JPH0481561B2 - - Google Patents
Info
- Publication number
- JPH0481561B2 JPH0481561B2 JP59068818A JP6881884A JPH0481561B2 JP H0481561 B2 JPH0481561 B2 JP H0481561B2 JP 59068818 A JP59068818 A JP 59068818A JP 6881884 A JP6881884 A JP 6881884A JP H0481561 B2 JPH0481561 B2 JP H0481561B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- atom
- chloro
- cyclopropanecarboxylate
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 methylimino group Chemical group 0.000 claims description 34
- 125000005843 halogen group Chemical group 0.000 claims description 17
- 230000000895 acaricidal effect Effects 0.000 claims description 15
- 239000002917 insecticide Substances 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 239000000642 acaricide Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims description 6
- 125000004970 halomethyl group Chemical group 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 230000002503 metabolic effect Effects 0.000 claims description 5
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 241000238631 Hexapoda Species 0.000 description 10
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000749 insecticidal effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 241000238876 Acari Species 0.000 description 8
- 241000255925 Diptera Species 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000003814 drug Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 5
- YMGUBTXCNDTFJI-UHFFFAOYSA-M cyclopropanecarboxylate Chemical compound [O-]C(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-M 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229960005235 piperonyl butoxide Drugs 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 241000257226 Muscidae Species 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002728 pyrethroid Substances 0.000 description 4
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 241001674044 Blattodea Species 0.000 description 3
- 241000723353 Chrysanthemum Species 0.000 description 3
- 235000007516 Chrysanthemum Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000004783 oxidative metabolism Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229960005199 tetramethrin Drugs 0.000 description 3
- CXBMCYHAMVGWJQ-UHFFFAOYSA-N tetramethrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OCN1C(=O)C(CCCC2)=C2C1=O CXBMCYHAMVGWJQ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZCVAOQKBXKSDMS-AQYZNVCMSA-N (+)-trans-allethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-AQYZNVCMSA-N 0.000 description 2
- LNJXZKBHJZAIKQ-UHFFFAOYSA-N 1,1,1,2-tetrachloro-3-(2,3,3,3-tetrachloropropoxy)propane Chemical compound ClC(Cl)(Cl)C(Cl)COCC(Cl)C(Cl)(Cl)Cl LNJXZKBHJZAIKQ-UHFFFAOYSA-N 0.000 description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 2
- FMTFEIJHMMQUJI-NJAFHUGGSA-N 102130-98-3 Natural products CC=CCC1=C(C)[C@H](CC1=O)OC(=O)[C@@H]1[C@@H](C=C(C)C)C1(C)C FMTFEIJHMMQUJI-NJAFHUGGSA-N 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 241001414720 Cicadellidae Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- WLLGXSLBOPFWQV-UHFFFAOYSA-N MGK 264 Chemical compound C1=CC2CC1C1C2C(=O)N(CC(CC)CCCC)C1=O WLLGXSLBOPFWQV-UHFFFAOYSA-N 0.000 description 2
- 241000257159 Musca domestica Species 0.000 description 2
- 241001477931 Mythimna unipuncta Species 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 241001454295 Tetranychidae Species 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 229940024113 allethrin Drugs 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000017105 transposition Effects 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 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 1
- ADFXKUOMJKEIND-UHFFFAOYSA-N 1,3-dicyclohexylurea Chemical compound C1CCCCC1NC(=O)NC1CCCCC1 ADFXKUOMJKEIND-UHFFFAOYSA-N 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- JOCMKNDJEFJITQ-UHFFFAOYSA-N 2-[3-(4-fluorophenoxy)phenyl]-2-hydroxyacetonitrile Chemical compound N#CC(O)C1=CC=CC(OC=2C=CC(F)=CC=2)=C1 JOCMKNDJEFJITQ-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- 241001143309 Acanthoscelides obtectus Species 0.000 description 1
- 241000238657 Blattella germanica Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- STUSTWKEFDQFFZ-UHFFFAOYSA-N Chlordimeform Chemical compound CN(C)C=NC1=CC=C(Cl)C=C1C STUSTWKEFDQFFZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001465977 Coccoidea Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001555556 Ephestia elutella Species 0.000 description 1
