JPS6250458B2 - - Google Patents
Info
- Publication number
- JPS6250458B2 JPS6250458B2 JP55047233A JP4723380A JPS6250458B2 JP S6250458 B2 JPS6250458 B2 JP S6250458B2 JP 55047233 A JP55047233 A JP 55047233A JP 4723380 A JP4723380 A JP 4723380A JP S6250458 B2 JPS6250458 B2 JP S6250458B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- hydrogen atom
- formula
- atom
- halogen atom
- 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
Links
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 45
- -1 4-pentadienyl group Chemical group 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 36
- 125000005843 halogen group Chemical group 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 125000004970 halomethyl group Chemical group 0.000 claims description 18
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 15
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 125000004969 haloethyl group Chemical group 0.000 claims description 12
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 12
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 10
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002917 insecticide Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- SPAMRUYRVYMHPV-UHFFFAOYSA-N 3a,4,5,7a-tetrahydroisoindole-1,3-dione Chemical group C1=CCCC2C(=O)NC(=O)C21 SPAMRUYRVYMHPV-UHFFFAOYSA-N 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 5
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 5
- 125000005699 methyleneoxy group Chemical group [H]C([H])([*:1])O[*:2] 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 5
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 230000000895 acaricidal effect Effects 0.000 claims description 4
- 239000000642 acaricide Substances 0.000 claims description 4
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 239000002728 pyrethroid Substances 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims 1
- 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
- 239000000203 mixture Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 230000000749 insecticidal effect Effects 0.000 description 12
- AXLKXENSYFAPAH-UHFFFAOYSA-N 2,2,3-trimethyl-3-(trifluoromethyl)cyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(O)=O)C1(C)C(F)(F)F AXLKXENSYFAPAH-UHFFFAOYSA-N 0.000 description 10
- 241000255925 Diptera Species 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000004480 active ingredient Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 241000607479 Yersinia pestis Species 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 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 4
- 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 4
- NRUBUCXWQOAIRT-UHFFFAOYSA-N 2,2-dimethyl-3,3-bis(trifluoromethyl)cyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(O)=O)C1(C(F)(F)F)C(F)(F)F NRUBUCXWQOAIRT-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 241000723353 Chrysanthemum Species 0.000 description 4
- 235000007516 Chrysanthemum Nutrition 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
- 229940024113 allethrin Drugs 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 231100000053 low toxicity Toxicity 0.000 description 4
- 239000000463 material 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
- 150000003839 salts Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241001674044 Blattodea Species 0.000 description 3
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 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 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- YMGUBTXCNDTFJI-UHFFFAOYSA-M cyclopropanecarboxylate Chemical compound [O-]C(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-M 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229960005235 piperonyl butoxide Drugs 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 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
- YSZQWZJCJAJOJX-UHFFFAOYSA-N 2-(difluoromethyl)-3,3-dimethyl-2-(trifluoromethyl)cyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(O)=O)C1(C(F)F)C(F)(F)F YSZQWZJCJAJOJX-UHFFFAOYSA-N 0.000 description 2
- UVVQTFPCAKHPIU-UHFFFAOYSA-N 2-chloro-2-(chloromethyl)-3,3-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(O)=O)C1(Cl)CCl UVVQTFPCAKHPIU-UHFFFAOYSA-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
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical class [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 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
- 241001465754 Metazoa Species 0.000 description 2
- 241000257226 Muscidae Species 0.000 description 2
- 241001477931 Mythimna unipuncta Species 0.000 description 2
- 241000320508 Pentatomidae Species 0.000 description 2
- 241000500437 Plutella xylostella Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241001454295 Tetranychidae Species 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 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
- 239000012267 brine Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000003958 fumigation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 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 2
- 239000003960 organic solvent 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
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229960005199 tetramethrin Drugs 0.000 description 2
- 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 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
- AFEOKIGLYCQHAZ-UHFFFAOYSA-N (5-benzylfuran-3-yl)methanol Chemical compound OCC1=COC(CC=2C=CC=CC=2)=C1 AFEOKIGLYCQHAZ-UHFFFAOYSA-N 0.000 description 1
- ADFXKUOMJKEIND-UHFFFAOYSA-N 1,3-dicyclohexylurea Chemical compound C1CCCCC1NC(=O)NC1CCCCC1 ADFXKUOMJKEIND-UHFFFAOYSA-N 0.000 description 1
- SKCBKBCACWDALV-UHFFFAOYSA-N 1-(trifluoromethyl)cyclopropane-1-carboxylic acid Chemical compound OC(=O)C1(C(F)(F)F)CC1 SKCBKBCACWDALV-UHFFFAOYSA-N 0.000 description 1
- SMDCLAVUGJPMMI-UHFFFAOYSA-N 2,2,3-trimethyl-3-(2,2,2-trifluoroethyl)cyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(O)=O)C1(C)CC(F)(F)F SMDCLAVUGJPMMI-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
- CMBYXVYOHCDKNN-UHFFFAOYSA-N 2,2-dimethyl-3-(2,2,2-trifluoroethyl)-3-(trifluoromethyl)cyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(O)=O)C1(CC(F)(F)F)C(F)(F)F CMBYXVYOHCDKNN-UHFFFAOYSA-N 0.000 description 1
- WMXYOYLOFKGTFL-UHFFFAOYSA-N 2-(bromomethyl)-3,3-dimethyl-2-(2,2,2-trifluoroethyl)cyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(O)=O)C1(CBr)CC(F)(F)F WMXYOYLOFKGTFL-UHFFFAOYSA-N 0.000 description 1
- FHSWBYXUSTTZEW-UHFFFAOYSA-N 2-(chloromethyl)-2,3,3-trimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(O)=O)C1(C)CCl FHSWBYXUSTTZEW-UHFFFAOYSA-N 0.000 description 1
- UPROYBFQTDMSSJ-UHFFFAOYSA-N 2-(fluoromethyl)-2,3,3-trimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(O)=O)C1(C)CF UPROYBFQTDMSSJ-UHFFFAOYSA-N 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-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)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- TWTQFKSGHJHVJY-UHFFFAOYSA-N 2-bromo-2-[3-(4-chlorophenoxy)phenyl]acetonitrile Chemical compound C1=CC(Cl)=CC=C1OC1=CC=CC(C(Br)C#N)=C1 TWTQFKSGHJHVJY-UHFFFAOYSA-N 0.000 description 1
- GUOKRPAQJVKYFZ-UHFFFAOYSA-N 2-chloro-2-(chloromethyl)-1-(difluoromethyl)-3,3-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C(C1(C(F)F)C(=O)O)(CCl)Cl)C GUOKRPAQJVKYFZ-UHFFFAOYSA-N 0.000 description 1
- OAQZELWBCCJKSW-UHFFFAOYSA-N 2-chloro-2-(difluoromethyl)-3,3-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(O)=O)C1(Cl)C(F)F OAQZELWBCCJKSW-UHFFFAOYSA-N 0.000 description 1
- CWVBMPLGGNUYQK-UHFFFAOYSA-N 2-chloro-3,3-dimethyl-2-(trifluoromethyl)cyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(O)=O)C1(Cl)C(F)(F)F CWVBMPLGGNUYQK-UHFFFAOYSA-N 0.000 description 1
- WXNFLEJBSJJHBX-UHFFFAOYSA-N 2-fluoro-3,3-dimethyl-2-(trifluoromethyl)cyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(O)=O)C1(F)C(F)(F)F WXNFLEJBSJJHBX-UHFFFAOYSA-N 0.000 description 1
- WYYCRGGVHHJTTI-UHFFFAOYSA-N 3-(difluoromethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C(F)F)C1C(O)=O WYYCRGGVHHJTTI-UHFFFAOYSA-N 0.000 description 1
- IDHGYOQGMVANDO-UHFFFAOYSA-N 4-chloro-2,3-dihydro-1h-inden-1-ol Chemical compound C1=CC=C(Cl)C2=C1C(O)CC2 IDHGYOQGMVANDO-UHFFFAOYSA-N 0.000 description 1
- ISFGTDAAYLSOFY-UHFFFAOYSA-N 4-hydroxy-3-methyl-2-prop-2-ynylcyclopent-2-en-1-one Chemical compound CC1=C(CC#C)C(=O)CC1O ISFGTDAAYLSOFY-UHFFFAOYSA-N 0.000 description 1
- 241001143309 Acanthoscelides obtectus Species 0.000 description 1
- 241000238876 Acari 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001124134 Chrysomelidae Species 0.000 description 1
- 241001414720 Cicadellidae Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241000256054 Culex <genus> Species 0.000 description 1
- 239000005946 Cypermethrin Substances 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
- 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
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 239000005916 Methomyl Substances 0.000 description 1
- 241000721621 Myzus persicae Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 239000000292 calcium oxide Chemical class 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 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
- 235000013339 cereals Nutrition 0.000 description 1
- IXIYAEZKKVCJFK-UHFFFAOYSA-N chloromethyl cyclopropanecarboxylate Chemical compound ClCOC(=O)C1CC1 IXIYAEZKKVCJFK-UHFFFAOYSA-N 0.000 description 1
- 230000007665 chronic toxicity Effects 0.000 description 1
- 231100000160 chronic toxicity Toxicity 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
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 1
- 229960005424 cypermethrin Drugs 0.000 description 1
- KAATUXNTWXVJKI-UHFFFAOYSA-N cypermethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-UHFFFAOYSA-N 0.000 description 1
- 229960002483 decamethrin Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- OWZREIFADZCYQD-NSHGMRRFSA-N deltamethrin Chemical compound CC1(C)[C@@H](C=C(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 OWZREIFADZCYQD-NSHGMRRFSA-N 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
- 238000001035 drying Methods 0.000 description 1
- 244000013123 dwarf bean Species 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method 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
- 239000000417 fungicide Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000021331 green beans Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000005457 ice water 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
- 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
- 239000005645 nematicide Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000422 nocturnal effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003992 organochlorine insecticide Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000024241 parasitism Effects 0.000 description 1
- 229960000490 permethrin Drugs 0.000 description 1
- RLLPVAHGXHCWKJ-UHFFFAOYSA-N permethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-UHFFFAOYSA-N 0.000 description 1
- 229960003536 phenothrin Drugs 0.000 description 1
- 239000005648 plant growth regulator 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
- 229940108410 resmethrin Drugs 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
- 238000007789 sealing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical class [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000005068 transpiration Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
Landscapes
- Indole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Furan Compounds (AREA)
- Pyrrole Compounds (AREA)
Description
本発明は一般式
（式中、R1は水素原子、メチル基、エチル
基、ハロゲン原子、ハロメチル基又はハロエチル
基を示し、R2はハロメチル基又はハロエチル基
を表わす。ただしR1が水素原子の場合、R2はハ
ロメチル基を表わす。
Ｒは式（）、（）、（）、（）、（）で表
わ
される基を示す。
The present invention is based on the general formula (In the formula, R 1 represents a hydrogen atom, a methyl group, an ethyl group, a halogen atom, a halomethyl group, or a haloethyl group, and R 2 represents a halomethyl group or a haloethyl group. However, when R 1 is a hydrogen atom, R 2 Represents a halomethyl group. R represents a group represented by the formula (), (), (), (), ().
