | Reduced misting alkaline cleaners using elongational viscosity modifiers |
US20150141251A1 (en) * | 2012-10-15 | 2015-05-21 | Gowan Comercio Internacional E Servicos Limiada | Spontaneous self-forming mixed surfactant nano-emulsions from water insoluble pesticides in mixed water miscible solvents |
US9637708B2 (en) | 2014-02-14 | 2017-05-02 | Ecolab Usa Inc. | Reduced misting and clinging chlorine-based hard surface cleaner |
US10370626B2 (en) | 2016-05-23 | 2019-08-06 | Ecolab Usa Inc. | Reduced misting acidic cleaning, sanitizing, and disinfecting compositions via the use of high molecular weight water-in-oil emulsion polymers |
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WO2018160818A1 (en) | 2017-03-01 | 2018-09-07 | Ecolab Usa Inc. | Reduced inhalation hazard sanitizers and disinfectants via high molecular weight polymers |
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US4603214A (en) * | 1985-02-14 | 1986-07-29 | Bayer Aktiengesellschaft | Agents for combating pests |
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ES2053461T3 (es) | 1994-08-01 |
SK207587A3 (en) | 1997-07-09 |
AR241992A1 (es) | 1993-02-26 |
DK163887D0 (da) | 1987-03-31 |
CZ207587A3 (en) | 1997-02-12 |
MY101710A (en) | 1992-01-17 |
IL82049A0 (en) | 1987-10-20 |
DK163887A (da) | 1987-10-01 |
DE3783935T2 (de) | 1993-06-03 |
HUT46517A (en) | 1988-11-28 |
SK278483B6 (en) | 1997-07-09 |
CA1317875C (en) | 1993-05-18 |
PH24021A (en) | 1990-02-09 |
EP0243694A2 (en) | 1987-11-04 |
IL82049A (en) | 1992-12-01 |
DE3783935D1 (de) | 1993-03-18 |
HU205825B (en) | 1992-07-28 |
ATE85184T1 (de) | 1993-02-15 |
EP0243694B1 (en) | 1993-02-03 |
BR8701421A (pt) | 1987-12-29 |
CZ282064B6 (cs) | 1997-05-14 |
EP0243694A3 (en) | 1990-05-16 |
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