- 241001466042 Fulgoromorpha Species 0.000 description 1
- 241000258937 Hemiptera Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000005916 Methomyl Substances 0.000 description 1
- 241000721621 Myzus persicae Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000320508 Pentatomidae Species 0.000 description 1
- 241000500437 Plutella xylostella Species 0.000 description 1
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 description 1
- 244000088415 Raphanus sativus Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- ISRUGXGCCGIOQO-UHFFFAOYSA-N Rhoden Chemical compound CNC(=O)OC1=CC=CC=C1OC(C)C ISRUGXGCCGIOQO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 240000006677 Vicia faba Species 0.000 description 1
- 235000010749 Vicia faba Nutrition 0.000 description 1
- 235000002098 Vicia faba var. major Nutrition 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- IRUJZVNXZWPBMU-UHFFFAOYSA-N cartap Chemical compound NC(=O)SCC(N(C)C)CSC(N)=O IRUJZVNXZWPBMU-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 1
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 description 1
- 244000013123 dwarf bean Species 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- ZNOLGFHPUIJIMJ-UHFFFAOYSA-N fenitrothion Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C(C)=C1 ZNOLGFHPUIJIMJ-UHFFFAOYSA-N 0.000 description 1
- DIRFUJHNVNOBMY-UHFFFAOYSA-N fenobucarb Chemical compound CCC(C)C1=CC=CC=C1OC(=O)NC DIRFUJHNVNOBMY-UHFFFAOYSA-N 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000003958 fumigation Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000021331 green beans Nutrition 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- UHXUZOCRWCRNSJ-QPJJXVBHSA-N methomyl Chemical compound CNC(=O)O\N=C(/C)SC UHXUZOCRWCRNSJ-QPJJXVBHSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- VOEYXMAFNDNNED-UHFFFAOYSA-N metolcarb Chemical compound CNC(=O)OC1=CC=CC(C)=C1 VOEYXMAFNDNNED-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WLLGXSLBOPFWQV-OTHKPKEBSA-N molport-035-783-878 Chemical compound C([C@H]1C=C2)[C@H]2C2C1C(=O)N(CC(CC)CCCC)C2=O WLLGXSLBOPFWQV-OTHKPKEBSA-N 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000422 nocturnal effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000024241 parasitism Effects 0.000 description 1
- 229960003536 phenothrin Drugs 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- PWYIUEFFPNVCMW-UHFFFAOYSA-N propaphos Chemical compound CCCOP(=O)(OCCC)OC1=CC=C(SC)C=C1 PWYIUEFFPNVCMW-UHFFFAOYSA-N 0.000 description 1
- 239000003380 propellant Substances 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
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound 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 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 description 1
- 229940048383 pyrethrum extract Drugs 0.000 description 1
- 230000000384 rearing effect Effects 0.000 description 1
- VEMKTZHHVJILDY-FIWHBWSRSA-N resmethrin Chemical compound CC1(C)[C@H](C=C(C)C)C1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-FIWHBWSRSA-N 0.000 description 1
- 229940108410 resmethrin Drugs 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 210000000115 thoracic cavity Anatomy 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は一般式
(式中、Aは式()、()、()で表わされる
基を示す。ただし、Bが酸素原子の場合、Aは式
()で表わされる基のみを示す。
ここにR6、R7は同一又は相異なつてハロゲン
原子又はハロメチル基を表わし、Xはハロゲン原
子を示す。R8はハロゲン原子又はシアノ基を、
R9はハロゲン原子、メチル基、ハロメチル基又
はハロメトキシ基を示し、R1はクロル原子又は
メチル基を表わす。
R2は水素原子、シアノ基又はエチニル基であ
り、R3、R4は水素原子又はフツ素原子を表わす。
Bは酸素原子、イオウ原子、メチレン基、イミノ
基又はメチルイミノ基を示し、R5は水素原子又
はハロゲン原子を表わす。)で示される抗酸化代
謝性ハロゲン置換シクロプロパンカルボン酸エス
テル誘導体、その製造法及びそれを有効成分とし
て含有することを特徴とする殺虫、殺ダニ剤に関
する。
一般式()、()で表わされるピレスロイド
は
(ここにR2は水素原子又はシアノ基を表わす。)
現在、家庭用、防疫用、農業用殺虫剤として広く
使用されている。ところで殺虫、殺ダニ剤が分解
して効力を失なう過程に、光、酸化による分解と
昆虫、ダニ体内における代謝による分解がある。
一般式()で表わされる菊酸エステルは酸部分
に光に不安定なイソブテニル基を有し、従つて屋
外での使用には制限を受けてきた。近年光安定性
に富む酸部の研究が盛んになり、その結果発明さ
れた一般式()のハロゲン置換菊酸エステルは
光安定性が著しく改善されて農業用殺虫剤として
の条件を満たすに至つた。一方、代謝分解の基礎
研究も精力的に続けられ、例えば一般式()に
おいて○※印の位置すなわち、カルボキシル基に対
してトランス位のメチル基、フエノキシ基の4位
の水素原子、ベンジル基の6位の水素原子が、昆
虫体内で酸化的分解を受けやすいことが明らかと
なつた。又、最近、実使用の場で、ピレスロイド
剤に対して感受性のやや低下したイエバエの出現
が報告されたが、これらの系統においては、ピレ
スロイドの酸化的代謝阻害剤であるピペロニルブ
トキサイドをピレスロイドに加えることによつて
感受性が回復することが認められた。
薬剤に対する抵抗性発達の一メカニズムとし
て、昆虫あるいはダニ体内における代謝酵素活性