【式】【formula】
【式】―CH2―R11 …（）
―CH2―Ｃ≡Ｃ―CH2―R12 …（）
ここにR3は水素原子又はメチル基を、R4はア
リル基、プロパルギル基、ベンジル基又は２，４
―ペンタジエニル基を示す。Ｘは酸素原子、イオ
ウ原子又は（―CH＝CH―）グループであり、
R5は水素原子、シアノ基、エチニル基、プロピ
ニル基又はトリフルオロメチル基を示す。R6は
水素原子、メチル基、ハロゲン原子又はトリフル
オロメチル基を示し、ｎは１〜４の整数を表わ
す。R7はハロゲン原子、低級アルキル基、低級
ハロアルコキシ基、低級ハロアルコキシメチル
基、アリル基、プロパルギル基、ベンジル基、ベ
ンゾイル基、フエノキシ基、ベンゼン環の１個の
水素原子がハロゲン原子で置換されたフエノキシ
基又はジクロロビニルオキシ基を示す。ここで
R6とR7は共に末端で結合してトリメチレン又は
テトラメチレン鎖を形成する場合およびR5とR6
が末端で結合してエチレン又はメチレンオキシ鎖
を形成する場合も含まれる。R8は水素原子又は
エチニル基であり、R9およびR′9は水素原子、メ
チル基又はハロゲン原子を示す。R10はフエニル
基、ベンジル基または炭素数が２〜４までのアル
キル基、アルケニル基またはアルキニル基を表わ
す。R11はテトラヒドロフタルイミド基又はジア
ルキルマレイミド基を表わし、R12はフエニル基
又はフエノキシ基を表わす。）で示される新規シ
クロプロパンカルボン酸エステル誘導体及びその
光学ならびに幾何異性体、その製造法およびこの
化合物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。
菊酸エステルのアルコール成分については種々
のものが研究され実用に供されているが光によつ
て酸化分解を起こしやすく屋外での使用には制約
を受けてきた。最近、酸成分についての研究が盛
んになり、メチル基をハロゲン原子に置換するこ
とによつて従来のピレスロイドに比べ光に安定な
化合物が発見された。しかし環境汚染や慢性毒性
等の問題を考慮する時、炭素、水素、酸素、窒素
を中心とし、天然に存在する有機化合物と類似し
た構造を有する化合物がこれからの殺虫成分とし
て有利であると考えられる。本発明者は研究を重
ねた結果、上記式（）で示される化合物が殺虫
成分として種々の衛生害虫及び農園芸用害虫に極
めてすぐれた殺虫効果を奏する一方温血動物に対
する毒性が極めて低く、光に対しても従来の菊酸
エステルに比べ非常に安定であることを知つた。
このように上記式（）で示される化合物は光に
不安定であるという従来の菊酸エステル系ピレス
ロイドの欠点を克服し、広い殺虫スペクトルと低
毒性を兼備した優れた害虫防除組成物であり、し
かも上記式（）を構成するシクロプロパンカル
ボン酸は容易に安価に得ることができる。本発明
は以上の知見に基づいて完成されたものである。
本発明で有効成分として用いる上記式（）で示
される化合物はエステル製造の一般方法に準じて
一般式
（式中、R1は水素原子、メチル基、エチル
基、ハロゲン原子、ハロメチル基又はハロエチル
基を示し、R2はハロメチル基又はハロエチル基
を表わす。ただしR1が水素原子の場合、R2はハ
ロメチル基を表わす。）で表わされるカルボン酸
又はその反応性誘導体と一般式
HO―Ｒ …（）
式中、Ｒは（）、（）、（）、（）、（）
で
表わされる基を示す。[Formula] -CH 2 -R 11 ...() -CH 2 -C≡C-CH 2 -R 12 ...() Here, R 3 is a hydrogen atom or a methyl group, and R 4 is an allyl group, a propargyl group, or a benzyl group. group or 2,4
- indicates a pentadienyl group. X is an oxygen atom, a sulfur atom or a (-CH=CH-) group,
R 5 represents a hydrogen atom, a cyano group, an ethynyl group, a propynyl group, or a trifluoromethyl group. R 6 represents a hydrogen atom, a methyl group, a halogen atom or a trifluoromethyl group, and n represents an integer of 1 to 4. R 7 is a halogen atom, a lower alkyl group, a lower haloalkoxy group, a lower haloalkoxymethyl group, an allyl group, a propargyl group, a benzyl group, a benzoyl group, a phenoxy group, or one hydrogen atom of the benzene ring is substituted with a halogen atom. represents a phenoxy group or a dichlorovinyloxy group. here
When R 6 and R 7 are combined at the ends to form a trimethylene or tetramethylene chain, and R 5 and R 6
This also includes the case where they are bonded at the terminal to form an ethylene or methyleneoxy chain. R 8 is a hydrogen atom or an ethynyl group, and R 9 and R' 9 are a hydrogen atom, a methyl group, or a halogen atom. R 10 represents a phenyl group, a benzyl group, or an alkyl group having 2 to 4 carbon atoms, an alkenyl group, or an alkynyl group. R 11 represents a tetrahydrophthalimide group or a dialkylmaleimide group, and R 12 represents a phenyl group or a phenoxy group. The present invention relates to a novel cyclopropanecarboxylic acid ester derivative represented by () and its optical and geometrical isomers, a method for producing the same, and an insecticide and acaricide characterized by containing this compound as an active ingredient. Various alcohol components of chrysanthemum acid esters have been studied and put to practical use, but they are susceptible to oxidative decomposition by light, which has limited their use outdoors. Recently, research into acid components has become active, and a compound that is more stable to light than conventional pyrethroids by replacing the methyl group with a halogen atom has been discovered. However, when considering issues such as environmental pollution and chronic toxicity, compounds with structures similar to naturally occurring organic compounds, mainly consisting of carbon, hydrogen, oxygen, and nitrogen, are considered to be advantageous as future insecticidal ingredients. . As a result of repeated research, the present inventor has found that the compound represented by the above formula () has an extremely excellent insecticidal effect on various sanitary pests and agricultural and horticultural pests as an insecticidal ingredient, has extremely low toxicity to warm-blooded animals, and has an extremely low toxicity to warm-blooded animals. It was also found that it is much more stable than conventional chrysanthemum acid esters.
As described above, the compound represented by the above formula () overcomes the drawback of conventional chrysanthemum acid ester pyrethroids of being unstable to light, and is an excellent pest control composition that has a wide insecticidal spectrum and low toxicity. Moreover, the cyclopropanecarboxylic acid constituting the above formula () can be easily obtained at low cost. The present invention was completed based on the above findings.
The compound represented by the above formula () used as an active ingredient in the present invention can be prepared using the general formula (In the formula, R 1 represents a hydrogen atom, a methyl group, an ethyl group, a halogen atom, a halomethyl group, or a haloethyl group, and R 2 represents a halomethyl group or a haloethyl group. However, when R 1 is a hydrogen atom, R 2 represents a halomethyl group) or its reactive derivative and the general formula HO-R...() where R is (), (), (), (), ()
The group represented by is shown below.