の増大があげられており、従つて上記の知見は、
酸化的代謝を受けやすい部分の構造を修飾するこ
とによつてこの種の抵抗性発達を抑制できうるこ
とを示唆している。
そこで本発明者らは、抗酸化代謝性ピレスロイ
ドの開発を目的として鋭意研究を続けた結果、一
般式()で表わされるシクロプロパンカルボン
酸エステル誘導体、すなわち、カルボキシル基に
対してトルエン位の従来のメチル基を酸化分解を
受けにくいクロル原子に変換し、更に好ましく
は、R3、R8の位置にハロゲン原子を導入した化
合物が、ピレスロイド剤に対して感受性が低下し
た昆虫、ダニ類にも共力剤を添加することなくも
との感受性系統に対するのと同等の殺虫、殺ダニ
活性を示すことを見い出し本発明を完成した。
一般式()の化合物は、カルボキシル基に対
してトランスの位置にクロル原子を導入した点に
特徴があり、かつ、ピレスロイド剤に対して感受
性が低下した昆虫、ダニ類にも同様に高い活性を
発揮することは従来にはない知見である。更に、
理想的な殺虫、殺ダニ剤であるピレスロイド剤を
将来にむけてずつと実用に供するためには、抵抗
性の発達は回避しなければならない問題である
が、本発明化合物及びその組成物はその意味で極
めて有用な手段を提供するものである。
本発明化合物(一般式())はエステル製造
の一般方法に準じて一般式
(式中、Aは式()、()、()で表わされる
基を示す。ただし、Bが酸素原子の場合、Aは式
()で表わされる基のみを示す。
ここにR6、R7は同一又は相異なつてハロゲン
原子又はハロメチル基を表わし、Xはハロゲン原
子を示す。R8はハロゲン原子又はシアノ基を、
R9はハロゲン原子、メチル基、ハロメチル基又
はハロメトキシ基を示し、R1はクロル原子又は
メチル基を表わす。)で表わされるシクロプロパ
ンカルボン酸又はその反応性誘導体と、一般式
(式中、R2は水素原子、シアノ基又はエチニル
基であり、R3、R6は水素原子又はフツ素原子を
表わす。Bは酸素原子、イオウ原子、メチレン
基、イミノ基又はメチルイミノ基を示し、R5は
水素原子又はハロゲン原子を表わす。)で示され
るアルコール又はその反応性誘導体とを反応させ
ることによつて調製しえる。シクロプロパンカル
ボン酸の反応性誘導体としては例えば、酸ハライ
ド、酸無水物、低級アルキルエステル、アルカリ
金属塩などがあげられる。アルコールの反応性誘
導体としては例えばクロライド、ブロマイド、p
−トルエンスルホン酸エステルなどがあげられ
る。反応は適当な溶媒中で必要により脱酸剤また
は触媒としての有機または無機塩基又は酸の存在
下に必要により加熱下に行なわれる。一般式
()の本発明化合物は2つ以上の不斉炭素原子
を有する。本発明化合物はそれらの光学異性体お
よびラセミ体混合物を含むが、後述する実施例、
化合物例において特記せぬ限り製造した化合物は
ラセミ体混合物である。次に上記式()で示さ
れる化合物の代表例を示すが本発明はもちろんこ
れらのみに限定されるものではない。
3′−(4−フルオロアニリノ)−4′−フルオロ−
α′−シアノベンジル2,2−ジクロロ−3−
(2,2−ジクロロビニル)シクロプロパンカ
ルボキシレート n20 D1.5763
3′−(4−クロロアニリノ)−4′,6′−ジフルオ
ロ−α′−シアノベンジル2,2−ジクロロ−3
−(2,2−ジブロモビニル)シクロプロパン
カルボキシレート n20 D1.5790
3′−(4−ブロモベンジル)−α′−シアノベンジ
ル2,2−ジクロロ−3−(2,2−ジクロロ
ビニル)シクロプロパンカルボキシレート
n20 D1.5738
3′−(4−フルオロベンジル)−6′−フルオロ−
α′−シアノベンジル2,2−ジクロロ−3−
(2,2−ジブロモビニル)シクロプロパンカ
ルボキシレート n20 D1.5776
3′−(4−クロロアニリノ)−4′−フルオロ−
α′−シアノベンジル2,2−ジクロロ−3−
(2−クロロ−2−トリフルオロメチルビニル)
シクロプロパンカルボキシレート n20 D1.5716
3′−(4−ブロモベンジル)ベンジル2−メチ
ル−2−クロロ−3−(2−フルオロ−2−ジ
フルオロクロロメチルビニル)シクロプロパン
カルボキシレート n20 D1.5727
3′フエニルチオ−4′−フルオロ−α′−エチニル
ベンジル2−メチル−2−クロロ−3−(2,
2−ジトリフルオロメチルビニル)シクロプロ
パンカルボキシレート n20 D1.5704
3′−(4−フルオロフエノキシ)−α′−シアノベ
ンジル2,2−ジクロロ−3−{2−クロロ−
2−(4−クロロフエニル)ビニル}シクロプ
ロパンカルボキシレート n20 D1.5809
3′−(N−メチルアニリノ)−6′−フルオロ−
α′−シアノベンジル2,2−ジクロロ−3−
{2−シアノ−2−(4−メチルフエニル)ビニ
ル}シクロプロパンカルボキシレート
n20 D1.5821
3′(4−クロロフエニルチオ)−4′,6′−ジフル
オロ−α′−シアノベンジル2−メチル−2−ク
ロロ−3−{2−ブロモ−2−(4−トリフルオ
ロメチルフエニル)ビニル}シクロプロパンカ
ルボキシレート n20 D1.5833
3′−(4−ブロモアニリノ)−6′−フルオロベン
ジル2,2−ジクロロ−3−{2−フルオロ−
2−(4−ジフルオロメトキシフエニル)ビニ
ル}イクロプロパンカルボキシレート
n20 D1.5826
3′−(4−フルオロ−N−メチルアニリノ)−
4′−フルオロ−α′−エチニルベンジル2−メチ
ル−2−クロロ−3−(2,2−ジクロロビニ
ル)シクロプロパンカルボキシレート
n20 D1.5759
3′−(4−クロロフエニルチオ)−6′−フルオロ
ベンジル2,2−ジクロロ−3−(2,2−ジ
フルオロビニル)シクロプロパンカルボキシレ
ート n20 D1.5762
3′(4−ブロモアニリノ)ベンジル2−メチル
−2−クロロ−3−(1,2−ジブロモ−2,
2−ジクロロエチル)シクロプロパンカルボキ
シレート n20 D1.5816
3′(4−フルオロベンジル)−6′−フルオロ−
α′−エチニルベンジル2,2−ジクロロ−3−
(1,2−ジクロロ−2,2−ジフルオロエチ
ル)シクロプロパンカルボキシレート
n20 D1.5791
3′(4−ブロモフエニルチオ)−4′−フルオロ−
α′−シアノベンジル2−クロロ−2−メチル−
3−(1,2,2,2−テトラブロモエチル)
シクロプロパンカルボキシレート n20 D1.5814
3′(4−フルオロ−N−メチルアニリノ)ベン
ジル2,2−ジクロロ−3−(1,2−ジフル
オロ−2,2−ジクロロエチル)シクロプロパ
ンカルボキシレート n20 D1.5788
3′−(4−クロロベンジル)−4′−フルオロ−
α′−エチニルベンジル2−メチル−2−クロロ
−3−{2−シアノ−2−(4−ブロモフエニ
ル)ビニル}シクロプロパンカルボキシレート
n20 D1.5809
3′−(4−ブロモ−N−メチルアニリノ)−4′,
6′−ジフルオロベンジル2−メチル−2−クロ
ロ−3−{2−クロロ−2−(4−トリフルオロ
メトキシフエニル)ビニル}シクロプロパンカ
ルボキシレート n20 D1.5830
3′−(4−フルオロフエニルチオ)−4′,6′−ジ
フルオロ−α′−エチニルベンジル2−メチル−
2−クロロ−3−(2−クロロ−2−ブロモビ
ニル)シクロプロパンカルボキシレート
n20 D1.5734
3′(−N−メチルアニリノ)−6′−フルオロ−α
−′−シアノベンジル2,2−ジクロロ−3−
(2−ブロモ−2−フルオロジクロロメチルビ
ニル)シクロプロパンカルボキシレート
n20 D1.5713
3′(4−クロロアニリノ)−4′−フルオロ−α′−
エチニルベンジル2−メチル−2−クロロ−3
−{2−クロロ−2−(4−フルオロフエニル)
ビニル}シクロプロパンカルボキシレート
n20 D1.5829
3′(4−クロロフエノキシ)ベンジル2,2−
ジクロロ−3−(2−クロロ−3−トリフルオ
ロメチルビニル)シクロプロパンカルボキシレ
ート n20 D1.5708
本発明で有効成分として用いる化合物は常温で
固体または液体であつて有機溶剤一般に易溶であ
る。従つて散布用殺虫、殺ダニ剤としては乳剤、
油剤、粉剤、水和剤、エアゾール剤などとして用
いることができ、又木粉その他適当な基材と混合
して蚊取線香の如き燻蒸用殺虫、殺ダニ剤として
使用することができる。又、この有効成分を適当
な有機溶剤に溶かして台紙に浸ませ、または適当
な溶剤に溶解して適当な加熱体によつて加熱蒸散
させるいわゆる電気蚊取として使用する場合も蚊
取線香と同様すぐれた効果を示す。更に、本発明
の化合物は従来の菊酸エステル系ピレスロイドに
較べ光に安定であり、しかも殺虫、殺ダニスペク
トラムが広いこと、低毒性であること、安価であ
ることから従来の有機リン剤、有機塩素系殺虫剤
に替わる農園芸用殺虫、殺ダニ剤として使用する
ことができる。なお、本発明殺虫、殺ダニ剤は有
機リン剤、カーバメート剤抵抗性昆虫、ダニ類は
もちろん、従来のピレスロイド剤に対して感受性
が低下した昆虫、ダニ類にも極めて有効であり、
例えば、ハエ、蚊、ゴキブリ等の衛生害虫をはじ
め、ツマグロヨコバイ、ウンカ類や、ニカメイチ
ユウ、カメムシ類、ヨトウガ、コナガ、タバコ
ガ、マメゾウムシ、ヤガ、モンシロチヨウ、クリ
ケムシ、ハマキ、アブラムシ、カイガラムシ類等
の農業害虫、コクゾウ等の貯殻害虫、ダニ類等の
防除に極めて有用である。また本発明の殺虫、殺
ダニ剤にN−オクチルビシクロヘプテンジカルボ
キシイミド(商品名MGK−264)、N−オクチル
ビシクロヘプテンジカルボキシイミドとアリール
スルホン酸塩との混合物(商品名MGK−5026)、
サイネピリン500、オクタクロロジプロピルエー
テル、ピペロニルブトキサイドなどの共力剤を加
えるとその殺虫、殺ダニ効果を一層高めることが
できる。また本発明の殺虫、殺ダニ剤に他の殺虫
剤、例えば、フエニトロチオン、DDVP、ダイ
アジノン、プロパホス、ピリダフエンチオン等の