【式】【formula】
【式】―CH2―R11 …（）
―CH2―Ｃ≡Ｃ―CH2―R12 …（）
ここに、R3は水素原子又はメチル基を、R4は
アリル基、プロパルギル基、ベンジル基又は２，
４―ペンタジエニル基を示す。Ｘは酸素原子、イ
オウ原子、又は（―CH＝CH―）グループであ
り、R5は水素原子、シアノ基、エチニル基、プ
ロピニル基又はトリフルオロメチル基を示す。
R6は水素原子、メチル基、ハロゲン原子又はト
リフルオロメチル基を示し、ｎは１〜４の整数を
表わす。R7はハロゲン原子、低級アルキル基、
低級ハロアルコキシ基、低級ハロアルコキシメチ
ル基、アリル基、プロパルギル基、ベンジル基、
ベンゾイル基、フエノキシ基、ベンゼン環の１個
の水素原子がハロゲン原子で置換されたフエノキ
シ基又はジクロロビニルオキシ基を示す。ここで
R6とR7は共に末端で結合してトリメチレン又は
テトラメチレン鎖を形成す場合、およびR5とR6
が末端で結合してエチレン又はメチレンオキシ鎖
を形成する場合も含まれる。R8は水素原子又は
エチニル基であり、R9およびR′9は水素原子、メ
チル基又はハロゲン原子を示す。R10はフエニル
基、ベンジル基または炭素数が２〜４までのアル
キル基、アルケニル基またはアルキニル基を表わ
す。R11はテトラヒドロフタルイミド基又はジア
ルキルマレイミド基を表わし、R12はフエニル基
又はフエノキシ基を表わす。）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。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（）の酸成分において、R1
とR2が異なる場合は少なくとも２個、同じ場合
は少なくとも１個の不斉炭素が存在し、通常の合
成法で得られるものはこれらの混合物であるが、
これらの各々ももちろん本発明に含まれる。なお
アルコール成分に不斉炭素が存在する場合も同様
である。上記式（）で示される化合物の代表例
を示せば次の通りであるが、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。
(1)
3′―フエノキシ―α′―シアノベンジル２，
２，３―トリメチル―３―トリフルオロメチル
シクロプロパンカルボキシレート ｎ２０ Ｄ 1.5405
(2)
3′―フエノキシ―α′―シアノベンジル２，
２―ジメチル―３―クロロ―３―トリフルオロ
メチルシクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5436
(3)
3′―フエノキシ―α′―シアノベンジル２，
２―ジメチル―３，３―ジトリフルオロメチル
シクロプロパンカルボキシレート ｎ２０ Ｄ 1.5412
(4)
3′―フエノキシ―α′―シアノベンジル２，
２―ジメチル―３―ジフルオロメチル―３―
（２，２，２―トリフルオロエチル）シクロプ
ロパンカルボキシレート ｎ２０ Ｄ 1.5487
(5)
3′―フエノキシ―α′―シアノベンジル２，
２―ジメチル―３―クロロジフルオロメチルシ
クロプロパンカルボキシレートｎ２０ Ｄ 1.5465
(6)
3′―フエノキシ―α′―シアノベンジル２，
２，３―トリメチル―３―ジフルオロメチルシ
クロプロパンカルボキシレートｎ２０ Ｄ 1.5423
(7)
3′―フエノキシ―α′―シアノベンジル２，
２―ジメチル―３―クロロ―３―（２，２，２
―トリフルオロエチル）シクロプロパンカルボ
キシレート ｎ２０ Ｄ 1.5510
(8)
3′―フエノキシ―α′―シアノベンジル２，
２，３―トリメチル―３―（２，２，２―トリ
フルオロエチル）シクロプロパンカルボキシレ
ート ｎ２０ Ｄ 1.5481
(9)
2′―アリル―3′―メチル―2′―シクロペンテ
ン―1′―オン―4′―イル２，２，３―トリメチ
ル―３―トリフルオロメチルシクロプロパンカ
ルボキシレート ｎ２０ Ｄ 1.5240
(10)
2′―ベンジル―2′―シクロペンテン―1′―オ
ン―4′―イル２，２，３―トリメチル―３―ク
ロロメチルシクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5517
(11)
5′―プロパルギル―2′―フリルメチル２，
２，３―トリメチル―３―トリフルオロメチル
シクロプロパンカルボキシレート ｎ２０ Ｄ 1.5204
(12)
5′―アリル―2′―メチル―3′―フリルメチル
２，２―ジメチル―３―フルオロ―３―トリフ
ルオロメチルシクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5233
(13)
4′，5′―テトラメチレン―3′―テニル２，２
―ジメチル―３―クロロ―３―（２，２，２，
１，１―ペンタフルオロエチル）シクロプロパ
ンカルボキシレート ｎ２０ Ｄ 1.5429
(14)
4′トリフルオロメチル―5′―（２，２，２―
トリフルオロエトキシメチル）―α′―プロピ
ニル―2′―テニル２，２―ジメチル―３―エチ
ル―３―ブロモメチルシクロプロパンカルボキ
シレート ｎ２０ Ｄ 1.5658
(15)
5′ベンジル―3′フリルメチル２，２，３―ト
リメチル―３―トリフルオロメチルシクロプロ
パンカルボキシレート ｎ２０ Ｄ 1.5492
(16)
2′―（２，４―ペンタジエニル）―3′―メチ
ル―2′―シクロペンテン―1′―オン―4′―イル
２，２，３―トリメチル―３―（２，２，２―
トリフルオロエチル）シクロプロパンカルボキ
シレート ｎ２０ Ｄ 1.5386
(17)
2′―プロパルギル―３―メチル―2′―シクロ
ペンテン―1′―オン―4′―イル２，２，３―ト
リメチル―３―トリフルオロメチルシクロプロ
パンカルボキシレート ｎ２０ Ｄ 1.5264
(18)
2′，3′，4′，5′，6′―ペンタフルオロベンジ
ル２，２―ジメチル―３，３―ジトリフルオロ
メチルシクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5271
(19)
4′―（２，２，２―トリフルオロエトキシメ
チル）ベンジル２，２―ジメチル―３―クロロ
―３―クロロメチルシクロプロパンカルボキシ
レート ｎ２０ Ｄ 1.5366
(20)
3′―（２，２，２―トリフルオロエトキシ）
―4′―トリフルオロメチル―α′―トリフルオ
ロメチルベンジル２，２―ジメチル―３―ブロ
モメチルシクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5405
(21)
2′，6′―ジクロロ―4′―アリルベンジル２，
２，３―トリメチル―３―フルオロメチルシク
ロプロパンカルボキシレート ｎ２０ Ｄ 1.5487
(22)
3′，4′―トリメチレン―α′―エチニルベン
ジル２，２―ジメチル―３―エチル―３―（２
―クロロエチル）シクロプロパンカルボキシレ
ート ｎ２０ Ｄ 1.5504
(23)
7′―メチル―2′，3′―ジヒドロベンゾフラン
―3′―イル２，２，３―トリメチル―３―トリ
フルオロメチルシクロプロパンカルボキシレー
ト ｎ２０ Ｄ 1.5536
(24)
7′―クロルインダン―3′―イル２，２―ジメ
チル―３―ジフルオロメチル―３―トリフルオ
ロメチルシクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5529
(25)
3′―ベンジル―α′―トリフルオロメチルベ
ンジル２，２―ジメチル―３―クロロ―３―ト
リフルオロメチルシクロプロパンカルボキシレ
ート ｎ２０ Ｄ 1.5615
(26)
3′―ベンゾイル―α′―エチニルベンジル
２，２―ジメチル―３―ブロモメチル―３―
（２，２，２―トリフルオロエチル）シクロプ
ロパンカルボキシレート ｎ２０ Ｄ 1.5703
(27)
3′―（２，２―ジクロロビニルオキシ）―
α′―シアノベンジル２，２―ジメチル―３―
ブロモ―３―（２，２，２，１，１―ペンタフ
ルオロエチル）シクロプロパンカルボキシレー
ト ｎ２０ Ｄ 1.5628
(28)
3′―（４―フルオロフエノキシ）―α′―シ
アノベンジル２，２，３―トリメチル―３―ト
リフルオロメチルシクロプロパンカルボキシレ
ート ｎ２０ Ｄ 1.5420
(29)
3′―フエノキシ―6′―フルオロ―α′―シア
ノベンジル２，２，３―トリメチル―３―トリ
フルオロメチルシクロプロパンカルボキシレー
ト ｎ２０ Ｄ 1.5417
(30)
3′（４―クロロフエノキシ）―α′―シアノ
ベンジル２，２―ジメチル―３―クロロ―３―
クロロメチルシクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5449
(31)
3′―（４―フルオロフエノキシ）―4′―フル
オロ―α′―シアノベンジル２，２―ジメチル
―３―フルオロ―３ジフルオロメチルシクロプ
ロパンカルボキシレート ｎ２０ Ｄ 1.5376
(32)
4′―ベンジルベンジル２，２―ジメチル―
３，３―ジ（２，２，２―トリフルオロエチ
ル）シクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5680
(33)
3′―ジフルオロメトキシ―6′―クロロ―α′
―シアノベンジル２，２，３トリメチル―３ト
リフルオロメチルシクロプロパンカルボキシレ
ート ｎ２０ Ｄ 1.5314
(34)
2′，3′，4′，5′，6′―ペンタクロロベンジル
２，２―ジメチル―３―クロロ―３―クロロメ
チルシクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5683
(35)
1′―エチニル―2′―メチル―2′―ペンテン―
1′―イル２，２，３―トリメチル―３―トリフ
ルオロメチルシクロプロパンカルボキシレート
ｎ２０ Ｄ 1.4970
(36)
2′―クロロ―3′―フエニルアリル２，２―ジ
メチル―３―（２，２，２―トリフルオロエチ
ル）―３―（２―ブロモエチル）シクロプロパ
ンカルボキシレート ｎ２０ Ｄ 1.5306
(37)
1′―エチニル―2′―メチル―3′―プロパルギ
ルアリル―1′―イル２，２，３―トリメチル―
３―トリフルオロメチルシクロプロパンカルボ
キシレート ｎ２０ Ｄ 1.5012
(38)
2′―ブロモ―2′，5′―ヘプタジエン―1′―イ
ル２，２―ジメチル―３―クロロ―３―ジフル
オロメチルシクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5241
(39)
1′―エチニル―2′―メチル―2′―ペンテン―
1′―イル２，２―ジメチル―３，３―ジトリフ
ルオロメチルシクロプロパンカルボキシレート
ｎ２０ Ｄ 1.4939
(40)
4′―フエニル―3′―クロロ―2′―ブテン―
1′―イル２，２―ジメチル―３―クロロ―３―
トリフルオロメチルシクロプロパンカルボキシ
レート ｎ２０ Ｄ 1.5405
(41)
3′，4′，5′，6′―テトラヒドロフタルイミド
メチル２，２，３―トリメチル―３―トリフル
オロメチルシクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5426
(42)
ジメチルマレイミドメチル２，２―ジメチル
―３―クロロ―３―（２，２，２―トリフルオ
ロエチル）シクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5430
(43)
4′―フエニル―2′―ブチン―1′―イル２，２
―ジメチル―３―エチル―３―フルオロメチル
シクロプロパンカルボキシレート ｎ２０ Ｄ 1.5382
(44)
4′―フエノキシ―2′―ブチン―1′―イル２，
２―ジメチル―３―クロロメチル―３―クロロ
ジフルオロメチルシクロプロパンカルボキシレ
ート ｎ２０ Ｄ 1.5403
(45)
3′，4′，5′，6′―テトラヒドロフタルイミド
メチル２，２―ジメチル―３―トリフルオロメ
チル―３―（２，２，２―トリフルオロエチ
ル）シクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5454
(46)
4′―フエニル―3′―メチル―2′―ブテン―
1′―イル２，２，３―トリメチル―３―（２，
２，２，１，１―ペンタフルオロエチル）シク
ロプロパンカルボキシレート ｎ２０ Ｄ 1.5395
(47)
7′―トリフルオロメチル―2′，3′―ジヒドロ
ベンゾフラン―3′―イル２，２―ジメチル―３
―ジフルオロメチルシクロプロパンカルボキシ
レート ｎ２０ Ｄ 1.5418
(48)
2′―メチル―4′―プロパルギル―α′―プロ
ビニルベンジル２，２―ジメチル―３―エチル
―３―（２，２，２―トリフルオロエチル）シ
クロプロパンカルボキシレートｎ２０ Ｄ 1.5477
(49)
3′―（３―ブロモベンゾイル）―α′―シア
ノベンジル２，２―ジメチル―３―フルオロ―
３―トリフルオロメチルシクロプロパンカルボ
キシレート ｎ２０ Ｄ 1.5678
(50)
5′―プロパルギル―2′―フリルメチル２，２
―ジメチル―３，３―ジトリフルオロメチルシ
クロプロパンカルボキシレートｎ２０ Ｄ 1.5211
(51)
2′―アリル―3′―メチル―2′―シクロペンテ
ン―1′―オン―4′―イル２，２―ジメチル―
３，３―ジトリフルオロメチルシクロプロパン
カルボキシレート ｎ２０ Ｄ 1.5245
(52)
2′，3′，4′，5′，6′―ペンタルフルオロベン
ジル２，２―ジメチル―３―フルオロ―３―
（１―クロロ―２，２，２―トリフルオロエチ
ル）シクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5304
(53)
3′―フエノキシベンジル２，２，３―トリメ
チル―３―トリフルオロメチルシクロプロパン
カルボキシレート ｎ２０ Ｄ 1.5356
(54)
3′―フエノキシベンジル２，２―ジメチル―
３―クロロ―３―トリフルオロメチルシクロプ
ロパンカルボキシレート ｎ２０ Ｄ 1.5329
(55)
5′―ベンジル―3′―フリルメチル２，２―ジ
メチル―３―ジフルオロメチル―３―トリフル
オロメチルシクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5470
本発明の化合物は新規化合物であり、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解
して台紙に浸ませ又は適当な溶剤に溶かして適当
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や、化学発熱体（例えば硫
化ソーダとカーボンからなる組成物、食塩、鉄、
カーボンからなる組成物、食塩、鉄、カーボン、
メタケイ酸ソーダの含水塩からなる組成物、生石
灰等があり、これらに空気あるいは水を接触させ
ることによつて発熱がおこる）やあるいはアダマ
ンタン、シクロドデカン、トリメチレンノルボル
ナン等の昇華性物質を補助剤として用いて蒸散さ
せる場合も蚊取線香と同様すぐれた効果を示す。
なお本発明の化合物は従来の菊酸エステル系ピレ
スロイドに比べ光に安定であり、しかも殺虫スペ
クトルが広いこと、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剤として使用することがで
きる。本発明化合物の用途として、ハエ、蚊、ゴ
キブリ等の衛生害虫をはじめ、有機リン剤、カー
バメート剤抵抗性ツマグロヨコバイ、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、コクゾウ等の貯穀害
虫、ダニ類等の防除に極めて有用である。また本
発明の化合物に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効果を一層高めることがで
きる。なお必要があれば本発明化合物にBHTや
DBHQ等の安定剤、酸化防止剤を加えることによ
つて安定性を一層向上させることができる。また
本発明の化合物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、ペルメトリン、サイペ
ルメトリン、デカメトリン、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)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
２，２，３―トリメチル―３―トリフルオロメ
チルシクロプロパンカルボン酸クロライド4.3ｇ
を乾燥ベンゼン15mlに溶解し、これに５―ベンジ
ル―３―フリルメチルアルコール3.7ｇ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
酸塩の結晶が析出する。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5′―ベンジル―3′―フリルメチル２，２，３―
トリメチル―３―トリフルオロメチルシクロプロ
パンカルボキシレート6.7ｇ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
２，２，３―トリメチル―３―（２，２，２，
１，１―ペンタフルオロエチル）シクロプロパン
カルボン酸5.0ｇと４―フエニル―３―メチル―
２―ブテン―１―オール3.3ｇを乾燥ベンゼン50
ml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ろ別した。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に
流下させて4′―フエニル―3′―メチル―2′―ブテ
ン―1′―イル２，２，３―トリメチル―３―
（２，２，２，１，１―ペンタフルオロエチル）
シクロプロパンカルボキシレート6.3ｇ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
ン酸との反応による方法
２，２―ジメチル―３―クロロ―３―（２，
２，２―トリフルオロエチル）シクロプロパンカ
ルボン酸のナトリウム塩5.2ｇと、ジメチルマレ
イミドメチルクロライド3.5ｇをベンゼン50mlに
懸濁させ、還流下に３時間窒素気流中で反応させ
た後食塩水で充分洗浄後ぼう硝で乾燥し、ベンゼ
ンを減圧下に留去してジメチルマレイミドメチル
２，２―ジメチル―３―クロロ―３―（２，２，
２―トリフルオロエチル）シクロプロパンカルボ
キシレート5.9ｇ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―ジメチル―３―ジフルオロメチル―３
―トリフルオロメチルシクロプロパンカルボン酸
のメチルエステル5.1ｇと７―クロロ―インダン
―３―オール3.2ｇ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、7′―クロロインダン―3′―イル２，２
―ジメチル―３―ジフルオロメチル―３―フルオ
ロメチルシクロプロパンカルボキシレート6.1ｇ
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
２，２，３―トリメチル―３―トリフルオロメ
チルシクロプロパンカルボン酸無水物7.5ｇと２
―プロパルギル―３―メチル―２―シクロペンテ
ン―１―オン―４―オール3.1ｇを50mlの乾燥ピ
リジンに溶解し室温下で一晩かく拌した。翌日反
応液を100ｇの氷水に注加し、エーテル20mlを用
いて３回抽出した。エーテル層を併せ、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。エーテル層はさら
に希塩酸、重曹水、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2′―プロパルギル―3′―メチル―2′―シクロペ
ンテン―1′―オン―4′―イル２，２，３―トリメ
チル―３―トリフルオロメチルシクロプロパンカ
ルボキシレート6.0ｇ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―ジメチル―３―クロロ―３―クロロメ
チルシクロプロパンカルボン酸4.1ｇをアセトン
50mlに溶解し、これに３―（４―クロロフエノキ
シ）―α―シアノベンジルブロマイド6.4ｇを加
える。撹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
エーテル溶液を希塩酸、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―クロロフエノキシ）―α′―シアノ
ベンジル２，２―ジメチル―３―クロロ―３―ク
ロロメチルシクロプロパンカルボキシレート7.1
ｇを得た。
次に本発明によつて提供される組成物がすぐれ
たものであることをより明らかにするため効果の
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％とピペ
ロニルブトキサイド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。[Formula] -CH 2 -R 11 ...() -CH 2 -C≡C-CH 2 -R 12 ...() Here, R 3 is a hydrogen atom or a methyl group, R 4 is an allyl group, a propargyl group, benzyl group or 2,
Indicates a 4-pentadienyl group. X is an oxygen atom, a sulfur atom, or a (-CH=CH-) group, and R 5 is a hydrogen atom, a cyano group, an ethynyl group, a propynyl group, or a trifluoromethyl group.