有機リン剤、NAC、MTMC、BPMC、PHCな
どのカーバメート剤、ピレトリン、アレスリン、
フタールスリン、フラメトリン、フエノトリン、
フエンバレレート、フエンプロパネートなどの従
来のピレスロイド系殺虫、殺ダニ剤、カルタツ
プ、クロルフエナミジン、メソミルなどの殺虫
剤、あるいは殺ダニ剤、殺菌剤、殺線虫剤、除草
剤、植物生長調整剤、肥料その他の農薬を混合す
ることによつて効果のすぐれた多目的組成物が得
られ、労力の省力化、薬剤間の相乗効果も充分期
待しえるものである。
次に代表例について合成実施例を示すが他の本
発明化合物も同様の傾向を示し、合成法(A)、(B)、
(C)、(D)、(E)、(F)のいずれの方法によつても収率よ
く得ることができた。
合成実施例 1
(A) アルコールとカルボン酸ハライドとの反応に
よる方法
2,2−ジクロロ−3−{2−クロロ−2−
(4−クロロフエニル)ビニル}シクロプロパ
ンカルボン酸クロライド6.6gを乾燥ベンゼン
15mlに溶解し、これに3−(4−フルオロフエ
ノキシ)−α−シアノベンジルアルコール5.2g
を乾燥ベンゼン20mlに溶解したものを加え、さ
らに縮合助剤として乾燥ピリジン3mlを加える
とピリジン塩酸塩が析出する。密栓して室温で
一夜放置後、ピリジン塩酸塩の結晶を別した
後ベンゼン溶液をぼう硝で乾燥しベンゼンを減
圧下に留去して3′−(4−フルオロフエノキシ)
−α′−シアノベンジル2,2−ジクロロ−3−
{2−クロロ−2−(4−クロロフエニル)ビニ
ル}シクロプロパンカルボキシレート9.8gを
得た。
合成実施例 2
(B) アルコールとカルボン酸との反応による方法
2−メチル−2−クロロ−3−(1,2−ジ
ブロモ−2,2−ジクロロエチル)シクロプロ
パンカルボン酸8.0gと3−(4−ブロモアニリ
ノ)ベンジルアルコール5.7gとを50mlの乾燥
ベンゼンに溶解し、6.2gのジシクロヘキシル
カルボジイミドを添加して一晩密栓放置した。
翌日、4時間加熱還流して反応を完結させ、冷
却後析出したジシクロヘキシル尿素を別し
た。ろ液を濃縮して得られた油状物質を100g
のシリカゲルカラムを流下させて3′−(4−ブ
ロモアニリノ)ベンジル2−メチル−2−クロ
ロ−3−(1,2−ジブロモ−2,2−ジクロ
ロエチル)シクロプロパンカルボキシレート
11.1gを得た。
合成実施例 3
(C) アルコールのハライドとアルカリ金属カルボ
ン酸塩との反応による方法
2−メチル−2−クロロ−3−{2−シアノ
−2−(4−ブロモフエニル)ビニル}シクロ
プロパンカルボン酸のナトリウム塩7.3gと3
−(4−クロロベンジル)−4−フルオロ−α−
エチニルベンジルクロライド6.0gをベンゼン
50mlに懸濁させ、還流下に3時間窒素気流虫で
反応させた後、反応液を冷却し、析出する食塩
をろ別した後、食塩水で充分洗浄後ぼう硝で乾
燥しベンゼンを減圧下に流去して3′−(4−ク
ロロベンジル)−4′−フルオロ−α′−エチニル
ベンジル2−メチル−2−クロロ−3−{2−
シアノ−2−(4−ブロモフエニル)ビニル}
シクロプロパンカルボキシレート10.2gを得
た。
合成実施例 4
(D) アルコールとカルボン酸の低級アルキルエス
テルとのエステル交換反応による方法
2,2−ジクロロ−3−(2,2−ジフルオ
ロビニル)シクロプロパンカルボン酸のメチル
エステル4.8gと3−(4−クロロフエニルチ
オ)−6−フルオロベンジルアルコール5.3gを
150℃に加熱する。温度が150℃に達した時にナ
トリウム0.25gを加えメタノールの留去を開始
する。メタノールの留去が停止したらさらにナ
トリウム0.25gを加え、理論量のメタノールを
得るまで温度を150℃前後に保ち前記操作を繰
返し行なう。ついで混合物を冷却し、エーテル
に溶解しエーテル溶液を希塩酸、重曹水、食塩
水で洗浄後ぼう硝で乾燥しエーテルを減圧下に
留去して3′−(4−クロロフエニルチオ)−6′−
フルオロベンジル2,2−ジクロロ−3−(2,
2−ジフルオロビニル)シクロプロパンカルボ
キシレート8.0gを得た。
合成実施例 5
(E) アルコールとカルボン酸無水物との反応によ
る方法
2−メチル−2−クロロ−3−{2−クロロ
−2−(4−トリフルオロメトキシフエニル)
ビニル}シクロプロパンカルボン酸無水物14.0
gと3−(4−ブロモ−N−メチルアニリノ)−
4,6−ジフルオロベンジルアルコール6.5g
とを50mlの乾燥ピリジンに溶解し室温で一晩か
く拌した。翌日、反応液を100gの氷水に注加
してエーテル20mlを用いて3回抽出した。エー
テル層を併せて、5%水酸化ナトリウム水溶液
20mlを用いて2回抽出して副生したカルボン酸
を除去した。エーテル層は更に希塩酸、重層
水、食塩水で洗浄後、ぼう硝で乾燥し減圧下に
エーテルを除去して粗エステルを得、これを活
性アルミナ20gのカラムを流下させて3′−(4
−ブロモ−N−メチルアニリノ)−4′,6′−ジ
フルオロベンジル 2−メチル−2−クロロ−
3−{2−クロロ−2−(4−トリフルオロメト
キシフエニル)ビニル}シクロプロパンカルボ
キシレート11.4gを得た。
合成実施例 6
(F) アルコールのハライドと有機第3級塩基のカ
ルボン酸塩との反応による方法
2,2−ジクロロ−3−(2,2−ジクロロ
ビニル)シクロプロパンカルボン酸5.2gをア
セトン50mlに溶解し、これに3−(4−フルオ
ロアニリノ)−4−フルオロ−α−シアノベン
ジルブロマイド6.5gを加える。かく拌下にト
リエチルアミン4mlを加え60〜80℃で3時間反
応させたのち、エーテルで溶解し、エーテル溶
液を希酸塩、重曹水、食塩水で充分洗浄後ぼう
硝で乾燥しエーテルを減圧下に留去して3′−
(4−フロオロアニリノ)−4′−フルオロ−α′−
シアノベンジル2,2−ジクロロ−3−(2,
2−ジクロロビニル)シクロプロパンカルボキ
シレート8.9gを得た。
次に本発明の化合物がすぐれたものであること
をより明らかにするために効果の試験成績を示
す。
試験例 1
散布による殺虫試験
本発明化合物の0.2%白灯溶液(A)、0.2%とサイ
ネピリン500 0.8%の白灯溶液(B)、0.1%とフター
ルスリン0.1%の白灯溶液(C)およびアレスリン、
フタールスリンの夫々0.2%の白灯溶液につき感
受性イエバエの落下仰転率を求め供試薬剤の相対
有効度を算出し、更に24時間後の致死率を求めた
ところ次の如くである。
( )内は24時間後の致死率を示す。
The present invention is based on the general formula (In the formula, A represents a group represented by formula (), (), or (). However, when B is an oxygen atom, A represents only a group represented by formula (). Here, R 6 and R 7 are the same or different and represent a halogen atom or a halomethyl group, and X represents a halogen atom. R 8 is a halogen atom or a cyano group,
R 9 represents a halogen atom, a methyl group, a halomethyl group, or a halomethoxy group, and R 1 represents a chloro atom or a methyl group. R 2 represents a hydrogen atom, a cyano group or an ethynyl group, and R 3 and R 4 represent a hydrogen atom or a fluorine atom.
B represents an oxygen atom, a sulfur atom, a methylene group, an imino group or a methylimino group, and R 5 represents a hydrogen atom or a halogen atom. The present invention relates to an antioxidant metabolic halogen-substituted cyclopropane carboxylic acid ester derivative represented by (), a method for producing the same, and an insecticide or acaricide containing the same as an active ingredient. The pyrethroids represented by the general formulas () and () are (R 2 here represents a hydrogen atom or a cyano group.)
Currently, it is widely used as an insecticide for household use, epidemic prevention, and agriculture. By the way, the processes by which insecticides and acaricides decompose and lose their effectiveness include decomposition due to light and oxidation, and decomposition due to metabolism within the bodies of insects and mites.
The chrysanthemum acid ester represented by the general formula () has an isobutenyl group which is unstable to light in the acid moiety, and therefore its use outdoors has been restricted. In recent years, research on acid moieties with high photostability has become active, and as a result, the halogen-substituted chrysanthemum acid ester of the general formula () has been invented, which has significantly improved photostability and now satisfies the requirements as an agricultural insecticide. Ivy. On the other hand, basic research on metabolic decomposition continues energetically.For example, in the general formula (), the positions marked with ○*, that is, the methyl group at the trans position to the carboxyl group, the hydrogen atom at the 4-position of the phenoxy group, and the hydrogen atom at the benzyl group It has become clear that the hydrogen atom at position 6 is susceptible to oxidative decomposition within the insect body. In addition, it has recently been reported that houseflies with slightly reduced susceptibility to pyrethroid drugs have appeared in actual use; Addition to pyrethroids was found to restore susceptibility. One mechanism for the development of resistance to drugs is an increase in metabolic enzyme activity within the body of insects or ticks; therefore, the above findings suggest that
This suggests that the development of this type of resistance can be suppressed by modifying the structure of parts that are susceptible to oxidative metabolism. Therefore, as a result of intensive research aimed at developing antioxidant metabolic pyrethroid, the present inventors discovered a cyclopropanecarboxylic acid ester derivative represented by the general formula ( Compounds in which a methyl group is converted to a chlorine atom that is less susceptible to oxidative decomposition, and more preferably a halogen atom is introduced at the R 3 and R 8 positions, are compatible with insects and mites that have reduced sensitivity to pyrethroids. We have completed the present invention by discovering that the product exhibits insecticidal and acaricidal activity equivalent to that of the original susceptible strain without the addition of a potent agent. The compound of general formula () is characterized by the introduction of a chlorine atom in the trans position relative to the carboxyl group, and also has high activity against insects and mites that have reduced sensitivity to pyrethroids. What it brings to the table is unprecedented knowledge. Furthermore,
In order to put pyrethroids, which are ideal insecticides and acaricides, into practical use in the future, the development of resistance must be avoided. In this sense, it provides an extremely useful means. The compound of the present invention (general formula ()) can be prepared using the general formula (2) according to the general method for producing esters. (In the formula, A represents a group represented by formula (), (), or (). However, when B is an oxygen atom, A represents only a group represented by formula (). Here, R 6 and R 7 are the same or different and represent a halogen atom or a halomethyl group, and X represents a halogen atom. R 8 is a halogen atom or a cyano group,
R 9 represents a halogen atom, a methyl group, a halomethyl group, or a halomethoxy group, and R 1 represents a chloro atom or a methyl group. ) Cyclopropanecarboxylic acid or its reactive derivative represented by the general formula (In the formula, R 2 represents a hydrogen atom, a cyano group, or an ethynyl group, and R 3 and R 6 represent a hydrogen atom or a fluorine atom. B represents an oxygen atom, a sulfur atom, a methylene group, an imino group, or a methylimino group. and R 5 represents a hydrogen atom or a halogen atom) or a reactive derivative thereof. Examples of reactive derivatives of cyclopropanecarboxylic acid include acid halides, acid anhydrides, lower alkyl esters, and alkali metal salts. Examples of reactive derivatives of alcohol include chloride, bromide, p
-Toluenesulfonic acid esters, etc. The reaction is carried out in a suitable solvent, optionally in the presence of an organic or inorganic base or acid as a deoxidizing agent or catalyst, and optionally with heating. The compound of the present invention of general formula () has two or more asymmetric carbon atoms. The compounds of the present invention include their optical isomers and racemic mixtures, but the examples described below,
Unless otherwise specified in the compound examples, the compounds produced are racemic mixtures. Next, representative examples of the compound represented by the above formula () will be shown, but the present invention is of course not limited to these. 3′-(4-fluoroanilino)-4′-fluoro-
α'-cyanobenzyl 2,2-dichloro-3-
(2,2-dichlorovinyl)cyclopropanecarboxylate n 20 D 1.5763 3'-(4-chloroanilino)-4',6'-difluoro-α'-cyanobenzyl 2,2-dichloro-3
-(2,2-dibromovinyl)cyclopropanecarboxylate n 20 D 1.5790 3'-(4-bromobenzyl)-α'-cyanobenzyl 2,2-dichloro-3-(2,2-dichlorovinyl)cyclopropanecarboxylate
n 20 D 1.5738 3'-(4-fluorobenzyl)-6'-fluoro-
α'-cyanobenzyl 2,2-dichloro-3-
(2,2-dibromovinyl)cyclopropanecarboxylate n 20 D 1.5776 3'-(4-chloroanilino)-4'-fluoro-
α'-cyanobenzyl 2,2-dichloro-3-
(2-chloro-2-trifluoromethylvinyl)
Cyclopropane carboxylate n 20 D 1.5716 3'-(4-bromobenzyl)benzyl 2-methyl-2-chloro-3-(2-fluoro-2-difluorochloromethylvinyl)cyclopropanecarboxylate n 20 D 1.5727 3′phenylthio-4′-fluoro-α′-ethynylbenzyl 2-methyl-2-chloro-3-(2,
2-ditrifluoromethylvinyl)cyclopropanecarboxylate n 20 D 1.5704 3'-(4-fluorophenoxy)-α'-cyanobenzyl 2,2-dichloro-3-{2-chloro-
2-(4-chlorophenyl)vinyl}cyclopropanecarboxylate n 20 D 1.5809 3'-(N-methylanilino)-6'-fluoro-
α'-cyanobenzyl 2,2-dichloro-3-
{2-cyano-2-(4-methylphenyl)vinyl}cyclopropanecarboxylate
n 20 D 1.5821 3'(4-chlorophenylthio)-4',6'-difluoro-α'-cyanobenzyl 2-methyl-2-chloro-3-{2-bromo-2-(4-trifluoromethylphenyl)vinyl }Cyclopropanecarboxylate n 20 D 1.5833 3'-(4-bromoanilino)-6'-fluorobenzyl 2,2-dichloro-3-{2-fluoro-
2-(4-difluoromethoxyphenyl)vinyl}cyclopropanecarboxylate
n 20 D 1.5826 3'-(4-fluoro-N-methylanilino)-
4'-Fluoro-α'-ethynylbenzyl 2-methyl-2-chloro-3-(2,2-dichlorovinyl)cyclopropanecarboxylate
n 20 D 1.5759 3'-(4-chlorophenylthio)-6'-fluorobenzyl 2,2-dichloro-3-(2,2-difluorovinyl)cyclopropanecarboxylate n 20 D 1.5762 3'(4-bromoanilino)benzyl 2-methyl-2-chloro-3-(1,2-dibromo-2,
2-dichloroethyl)cyclopropanecarboxylate n 20 D 1.5816 3'(4-fluorobenzyl)-6'-fluoro-
α'-ethynylbenzyl 2,2-dichloro-3-
(1,2-dichloro-2,2-difluoroethyl)cyclopropanecarboxylate
n 20 D 1.5791 3'(4-bromophenylthio)-4'-fluoro-
α′-cyanobenzyl 2-chloro-2-methyl-
3-(1,2,2,2-tetrabromoethyl)
Cyclopropane carboxylate n 20 D 1.5814 3'(4-Fluoro-N-methylanilino)benzyl 2,2-dichloro-3-(1,2-difluoro-2,2-dichloroethyl)cyclopropanecarboxylate n 20 D 1.5788 3'-(4-chlorobenzyl)-4'-fluoro-
α'-ethynylbenzyl 2-methyl-2-chloro-3-{2-cyano-2-(4-bromophenyl)vinyl}cyclopropanecarboxylate
n 20 D 1.5809 3'-(4-bromo-N-methylanilino)-4',
6'-difluorobenzyl 2-methyl-2-chloro-3-{2-chloro-2-(4-trifluoromethoxyphenyl)vinyl}cyclopropanecarboxylate n 20 D 1.5830 3'-(4-fluorophenylthio)-4',6'-difluoro-α'-ethynylbenzyl 2-methyl-
2-chloro-3-(2-chloro-2-bromovinyl)cyclopropanecarboxylate
n 20 D 1.5734 3′(-N-methylanilino)-6′-fluoro-α
-'-cyanobenzyl 2,2-dichloro-3-
(2-bromo-2-fluorodichloromethylvinyl)cyclopropanecarboxylate
n 20 D 1.5713 3′(4-chloroanilino)-4′-fluoro-α′-
Ethynylbenzyl 2-methyl-2-chloro-3
-{2-chloro-2-(4-fluorophenyl)
vinyl}cyclopropanecarboxylate
n 20 D 1.5829 3'(4-chlorophenoxy)benzyl 2,2-
Dichloro-3-(2-chloro-3-trifluoromethylvinyl)cyclopropanecarboxylate n 20 D 1.5708 The compound used as an active ingredient in the present invention is solid or liquid at room temperature and is generally easily soluble in organic solvents. Therefore, as insecticides and acaricides for spraying, emulsions,
It can be used as an oil, powder, wettable powder, aerosol, etc. It can also be used as an insecticide or acaricide for fumigation such as mosquito coils by mixing with wood flour or other suitable base material. Also, when used as a so-called electric mosquito repellent, in which the active ingredient is dissolved in an appropriate organic solvent and soaked in a mount, or dissolved in an appropriate solvent and heated and evaporated with an appropriate heating element, it can be used in the same way as a mosquito coil. Shows excellent effects. Furthermore, the compounds of the present invention are more photo-stable than conventional chrysanthemum acid ester-based pyrethroids, have a broader spectrum of insecticidal and acaricidal properties, have low toxicity, and are inexpensive, so they are less expensive than conventional organic phosphorus agents and organic pyrethroids. It can be used as an agricultural and horticultural insecticide and acaricide in place of chlorine-based insecticides. In addition, the insecticide and acaricide of the present invention is extremely effective not only for insects and mites resistant to organophosphorus agents and carbamate agents, but also for insects and mites that have decreased susceptibility to conventional pyrethroids.