R 6 represents a hydrogen atom, a methyl group, a halogen atom or a trifluoromethyl group, and n represents an integer of 1 to 4. R 7 is a halogen atom, a lower alkyl group,
Lower haloalkoxy group, lower haloalkoxymethyl group, allyl group, propargyl group, benzyl group,
It represents a benzoyl group, a phenoxy group, a phenoxy group or a dichlorovinyloxy group in which one hydrogen atom of the benzene ring is substituted with a halogen atom. here
When R 6 and R 7 are joined together at the ends to form a trimethylene or tetramethylene chain, and R 5 and R 6
This also includes the case where they are bonded at the terminal to form an ethylene or methyleneoxy chain. R 8 is a hydrogen atom or an ethynyl group, and R 9 and R' 9 are a hydrogen atom, a methyl group, or a halogen atom. R 10 represents a phenyl group, a benzyl group, or an alkyl group having 2 to 4 carbon atoms, an alkenyl group, or an alkynyl group. R 11 represents a tetrahydrophthalimide group or a dialkylmaleimide group, and R 12 represents a phenyl group or a phenoxy group. ) or a reactive derivative thereof. Examples of reactive derivatives of carboxylic acids include acid halides, acid anhydrides, lower alkyl esters, and alkali metal salts.
Examples of reactive derivatives of alcohol include chloride, bromide, and P-toluenesulfonic acid ester. The reaction is carried out in a suitable solvent, optionally in the presence of an organic or inorganic base or acid as a deoxidizer or catalyst, and optionally with heating. In the acid component of general formula (), R 1
When and R 2 are different, there are at least two asymmetric carbons, and when they are the same, there is at least one asymmetric carbon, and what can be obtained by normal synthesis methods is a mixture of these,
Of course, each of these is also included in the present invention. The same applies when an asymmetric carbon is present in the alcohol component. Representative examples of the compound represented by the above formula () are as follows, but the present invention is of course not limited to these. (1) 3′-phenoxy-α′-cyanobenzyl 2,
2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate n 20 D 1.5405 (2) 3′-phenoxy-α′-cyanobenzyl 2,
2-dimethyl-3-chloro-3-trifluoromethylcyclopropanecarboxylate
n 20 D 1.5436 (3) 3′-phenoxy-α′-cyanobenzyl 2,
2-dimethyl-3,3-ditrifluoromethylcyclopropanecarboxylate n 20 D 1.5412 (4) 3′-phenoxy-α′-cyanobenzyl 2,
2-dimethyl-3-difluoromethyl-3-
(2,2,2-trifluoroethyl)cyclopropanecarboxylate n 20 D 1.5487 (5) 3′-phenoxy-α′-cyanobenzyl 2,
2-dimethyl-3-chlorodifluoromethylcyclopropanecarboxylate n 20 D 1.5465 (6) 3′-phenoxy-α′-cyanobenzyl 2,
2,3-trimethyl-3-difluoromethylcyclopropanecarboxylate n 20 D 1.5423 (7) 3′-phenoxy-α′-cyanobenzyl 2,
2-dimethyl-3-chloro-3-(2,2,2
-Trifluoroethyl)cyclopropanecarboxylate n 20 D 1.5510 (8) 3′-phenoxy-α′-cyanobenzyl 2,
2,3-trimethyl-3-(2,2,2-trifluoroethyl)cyclopropanecarboxylate n 20 D 1.5481 (9) 2'-Allyl-3'-methyl-2'-cyclopenten-1'-one-4'-yl 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate n 20 D 1.5240 (10) 2'-benzyl-2'-cyclopenten-1'-one-4'-yl 2,2,3-trimethyl-3-chloromethylcyclopropanecarboxylate
n 20 D 1.5517 (11) 5′-propargyl-2′-furylmethyl 2,
2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate n 20 D 1.5204 (12) 5'-allyl-2'-methyl-3'-furylmethyl 2,2-dimethyl-3-fluoro-3-trifluoromethylcyclopropanecarboxylate
n 20 D 1.5233 (13) 4′,5′-tetramethylene-3′-tenyl 2,2
-dimethyl-3-chloro-3-(2,2,2,
1,1-pentafluoroethyl)cyclopropanecarboxylate n 20 D 1.5429 (14) 4'trifluoromethyl-5'-(2,2,2-
trifluoroethoxymethyl)-α'-propynyl-2'-thenyl 2,2-dimethyl-3-ethyl-3-bromomethylcyclopropanecarboxylate n 20 D 1.5658 (15) 5'Benzyl-3'furylmethyl 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate n 20 D 1.5492 (16) 2'-(2,4-pentadienyl)-3'-methyl-2'-cyclopenten-1'-one-4'-yl 2,2,3-trimethyl-3-(2,2,2-
Trifluoroethyl)cyclopropanecarboxylate n 20 D 1.5386 (17) 2'-Propargyl-3-methyl-2'-cyclopenten-1'-one-4'-yl 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate n 20 D 1.5264 (18) 2',3',4',5',6'-pentafluorobenzyl 2,2-dimethyl-3,3-ditrifluoromethylcyclopropanecarboxylate
n 20 D 1.5271 (19) 4'-(2,2,2-trifluoroethoxymethyl)benzyl 2,2-dimethyl-3-chloro-3-chloromethylcyclopropanecarboxylate n 20 D 1.5366 (20) 3′-(2,2,2-trifluoroethoxy)
-4'-trifluoromethyl-α'-trifluoromethylbenzyl 2,2-dimethyl-3-bromomethylcyclopropanecarboxylate
n 20 D 1.5405 (21) 2′,6′-dichloro-4′-allylbenzyl 2,
2,3-trimethyl-3-fluoromethylcyclopropanecarboxylate n 20 D 1.5487 (22) 3',4'-trimethylene-α'-ethynylbenzyl 2,2-dimethyl-3-ethyl-3-(2
-chloroethyl)cyclopropanecarboxylate n 20 D 1.5504 (23) 7'-Methyl-2',3'-dihydrobenzofuran-3'-yl 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate n 20 D 1.5536 (24) 7'-Chlorindan-3'-yl 2,2-dimethyl-3-difluoromethyl-3-trifluoromethylcyclopropanecarboxylate
n 20 D 1.5529 (25) 3'-Benzyl-α'-trifluoromethylbenzyl 2,2-dimethyl-3-chloro-3-trifluoromethylcyclopropanecarboxylate n 20 D 1.5615 (26) 3'-benzoyl-α'-ethynylbenzyl 2,2-dimethyl-3-bromomethyl-3-
(2,2,2-trifluoroethyl)cyclopropanecarboxylate n 20 D 1.5703 (27) 3'-(2,2-dichlorovinyloxy)-
α′-cyanobenzyl 2,2-dimethyl-3-
Bromo-3-(2,2,2,1,1-pentafluoroethyl)cyclopropanecarboxylate n 20 D 1.5628 (28) 3'-(4-fluorophenoxy)-α'-cyanobenzyl 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate n 20 D 1.5420 (29) 3'-Phenoxy-6'-fluoro-α'-cyanobenzyl 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate n 20 D 1.5417 (30) 3'(4-chlorophenoxy)-α'-cyanobenzyl 2,2-dimethyl-3-chloro-3-
Chloromethyl cyclopropane carboxylate
n 20 D 1.5449 (31) 3'-(4-fluorophenoxy)-4'-fluoro-α'-cyanobenzyl 2,2-dimethyl-3-fluoro-3 difluoromethylcyclopropanecarboxylate n 20 D 1.5376 (32) 4'-Benzylbenzyl 2,2-dimethyl-
3,3-di(2,2,2-trifluoroethyl)cyclopropanecarboxylate
n 20 D 1.5680 (33) 3′-difluoromethoxy-6′-chloro-α′
-Cyanobenzyl 2,2,3 trimethyl-3 trifluoromethylcyclopropanecarboxylate n 20 D 1.5314 (34) 2',3',4',5',6'-pentachlorobenzyl 2,2-dimethyl-3-chloro-3-chloromethylcyclopropanecarboxylate
n 20 D 1.5683 (35) 1′-ethynyl-2′-methyl-2′-pentene-
1'-yl 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate
n 20 D 1.4970 (36) 2'-Chloro-3'-phenylallyl 2,2-dimethyl-3-(2,2,2-trifluoroethyl)-3-(2-bromoethyl)cyclopropanecarboxylate n 20 D 1.5306 (37) 1'-ethynyl-2'-methyl-3'-propargylallyl-1'-yl 2,2,3-trimethyl-
3-Trifluoromethylcyclopropanecarboxylate n 20 D 1.5012 (38) 2'-Bromo-2',5'-heptadien-1'-yl 2,2-dimethyl-3-chloro-3-difluoromethylcyclopropanecarboxylate
n 20 D 1.5241 (39) 1′-ethynyl-2′-methyl-2′-pentene-
1'-yl 2,2-dimethyl-3,3-ditrifluoromethylcyclopropanecarboxylate
n 20 D 1.4939 (40) 4′-phenyl-3′-chloro-2′-butene-
1'-yl2,2-dimethyl-3-chloro-3-
Trifluoromethylcyclopropanecarboxylate n 20 D 1.5405 (41) 3′,4′,5′,6′-tetrahydrophthalimidomethyl 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate
n 20 D 1.5426 (42) Dimethylmaleimidomethyl 2,2-dimethyl-3-chloro-3-(2,2,2-trifluoroethyl)cyclopropanecarboxylate
n 20 D 1.5430 (43) 4′-phenyl-2′-butyn-1′-yl 2,2
-dimethyl-3-ethyl-3-fluoromethylcyclopropanecarboxylate n 20 D 1.5382 (44) 4'-phenoxy-2'-butyn-1'-yl 2,
2-dimethyl-3-chloromethyl-3-chlorodifluoromethylcyclopropanecarboxylate n 20 D 1.5403 (45) 3′,4′,5′,6′-tetrahydrophthalimidomethyl 2,2-dimethyl-3-trifluoromethyl-3-(2,2,2-trifluoroethyl)cyclopropanecarboxylate
n 20 D 1.5454 (46) 4′-phenyl-3′-methyl-2′-butene-
1′-yl2,2,3-trimethyl-3-(2,
2,2,1,1-pentafluoroethyl)cyclopropanecarboxylate n 20 D 1.5395 (47) 7′-trifluoromethyl-2′,3′-dihydrobenzofuran-3′-yl 2,2-dimethyl-3
-Difluoromethylcyclopropanecarboxylate n 20 D 1.5418 (48) 2'-Methyl-4'-propargyl-α'-provinylbenzyl 2,2-dimethyl-3-ethyl-3-(2,2,2-trifluoroethyl)cyclopropanecarboxylate n 20 D 1.5477 (49) 3'-(3-bromobenzoyl)-α'-cyanobenzyl 2,2-dimethyl-3-fluoro-
3-Trifluoromethylcyclopropanecarboxylate n 20 D 1.5678 (50) 5'-propargyl-2'-furylmethyl 2,2
-Dimethyl-3,3-ditrifluoromethylcyclopropanecarboxylate n 20 D 1.5211 (51) 2'-allyl-3'-methyl-2'-cyclopenten-1'-one-4'-yl 2,2-dimethyl-
3,3-ditrifluoromethylcyclopropanecarboxylate n 20 D 1.5245 (52) 2′,3′,4′,5′,6′-pentalfluorobenzyl 2,2-dimethyl-3-fluoro-3-
(1-chloro-2,2,2-trifluoroethyl)cyclopropanecarboxylate
n 20 D 1.5304 (53) 3'-Phenoxybenzyl 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate n 20 D 1.5356 (54) 3'-Phenoxybenzyl 2,2-dimethyl-
3-chloro-3-trifluoromethylcyclopropanecarboxylate n 20 D 1.5329 (55) 5'-Benzyl-3'-furylmethyl 2,2-dimethyl-3-difluoromethyl-3-trifluoromethylcyclopropanecarboxylate
n 20 D 1.5470 The compound of the present invention is a new compound, is solid or liquid at room temperature, and is generally easily soluble in organic solvents. Therefore, it can be used as an insecticide for spraying in the form of emulsions, oils, powders, wettable powders, aerosols, etc. It can also be used as an insecticide for fumigation such as mosquito coils by mixing with wood flour or other suitable base materials. can do. In addition, the active ingredient may be dissolved in an appropriate organic solvent and immersed in a mount, or dissolved in an appropriate solvent and heated and evaporated with an appropriate heating element to be used as a so-called electric mosquito repellent, or a chemical heating element (e.g. Composition consisting of soda sulfide and carbon, salt, iron,
Composition consisting of carbon, salt, iron, carbon,
There are compositions consisting of hydrated salts of sodium metasilicate, quicklime, etc., which generate heat when brought into contact with air or water), or sublimable substances such as adamantane, cyclododecane, trimethylenenorbornane, etc. as auxiliaries. When used as a mosquito coil for transpiration, it also shows excellent effects, similar to mosquito coils.
The compound of the present invention is more stable to light than conventional chrysanthemum acid ester-based pyrethroids, has a broader insecticidal spectrum, has low toxicity, and is inexpensive, so it can be used against conventional organophosphorus agents and organochlorine insecticides. It can be used as an alternative agricultural and horticultural insecticide. The compounds of the present invention can be used against sanitary pests such as flies, mosquitoes, and cockroaches, as well as organophosphorus agent- and carbamate-resistant leafhoppers, planthoppers, stink bugs, stink bugs, armyworm moth, diamondback moth, tobacco moth, bean weevil, nocturnal moth, and cabbage moth. It is extremely useful for controlling agricultural pests such as chestnut beetles, leaf beetles, aphids, and scale insects, grain storage pests such as brown elephant, and mites. In addition, the compounds of the present invention include N-octylbicycloheptenedicarboximide (trade name MGK-264) and a mixture of N-octylbicycloheptenedicarboximide and an arylsulfonate (trade name MGK-264).
5026), cinepirin 500, octachlorodipropyl ether, piperonyl butoxide, etc., the insecticidal effect can be further enhanced. If necessary, the compound of the present invention may include BHT or
Stability can be further improved by adding a stabilizer such as DBHQ or an antioxidant. The compound of the present invention may also be used with other insecticides such as organophosphorus agents such as fenitrothion, DDVP, diazinon, propaphos, and pyridafentione, NAC,
Carbamate agents such as MTMC, BPMC, PHC,
Pyrethrin, allethrin, phthalthrin, flamethrin, phenothrin, permethrin, cypermethrin, decamethrin, fuenvalerate,
Conventional pyrethroid insecticides such as fenpropanate, insecticides such as cartap, chlorphenamidine, methomyl, or acaricides, fungicides,
By mixing nematicides, herbicides, plant growth regulators, fertilizers, and other agricultural chemicals, highly effective multipurpose compositions can be obtained, and labor savings and synergistic effects among the drugs can be expected. It is something. Next, synthesis examples will be shown for representative examples, but other compounds of the present invention also show similar trends, and synthesis method (A),
(B), (C), (D), (E), and (F) could be obtained in good yields by any method. Synthesis Example 1 A Method by reaction of alcohol and carboxylic acid halide 4.3 g of 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylic acid chloride
was dissolved in 15 ml of dry benzene, 3.7 g of 5-benzyl-3-furyl methyl alcohol dissolved in 20 ml of dry benzene was added, and 3 ml of dry pyridine was added as a condensation aid to precipitate crystals of pyridine hydrochloride. do. After sealing the cap and leaving it overnight at room temperature, the crystals of pyridine hydrochloride were separated, and the benzene solution was dried with sulfuric acid and the benzene was distilled off under reduced pressure to give 5'-benzyl-3'-furylmethyl 2,2,3. ―
6.7 g of trimethyl-3-trifluoromethylcyclopropanecarboxylate was obtained. Synthesis Example 2 B Method by reaction of alcohol and carboxylic acid 2,2,3-trimethyl-3-(2,2,2,
5.0 g of 1,1-pentafluoroethyl)cyclopropanecarboxylic acid and 4-phenyl-3-methyl-
3.3g of 2-butene-1-ol dried benzene 50g
ml, 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 filtered off. The oily substance obtained by concentrating the filtrate was allowed to flow down a 100 g silica gel column to obtain 4'-phenyl-3'-methyl-2'-buten-1'-yl 2,2,3-trimethyl-3-
(2,2,2,1,1-pentafluoroethyl)
6.3 g of cyclopropane carboxylate was obtained. Synthesis Example 3C Method by reaction of alcohol halide with alkali metal carboxylic acid 2,2-dimethyl-3-chloro-3-(2,
Suspend 5.2 g of sodium salt of 2,2-trifluoroethyl)cyclopropanecarboxylic acid and 3.5 g of dimethylmaleimidomethyl chloride in 50 ml of benzene, react under reflux for 3 hours in a nitrogen atmosphere, and then add enough saline. After washing, the benzene was distilled off under reduced pressure and dimethylmaleimidomethyl 2,2-dimethyl-3-chloro-3-(2,2,
5.9 g of 2-trifluoroethyl)cyclopropanecarboxylate was obtained. Synthesis Example 4 D Method by transesterification reaction between alcohol and lower alkyl ester of carboxylic acid 2,2-dimethyl-3-difluoromethyl-3
- Heat 5.1 g of methyl ester of trifluoromethylcyclopropanecarboxylic acid and 3.2 g of 7-chloro-indan-3-ol to 150°C. temperature
When the temperature reached 150°C, 0.25 g of sodium was added and methanol distillation was started. When the distillation of methanol has stopped, add 0.25 g of sodium and repeat the above operation while keeping the temperature around 150° C. until the theoretical amount of methanol is obtained. The mixture was then cooled and 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 7'-chloroindan-3'-yl 2, 2
-Dimethyl-3-difluoromethyl-3-fluoromethylcyclopropanecarboxylate 6.1g
I got it. Synthesis Example 5 E Method by reaction of alcohol and carboxylic anhydride 7.5 g of 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylic anhydride and 2
-Propargyl-3-methyl-2-cyclopenten-1-one-4-ol (3.1 g) was dissolved in 50 ml of dry pyridine and stirred overnight at room temperature. The next day, the reaction solution was poured into 100 g of ice water and extracted three times with 20 ml of ether. The ether layers were combined and extracted twice with 20 ml of 5% aqueous sodium hydroxide solution to remove by-produced carboxylic acid. The ether layer was further washed with dilute hydrochloric acid, an aqueous sodium bicarbonate solution, and a saline solution, and then dried over sulfuric acid. The ether was removed under reduced pressure to obtain a crude ester, which was passed down a column containing 20 g of activated alumina to obtain 2'-propargyl-3. 6.0 g of '-methyl-2'-cyclopenten-1'-on-4'-yl 2,2,3-trimethyl-3-trifluoromethylcyclopropanecarboxylate was obtained. Synthesis Example 6 F Method by reaction of alcohol halide and organic tertiary base carboxylate 4.1 g of 2,2-dimethyl-3-chloro-3-chloromethylcyclopropanecarboxylic acid was dissolved in acetone.