For example, sanitary pests such as flies, mosquitoes, and cockroaches, as well as agricultural pests such as leafhoppers, planthoppers, stinkbugs, armyworms, mealybugs, tobacco moths, bean weevils, nocturnal moths, cabbage moths, chestnut beetles, leafhoppers, aphids, and scale insects. It is extremely useful for controlling insects such as mites, mites, etc. In addition, the insecticide and acaricide of the present invention include N-octylbicycloheptenedicarboximide (trade name MGK-264), a mixture of N-octylbicycloheptenedicarboximide and an aryl sulfonate (tradename MGK-5026),
The insecticidal and acaricidal effects can be further enhanced by adding synergists such as cinepirin 500, octachlorodipropyl ether, and piperonyl butoxide. In addition, other insecticides may be used in addition to the insecticides and acaricides of the present invention, such as organic phosphorus agents such as fenitrothion, DDVP, diazinon, propafos, and pyridafentione, carbamate agents such as NAC, MTMC, BPMC, and PHC, pyrethrin, and allethrin. ,
phthalthrin, flamethrin, phenothrin,
Conventional pyrethroid insecticides such as fuenvalerate, fuenpropanate, acaricides, cartap, chlorphenamidine, methomyl, or acaricides, fungicides, nematicides, herbicides, plant growth By mixing regulators, fertilizers, and other agricultural chemicals, highly effective multipurpose compositions can be obtained, and labor savings and synergistic effects among the drugs can be fully expected. Next, synthesis examples will be shown for representative examples, but other compounds of the present invention also show similar trends, and synthesis methods (A), (B),
It could be obtained in good yield by any method (C), (D), (E), or (F). Synthesis Example 1 (A) Method by reaction of alcohol and carboxylic acid halide 2,2-dichloro-3-{2-chloro-2-
(4-chlorophenyl)vinyl}cyclopropanecarboxylic acid chloride (6.6 g) in dry benzene
Dissolve in 15 ml and add 5.2 g of 3-(4-fluorophenoxy)-α-cyanobenzyl alcohol.
was dissolved in 20 ml of dry benzene, and then 3 ml of dry pyridine was added as a condensation aid to precipitate pyridine hydrochloride. After sealing the cap and leaving it overnight at room temperature, after separating the crystals of pyridine hydrochloride, the benzene solution was dried with sulfuric acid, and the benzene was distilled off under reduced pressure to give 3'-(4-fluorophenoxy).
-α'-cyanobenzyl 2,2-dichloro-3-
9.8 g of {2-chloro-2-(4-chlorophenyl)vinyl}cyclopropanecarboxylate was obtained. Synthesis Example 2 (B) Method by reaction of alcohol and carboxylic acid 8.0 g of 2-methyl-2-chloro-3-(1,2-dibromo-2,2-dichloroethyl)cyclopropanecarboxylic acid and 3-( 5.7 g of 4-bromoanilino)benzyl alcohol was dissolved in 50 ml of dry benzene, 6.2 g of dicyclohexylcarbodiimide was added, and the mixture was left sealed overnight.
The next day, the reaction was completed by heating under reflux for 4 hours, and after cooling, the precipitated dicyclohexyl urea was separated. 100g of the oily substance obtained by concentrating the filtrate
3'-(4-bromoanilino)benzyl 2-methyl-2-chloro-3-(1,2-dibromo-2,2-dichloroethyl)cyclopropanecarboxylate
11.1g was obtained. Synthesis Example 3 (C) Method by reaction of alcohol halide with alkali metal carboxylate 2-methyl-2-chloro-3-{2-cyano-2-(4-bromophenyl)vinyl}cyclopropanecarboxylic acid Sodium salt 7.3g and 3
-(4-chlorobenzyl)-4-fluoro-α-
6.0g of ethynylbenzyl chloride in benzene
Suspend in 50 ml and react under reflux with a nitrogen stream for 3 hours, cool the reaction solution, filter out the precipitated salt, wash thoroughly with brine, dry over sulfur and remove benzene under reduced pressure. 3'-(4-chlorobenzyl)-4'-fluoro-α'-ethynylbenzyl 2-methyl-2-chloro-3-{2-
Cyano-2-(4-bromophenyl)vinyl}
10.2 g of cyclopropane carboxylate was obtained. Synthesis Example 4 (D) Method using transesterification reaction between alcohol and lower alkyl ester of carboxylic acid 4.8 g of methyl ester of 2,2-dichloro-3-(2,2-difluorovinyl)cyclopropanecarboxylic acid and 3- (4-chlorophenylthio)-6-fluorobenzyl alcohol 5.3g
Heat to 150℃. When the temperature reaches 150°C, add 0.25 g of sodium and start distilling off methanol. When the distillation of methanol has stopped, an additional 0.25 g of sodium is added, and the above operation is repeated while keeping the temperature around 150°C until the theoretical amount of methanol is obtained. The mixture was then cooled, dissolved in ether, and the ether solution was washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over nitric acid, and the ether was distilled off under reduced pressure to give 3'-(4-chlorophenylthio)-6'. −
Fluorobenzyl 2,2-dichloro-3-(2,
8.0 g of 2-difluorovinyl) cyclopropanecarboxylate was obtained. Synthesis Example 5 (E) Method by reaction of alcohol and carboxylic acid anhydride 2-methyl-2-chloro-3-{2-chloro-2-(4-trifluoromethoxyphenyl)
vinyl}cyclopropanecarboxylic anhydride 14.0
g and 3-(4-bromo-N-methylanilino)-
4,6-difluorobenzyl alcohol 6.5g
was dissolved in 50 ml of dry pyridine and stirred at room temperature overnight. The next day, the reaction solution was poured into 100 g of ice water and extracted three times with 20 ml of ether. Combine the ether layers and add 5% aqueous sodium hydroxide solution.
The by-produced carboxylic acid was removed by extraction twice using 20 ml. The ether layer was further washed with dilute hydrochloric acid, multilayered water, and brine, dried over nitric acid, and the ether was removed under reduced pressure to obtain a crude ester.