Dissolve in 50 ml and add 6.4 g of 3-(4-chlorophenoxy)-α-cyanobenzyl bromide. Add 4 ml of triethylamine while stirring and add 60
After reacting at ~80°C for 3 hours, it was dissolved in ether, the ether solution was thoroughly washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over salt water, and the ether was distilled off under reduced pressure to give 3'-(4-chlorofluoride). enoxy)-α'-cyanobenzyl 2,2-dimethyl-3-chloro-3-chloromethylcyclopropanecarboxylate 7.1
I got g. Next, in order to make it clearer that the composition provided by the present invention is excellent, the results of testing the effectiveness will be shown. Test Example 1 Insecticidal test by spraying A 0.2% white light solution of the compound of the present invention (A), a white light solution of 0.2% and 0.8% piperonyl butoxide (B), a white light solution of 0.1% and phthalthrine 0.1% (C) ), and 0.2% white light solutions of allethrin and phthalthrin, respectively, to calculate the fall-upside-down rate of houseflies, calculate the relative effectiveness of the test agent, and further calculate the mortality rate after 24 hours, as shown below. . The numbers in parentheses indicate the mortality rate after 24 hours.
【表】【table】
【表】
試験例２ 燻蒸による殺虫試験
殺虫成分として0.5％を含有する蚊取線香を作
り、アカイエカの成虫を落下仰転せしめる効果を
試験した。この実験は防虫料学16巻（1951年）第
176頁 長沢、勝田等の方法に従い、前記線香の
相対有効度を算出したところ次の如くである。供
試薬剤番号は前記有効成分例のものと同一であ
る。[Table] Test Example 2 Insecticidal test by fumigation Mosquito coils containing 0.5% of insecticidal ingredients were prepared and tested for their effectiveness in causing adult Culex mosquitoes to fall and roll over. This experiment was published in Vol. 16 of Insect Control Materials (1951).
Page 176 The relative effectiveness of the above-mentioned incense sticks was calculated according to the method of Nagasawa, Katsuta et al. and was as follows. The sample drug number is the same as that of the active ingredient example above.
【表】【table】
【表】
試験例３ 微量滴下法による殺虫試験
アレスリン及び本発明化合物の各々とそれらに
サイネピリン500をそれぞれ有効成分の２倍量を
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、24時間後の死虫率からアレスリンに対する相
対殺虫効力及びサイネピリン500による共力効果
を調べたところ次の如くである。[Table] Test Example 3 Insecticidal test by microdropping method Allethrin and the compound of the present invention and Cinepirin 500 were added to them in an amount twice the amount of the active ingredient, and an acetone solution of a prescribed concentration was prepared, which was then used to prepare adult houseflies using a microsyringe. The relative insecticidal efficacy against allethrin and the synergistic effect with cinepirin 500 were investigated based on the insect mortality rate after 24 hours, and the results were as follows.
【表】
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(1)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(4)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(6)20部にソルポールSM―200（東
邦化学登録商標名）10部、キシロール70部を加え
て撹拌混合溶解して20％乳剤を得る。
参考例 ４
本発明化合物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 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（26）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（33）３部とクレー97部をよく粉
砕混合して３％粉剤を得る。
参考例 ８
本発明化合物（47）40部、硅藻土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 ４
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３によつて得られた乳剤
のうち本発明化合物(3)，(6)，，（18），（23），
（31），（38），（40），（48）および（53）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 ５
参考例３で得られた乳剤のうち本発明化合物
(1)，(6)，（12），（16），（21），（29），（34），
（42），
（46）および（52）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、２時間後の死虫率を求めた。[Table] Examples of formulations are shown next, but formulations do not require any special conditions similar to general agricultural chemicals and can be prepared by methods familiar to those skilled in the art. . Reference example 1 White kerosene was added to 0.2 parts of the present compound (1) and the whole
Obtain 0.2% oil solution as 100 parts. Reference Example 2 White kerosene is added to 0.2 parts of the present compound (4) and 0.8 parts of piperonyl butoxide to make a total of 100 parts to obtain an oil solution. Reference Example 3 To 20 parts of the compound (6) of the present invention, 10 parts of Solpol SM-200 (registered trademark of Toho Chemical) and 70 parts of xylol were added and mixed and dissolved with stirring to obtain a 20% emulsion. Reference Example 4 0.4 parts of the compound of the present invention, 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 5 0.5 g of the compound (18) of the present invention and 0.5 g of BHT were added to base materials for mosquito coils such as pyrethrum extract lees powder, wood flour, and starch powder.
Mix 99.0g of the mixture uniformly and obtain a mosquito coil by a known method. Reference example 6 Compound of the present invention (26) 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 3 parts of the compound (33) of the present invention and 97 parts of clay are thoroughly ground and mixed to obtain a 3% powder. Reference Example 8 40 parts of the present compound (47), 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 4 5 to 5 on a surface where a large number of green peach aphids appeared
Among the emulsions obtained in Reference Example 3 in a radish field at the 6-leaf stage, compounds of the present invention (3), (6),, (18), (23),
A 1000-fold diluted solution of each emulsion containing (31), (38), (40), (48) and (53) with water was sprayed at 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 5 Among the emulsions obtained in Reference Example 3, the compound of the present invention
(1), (6), (12), (16), (21), (29), (34),
(42),
Fresh leaves were immersed in the 2000-fold dilutions of (46) and (52) for about 5 seconds, and after drying, they were placed in a shear dish and 10 healthy armyworm larvae 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 after 2 hours.
【表】
試験例 ６
鉢植えのソラ豆へ殺虫有効成分を適用する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
(5)，（13），（17），（24），（28），（32），（36
），
（44），（47）および（55）の4000倍希釈液を害虫
がついた葉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 ７
参考例７によつて得られた(1)，(7)，（14），
（20），（27），（34），（39），（42），（49）およ
び
（54）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 ８
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３で得
られた乳剤(4)，(6)，，（15），（21），（26），
（32），（35），（43）および（50）を水で有効成分
100ppmに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においても寄生数10頭
以下であつた。[Table] Test Example 6 One day before applying the insecticidal active ingredient to potted fava beans, one tree was infested with approximately 200 aphids. Among the hydrating agents obtained by Reference Example 8
(5), (13), (17), (24), (28), (32), (36
),
A 4000-fold dilution of (44), (47), and (55) was applied to leaves infested with 10 ml/pot using a compressed air spray method, and the degree of damage was observed 2 days later. As a result, no increase in the degree of damage was observed in any of the cases. Test Example 7 (1), (7), (14), obtained by Reference Example 7
Each of the powders (20), (27), (34), (39), (42), (49) and (54) was uniformly sprinkled on the bottom of a waist-high glass shear dish with a diameter of 14 cm at a rate of 2 g/m2. , spread butter on the wall leaving about 1cm at the bottom. Inside, we release adult German cockroaches in groups of 10.
If you leave the cockroaches in contact for 30 minutes and transfer them to a new container, 3
After a few days, more than 80% of the cockroaches were killed with either powder. Test Example 8 1 for 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 (4), (6), , (15), (21), (26) obtained in Reference Example 3
(32), (35), (43) and (50) as active ingredients with water
A chemical solution diluted to 100 ppm was sprayed on a turntable in an amount of 10 ml per pot. After 10 days, the number of parasitized spider mites on the plants was less than 10 in all cases.