-bromo-N-methylanilino)-4',6'-difluorobenzyl 2-methyl-2-chloro-
11.4 g of 3-{2-chloro-2-(4-trifluoromethoxyphenyl)vinyl}cyclopropanecarboxylate was obtained. Synthesis Example 6 (F) Method by reaction of alcohol halide and organic tertiary base carboxylate 5.2 g of 2,2-dichloro-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid was added to 50 ml of acetone. and add 6.5 g of 3-(4-fluoroanilino)-4-fluoro-α-cyanobenzyl bromide. Add 4 ml of triethylamine with stirring and react at 60 to 80°C for 3 hours, then dissolve in ether, wash the ether solution thoroughly with diluted acid salts, sodium bicarbonate solution, and brine, dry with sulfuric acid, and remove the ether under reduced pressure. Distilled into 3′−
(4-fluoroanilino)-4'-fluoro-α'-
Cyanobenzyl 2,2-dichloro-3-(2,
8.9 g of 2-dichlorovinyl)cyclopropanecarboxylate was obtained. Next, in order to make it clearer that the compounds of the present invention are excellent, the results of efficacy tests will be shown. Test Example 1 Insecticidal test by spraying 0.2% white light solution of the compound of the present invention (A), 0.2% and Cinepirin 500 0.8% white light solution (B), 0.1% and phthalthrin 0.1% white light solution (C), and allethrin ,
The relative effectiveness of the test agent was calculated by determining the falling and turning rate of susceptible house flies for each 0.2% white light solution of phthalthrin, and the mortality rate after 24 hours was determined as follows. The numbers in parentheses indicate the mortality rate after 24 hours.
【表】【table】
【表】
試験例 2
微量滴下法による殺虫試験
本発明化合物及び従来の化合物の各々とそれら
にピペロニルブトキサイドをそれぞれ有効成分の
2倍量添加し所定濃度のアセトン溶液としたもの
をマイクロシリンジにてイエバエ成虫の胸部背板
に施用した。イエバエは感受性系統及び累代飼育
によりピレスロイド剤に感受性が低下したフイー
ルド系統を用いた。24時間後の死虫率から従来の
化合物の感受性系統に対する相対殺虫力及びピペ
ロニルブトキサイドによる共力効果を調べたとこ
ろ次の如くである。[Table] Test Example 2 Insecticidal test by microdropping method A microsyringe was prepared by adding twice the amount of piperonyl butoxide as the active ingredient to each of the compounds of the present invention and conventional compounds, and making an acetone solution of a predetermined concentration. It was applied to the thoracic dorsal plate of adult house flies. House flies used were susceptible strains and field strains whose sensitivity to pyrethroid drugs had decreased through successive rearing. The relative insecticidal power of conventional compounds against susceptible strains and the synergistic effect of piperonyl butoxide were investigated based on the insect mortality rate after 24 hours, and the results are as follows.
試験の結果、本発明化合物は低感受性フイール
ド系統イエバエに対して、感受性系統と同様の高
い殺虫効力を示した。一方、対照化合物(A)、(B)、
(C)、(D)の低感受性フイールド系統イエバエに対す
る殺虫力は低かつたが、酸化的代謝を抑えるピペ
ロニルブトキサイドを加えることによつて活性は
回復した。このことより、従来のピレスロイドの
酸化的代謝を受けやすい部位にハロゲン原子を導
入するなどの構造修飾を加えた本発明化合物は、
ピレスロイドに対する抵抗性発達抑制に極めて効
果的であることが明らかとなつた。
次に製剤化の実施例を示すが製剤化にあたつて
は一般農薬に準じて何らの特別な条件を必要とせ
ず当業技術者の熟知する方法によつて調製しえ
る。
参考例 1
本発明化合物(2)0.2部に白灯油を加えて全体を
100部として0.2%油剤を得る。
参考例 2
本発明化合物(6)0.2部とピペロニルブトキサイ
ド0.8部に白灯油を加えて全体を100部として油剤
を得る。
参考例 3
本発明化合物(11)0.4部、レスメトリン0.1部、オ
クタクロロジプロピルエーテル1.5部を精製灯油
28部に溶解し、エアゾール容器に充填しバルブ部
分を取り付けた後該バルブ部分を通じて噴射剤
(液化石油ガス)70部を加圧充填してエアゾール
を得る。
参考例 4
本発明化合物(15)20部にソルポールSM200(東邦
化学登録商品名)10部、キシロール70部を加えて
攪拌混合溶解して20%乳剤を得る。
参考例 5
本発明化合物(18)0.5g、BHT0.5gを除虫菊抽出
粕粉、木粉、デン粉などの蚊取線香用基材99.0g
に均一に混合し、公知の方法によつて蚊取線香を
得る。
参考例 6
本発明化合物(21)0.4g、MGK−5026 1.0g
を蚊取線香用基材98.6gに均一に混合し公知の方
法によつて蚊取線香を得る。
参考例 7
本発明化合物(24)0.3部とクレー99.7部をよ
く粉砕混合して0.3%粉剤を得る。
参考例 8
本発明化合物(29)40部、珪藻土35部、クレー
20部、ラウリルスルホン酸塩3部、カルボキシメ
チルセルローズ2部を粉砕混合して水和剤を得
る。
試験例 3
モモアカアブラムシの多数発生した一面の5〜
6葉期の大根畑に参考例4によつて得られた乳剤
のうち本発明化合物(4)、(12)、(15)、(19)、(23)お
よ
び(29)を含む各々の乳剤の水による1000倍希釈
液を100/反あたり散布した。2日後の寄生率
調査で散布前密度の1/10以下に各区共に減少して
いた。
試験例 4
参考例4で得られた乳剤のうち本発明化合物
(6)、(11)、(15)、(18)、(22)および(26)の2000倍
希
釈液にかんらん生葉を薬液中に約5秒間浸漬し、
薬液乾燥後シヤーレに入れヨトウムシの健全幼虫
10頭を放飼した。その供試虫の放飼は生葉浸漬当
日、5日後の2回行ない、24時間後の死虫率を求
めた。 As a result of the test, the compound of the present invention showed high insecticidal efficacy against the low-susceptibility field strain housefly, similar to that of the susceptible strain. On the other hand, control compounds (A), (B),
The insecticidal activity of (C) and (D) against the low-susceptibility field strain housefly was low, but the activity was restored by adding piperonyl butoxide, which inhibits oxidative metabolism. From this, the compounds of the present invention, which have undergone structural modifications such as introducing halogen atoms into sites susceptible to oxidative metabolism of conventional pyrethroids,
It has been revealed that it is extremely effective in suppressing the development of resistance to pyrethroids. Next, an example of formulation will be shown, and the formulation can be prepared by a method well known to those skilled in the art without requiring any special conditions in accordance with general agricultural chemicals. Reference example 1 White kerosene was added to 0.2 parts of the present compound (2) and the whole
Obtain 0.2% oil solution as 100 parts. Reference Example 2 White kerosene is added to 0.2 parts of the compound (6) of the present invention and 0.8 parts of piperonyl butoxide to make a total of 100 parts to obtain an oil agent. Reference Example 3 0.4 parts of the present compound (11), 0.1 parts of resmethrin, and 1.5 parts of octachlorodipropyl ether were added to refined kerosene.
After dissolving in 28 parts and filling it into an aerosol container and attaching a valve part, 70 parts of a propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain an aerosol. Reference Example 4 To 20 parts of the compound (15) of the present invention, 10 parts of Solpol SM200 (registered trade name of Toho Chemical) and 70 parts of xylol were added and mixed and dissolved with stirring to obtain a 20% emulsion. Reference Example 5 0.5 g of the present compound (18) and 0.5 g of BHT were added to 99.0 g of a base material for mosquito coils such as pyrethrum extract powder, wood flour, starch powder, etc.
A mosquito coil is obtained by a known method. Reference example 6 Compound of the present invention (21) 0.4g, MGK-5026 1.0g
The mixture was uniformly mixed with 98.6 g of a mosquito coil base material to obtain a mosquito coil by a known method. Reference Example 7 0.3 parts of the compound of the present invention (24) and 99.7 parts of clay are thoroughly ground and mixed to obtain a 0.3% powder. Reference Example 8 40 parts of the present compound (29), 35 parts of diatomaceous earth, clay
20 parts of lauryl sulfonate, 3 parts of lauryl sulfonate, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder. Test Example 3 5 to 5 on a surface where a large number of green peach aphids appeared
Among the emulsions obtained in Reference Example 4 in a radish field at the 6-leaf stage, each emulsion containing the compounds of the present invention (4), (12), (15), (19), (23) and (29) A solution diluted 1000 times with water was sprayed 100 times per area. Two days later, the parasitism rate was investigated and found that the density had decreased to less than 1/10 of the pre-spraying density in each plot. Test Example 4 Among the emulsions obtained in Reference Example 4, the compound of the present invention
(6), (11), (15), (18), (22) and (26) 2000-fold dilutions of fresh leaves are immersed in the chemical solution for about 5 seconds,
After drying the chemical solution, put it in a shear dish to make healthy armyworm larvae.
Ten animals were released. The test insects were released twice, once on the day of soaking the fresh leaves and 5 days later, and the mortality rate was determined 24 hours later.
【表】
試験例 5
鉢植えのソラ豆へ殺虫成分を適用する1日前に
1本の木に対してアブラムシを約200匹寄生させ
た。参考例8によつて得られた水和剤のうち(3)、
(10)、(14)、(17)、(21)、(25)および(29)の4000
倍
希釈液を害虫がついた薬へ圧縮空気スプレー法で
10ml/ポツトあたり散布し2日後の被害度を観察
した。その結果いずれによつても被害度の増大は
認められなかつた。
試験例 6
参考例7によつて得られた(5)、(13)、(16)、(20)、
(24)および(27)の各々の粉剤を直径14cmの腰
高ガラスシヤーレ底面に2g/m2の割合で均一に
散布し底部約1cmを残してバターを壁面に塗布す
る。その中にチヤバネゴキブリ成虫を1群10匹と
して放ち、30分間接触させ新しい容器にゴキブリ
を移せば3日後にはいずれの粉剤によつても80%
以上のゴキブリを殺虫することができた。
試験例 7
播種5日後の鉢植えツルナシインゲン4葉に1
葉あたり10頭のニセナミハダニ雌成虫を寄生さ
せ、27℃恒温室で保管する。6日後、参考例4で
得られた乳剤(6)、(10)、(15)、(18)、(23)、(27)
およ
び(29)を水で有効成分100ppmに希釈した薬液
をターンテーブル上で1鉢あたり10ml散布した。
10日後植物上のニセナミハダニの調査ではいずれ
の薬剤においても寄生数は10頭以下であつた。[Table] Test Example 5 Approximately 200 aphids were infested on one tree one day before applying the insecticidal ingredient to potted fava beans. Among the hydrating agents obtained in Reference Example 8, (3)
(10), (14), (17), (21), (25) and (29) 4000
Apply the diluted solution to the pest-infested medicine using the compressed air spray method.
The degree of damage was observed after 2 days after spraying 10ml/pot. As a result, no increase in the degree of damage was observed in any of the cases. Test Example 6 (5), (13), (16), (20) obtained by Reference Example 7,
Each of the powders (24) and (27) was uniformly spread at a rate of 2 g/m 2 on the bottom of a tall glass shear dish with a diameter of 14 cm, and the butter was applied to the wall leaving about 1 cm of the bottom. If you release 10 adult German cockroaches into the container, let them come into contact with each other for 30 minutes, and transfer the cockroaches to a new container, after 3 days, 80% of the time will be affected by any powder.
I was able to kill more than one cockroach. Test Example 7 1 per 4 leaves of potted green beans 5 days after sowing
Each leaf is infested with 10 female adult spider mites and stored in a constant temperature room at 27°C. After 6 days, emulsions (6), (10), (15), (18), (23), (27) obtained in Reference Example 4
and (29) diluted with water to 100 ppm of active ingredient, and sprayed 10 ml per pot on a turntable.
After 10 days, the number of parasitized spider mites on the plants was less than 10 for all drugs.
Claims (1)
基を示す。ただし、Bが酸素原子の場合、Aは式
()で表わされる基のみを示す。 ここにR6、R7は同一又は相異なつてハロゲン
原子又はハロメチル基を表わし、Xはハロゲン原
子を示す。R8はハロゲン原子又はシアノ基を、
R9はハロゲン原子、メチル基、ハロメチル基又
はハロメトキシ基を示し、R1はクロル原子又は
メチル基を表わす。R2は水素原子、シアノ基又
はエチニル基であり、R3、R4は水素原子又はフ
ツ素原子を表わす。Bは酸素原子、イオウ原子、
メチレン基、イミノ基又はメチルイミノ基を示
し、R5は水素原子又はハロゲン原子を表わす。)
で示される抗酸化代謝性ハロゲン置換シクロプロ
パンカルボン酸エステル誘導体を有効成分として
含有することを特徴とする殺虫、殺ダニ剤。[Claims] 1. General formula (In the formula, A represents a group represented by formula (), (), or (). However, when B is an oxygen atom, A represents only a group represented by formula (). Here, R 6 and R 7 are the same or different and represent a halogen atom or a halomethyl group, and X represents a halogen atom. R 8 is a halogen atom or a cyano group,
R 9 represents a halogen atom, a methyl group, a halomethyl group, or a halomethoxy group, and R 1 represents a chloro atom or a methyl group. R 2 represents a hydrogen atom, a cyano group or an ethynyl group, and R 3 and R 4 represent a hydrogen atom or a fluorine atom. B is an oxygen atom, a sulfur atom,
It represents a methylene group, an imino group or a methylimino group, and R 5 represents a hydrogen atom or a halogen atom. )
An insecticide and acaricide characterized by containing an antioxidant metabolic halogen-substituted cyclopropane carboxylic acid ester derivative as an active ingredient.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59068818A JPS60214760A (en) | 1984-04-05 | 1984-04-05 | Antioxidative metabolic halogen-substituted cyclopropanecarboxylic acid ester derivative, its preparation and insecticidal and miticidal agent containing said derivative as active component |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59068818A JPS60214760A (en) | 1984-04-05 | 1984-04-05 | Antioxidative metabolic halogen-substituted cyclopropanecarboxylic acid ester derivative, its preparation and insecticidal and miticidal agent containing said derivative as active component |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60214760A JPS60214760A (en) | 1985-10-28 |
JPH0481561B2 true JPH0481561B2 (en) | 1992-12-24 |
Family
ID=13384672
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59068818A Granted JPS60214760A (en) | 1984-04-05 | 1984-04-05 | Antioxidative metabolic halogen-substituted cyclopropanecarboxylic acid ester derivative, its preparation and insecticidal and miticidal agent containing said derivative as active component |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60214760A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20180064101A1 (en) * | 2015-03-05 | 2018-03-08 | Dainihon Jochugiku Co., Ltd. | Water-based insecticidal composition to be vaporized and diffused by being heated, and method for vaporizing and diffusing said composition by heating |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2326077C2 (en) * | 1972-05-25 | 1985-12-12 | National Research Development Corp., London | Unsaturated cyclopropanecarboxylic acids and their derivatives, their preparation and insecticides containing them |
JPS5134881B2 (en) * | 1973-12-13 | 1976-09-29 | ||
JPS5879909A (en) * | 1981-11-07 | 1983-05-13 | Yoshio Katsuta | Insecticidal and miticidal agent having low toxicity to fish, and its preparation |
-
1984
- 1984-04-05 JP JP59068818A patent/JPS60214760A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS60214760A (en) | 1985-10-28 |
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