Claims (1)
基、ハロゲン原子、ハロメチル基、又はハロエチ
ル基を示し、R2はハロメチル基又はハロエチル
基を表わす。ただしR1が水素原子の場合、R2は
ハロメチル基を表わす。 Ｒは式（），（），（），（），（）で表
わ
される基を示す。 【式】【式】 【式】―CH2―R11 …（） ―CH2―Ｃ≡Ｃ―CH2―R12 …（） ここに、R3は水素原子又はメチル基を、R4は
アリル基、プロパルギル基、ベンジル基又は２，
４―ペンタジエニル基を示す。Ｘは酸素原子、イ
オウ原子又は（−CH＝CH―）グループであり、
R5は水素原子、シアノ基、エチニル基、プロピ
ニル基又はトリフルオロメチル基を示す。R6は
水素原子、メチル基、ハロゲン原子又はトリフル
オロメチル基を示しｎは１〜４の整数を表わす。
R7はハロゲン原子、低級アルキル基、低級ハロ
アルコキシ基、低級ハロアルコキシメチル基、ア
リル基、プロパルギル基、ベンジル基、ベンゾイ
ル基、フエノキシ基、ベンゼン環の１個の水素原
子がハロゲン原子で置換されたフエノキシ基又は
ジクロロビニルオキシ基を示す。ここでR6とR7
は共に末端で結合してトリメチレン又はテトラメ
チレン鎖を形成する場合、およびR5とR6が末端
で結合してエチレン又はメチレンオキシ鎖を形成
する場合も含まれる。R6は水素原子又はエチニ
ル基であり、R9およびR′9は水素原子、メチル基
又はハロゲン原子を示す。R10はフエニル基、ベ
ンジル基または炭素数が２〜４までのアルキル
基、アルケニル基またはアルキニル基を表わす。
R11はテトラヒドロフタルイミド基又はジアルキ
ルマレイミド基を表わし、R12はフエニル基又は
フエノキシ基を表わす。）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及びその光学な
らびに幾何異性体。 ２ 一般式 （式中、R1は水素原子、メチル基、エチル
基、ハロゲン原子、ハロメチル基又はハロエチル
基を示し、R2はハロメチル基又はハロエチル基
を表わす。ただしR1が水素原子の場合R2はハロ
メチル基を表わす。又R5は水素原子、シアノ
基、エチニル基、プロピニル基又はトリフルオロ
メチル基を示す。）で示される化合物であること
を特徴とする特許請求の範囲第１項記載の化合
物。 ３ 一般式（）においてR2がトリフルオロメ
チル基を表わし、R5がシアノ基を表わす化合物
であることを特徴とする特許請求の範囲第２項記
載の化合物。 ４ 式 で示される化合物であることを特徴とする特許請
求の範囲第３項記載の化合物。 ５ 式 で示される化合物であることを特徴とする特許請
求の範囲第３項記載の化合物。 ６ 式 で示される化合物であることを特徴とする特許請
求の範囲第３項記載の化合物。 ７ 一般式（）のR1とR2が異なる場合におい
てシクロプロパン環の絶対配置が（1R，3R）又
は（1R，3S）である特許請求の範囲第１項記載
の化合物。 ８ 一般式（）においてR5が水素原子でな
く、R5が結合されている炭素原子の絶対配置が
（Ｓ）である特許請求の範囲第２項記載の化合
物。 ９ 一般式 （式中、R1は水素原子、メチル基、エチル
基、ハロゲン原子、ハロメチル基又はハロエチル
基を示し、R2はハロメチル基又はハロエチル基
を表わす。ただしR1が水素原子の場合R2はハロ
メチル基を表わす。）で表わされるカルボン酸又
はその反応性誘導体と一般式 HO―Ｒ …（） （式中、Ｒは式（），（），（），（），
（）で表わされる基を示す。 【式】【式】 【式】―CH2―R11 …（） ―CH2―Ｃ≡Ｃ―CH2―R12 （） R3は水素原子又はメチル基をR4はアリル基、
プロパルギル基、ベンジル基又は２，４―ペンタ
ジエニル基を示す。Ｘは酸素原子、イオウ原子又
は（―CH＝CH―）グループであり、R5は水素
原子、シアノ基、エチニル基、プロヒニル基又は
トリフルオロメチル基を示す。R6は水素原子、
メチル基、ハロゲン原子又はトリフルオロメチル
基を示しｎは１〜４の整数を表わす。R7はハロ
ゲン原子、低級アルキル基、低級ハロアルコキシ
基、低級ハロアルコキシメチル基、アリル基、プ
ロパルギル基、ベンジル基、ベンゾイル基、フエ
ノキシ基、ベンゼン環の１個の水素原子がハロゲ
ン原子で置換されたフエノキシ基又はジクロロビ
ニルオキシ基を示す。ここでR6とR7は共に末端
で結合してトリメチレン又はテトラメチレン鎖を
形成する場合、およびR5とR6が末端で結合して
エチレン又はメチレンオキシ鎖を形成する場合も
含まれる。R8は水素原子又はエチニル基であ
り、R9およびR′9は水素原子、メチル基又はハロ
ゲン原子を示す。R10はフエニル基、ベンジル基
または炭素数が２〜４までのアルキル基、アルケ
ニル基またはアルキニル基を表わす。R11はテト
ラヒドロフタルイミド基又はジアルキルマレイミ
ド基を表わし、R12はフエニル基又はフエノキシ
基を表わす。）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を特徴とする一般
式 （ここにR1，R2，Ｒは前述と同じ意味を表わ
す。）で示されるシクロプロパンカルボン酸エス
テル誘導体の製造法。 １０ 一般式 （式中、R1は水素原子、メチル基、エチル
基、ハロゲン原子、ハロメチル基又はハロエチル
基を示し、R2はハロメチル基又はハロエチル基
を表わす。ただしR1が水素原子の場合R2はハロ
メチル基を表わす。 Ｒは式（）、（）、（）、（）、（）で表
わ
される基を示す。 【式】【式】 【式】―CH2―R11 …（） ―CH2―Ｃ≡Ｃ―CH2―R12 …（） ここにR3は水素原子又はメチル基を、R4はア
リル基、プロパルギル基、ベンジル基又は２，４
―ペンタジエニル基を示す。Ｘは酸素原子、イオ
ウ原子又は（―CH＝CH―）グループであり、
R5は水素原子、シアノ基、エチニル基、プロピ
ニル基又はトリフルオロメチル基を示す。R6は
水素原子、メチル基、ハロゲン原子又はトリフル
オロメチル基を示し、ｎは１〜４の整数を表わ
す。R7はハロゲン原子、低級アルキル基、低級
ハロアルコキシ基、低級ハロアルコキシメチル
基、アリル基、プロパルギル基、ベンジル基、ベ
ンゾイル基、フエノキシ基、ベンゼン環の１個の
水素原子がハロゲン原子で置換されたフエノキシ
基又はジクロロビニルオキシ基を示す。ここで
R6とR7は共に末端で結合してトリメチレン又は
テトラメチレン鎖を形成する場合およびR5とR6
が末端で結合してエチレン又はメチレンオキシ鎖
を形成する場合も含まれる。R8は水素原子又は
エチニル基であり、R9およびR′9は水素原子、メ
チル基又はハロゲン原子を示す。R10はフエニル
基、ベンジル基または炭素数が２〜４までのアル
キル基、アルケニル基またはアルキニル基を表わ
す。R11はテトラヒドロフタルイミド基又はジア
ルキルマレイミド基を表わし、R12はフエニル基
又はフエノキシ基を表わす。）で示されるシクロ
プロパンカルボン酸エステル誘導体を含有するこ
とを特徴とする殺虫、殺ダニ剤。 １１ 補助剤としてピレスロイド用共力剤を含有
することを特徴とする特許請求の範囲第１０項記
載の殺虫、殺ダニ剤。[Claims] 1. General formula (In the formula, R 1 represents a hydrogen atom, a methyl group, an ethyl group, a halogen atom, a halomethyl group, or a haloethyl group, and R 2 represents a halomethyl group or a haloethyl group. However, when R 1 is a hydrogen atom, R 2 represents a halomethyl group. R represents a group represented by the formula (), (), (), (), (). [Formula] [Formula] [Formula] - CH 2 - R 11 ... () - CH 2 -C≡C-CH 2 -R 12 ... () Here, R 3 is a hydrogen atom or a methyl group, R 4 is an allyl group, propargyl group, benzyl group, or 2,
Indicates a 4-pentadienyl group. X is an oxygen atom, a sulfur atom or a (-CH=CH-) group,
R 5 represents a hydrogen atom, a cyano group, an ethynyl group, a propynyl group, or a trifluoromethyl group. R 6 represents a hydrogen atom, a methyl group, a halogen atom or a trifluoromethyl group, and n represents an integer of 1 to 4.
R 7 is a halogen atom, a lower alkyl group, a lower haloalkoxy group, a lower haloalkoxymethyl group, an allyl group, a propargyl group, a benzyl group, a benzoyl group, a phenoxy group, or one hydrogen atom of the benzene ring is substituted with a halogen atom. represents a phenoxy group or a dichlorovinyloxy group. Here R 6 and R 7
This also includes cases where R 5 and R 6 are bonded together at the ends to form a trimethylene or tetramethylene chain, and cases where R 5 and R 6 are bonded at the ends to form an ethylene or methyleneoxy chain. R 6 is a hydrogen atom or an ethynyl group, and R 9 and R' 9 are a hydrogen atom, a methyl group, or a halogen atom. R 10 represents a phenyl group, a benzyl group, or an alkyl group having 2 to 4 carbon atoms, an alkenyl group, or an alkynyl group.
R 11 represents a tetrahydrophthalimide group or a dialkylmaleimide group, and R 12 represents a phenyl group or a phenoxy group. ) and its optical and geometric isomers. 2 General formula (In the formula, R 1 represents a hydrogen atom, a methyl group, an ethyl group, a halogen atom, a halomethyl group, or a haloethyl group, and R 2 represents a halomethyl group or a haloethyl group. However, when R 1 is a hydrogen atom, R 2 represents a halomethyl group. The compound according to claim 1, wherein R 5 represents a hydrogen atom, a cyano group, an ethynyl group, a propynyl group, or a trifluoromethyl group. 3. The compound according to claim 2, wherein in the general formula (), R 2 represents a trifluoromethyl group and R 5 represents a cyano group. 4 formula The compound according to claim 3, which is a compound represented by: 5 formula The compound according to claim 3, which is a compound represented by: 6 formula The compound according to claim 3, which is a compound represented by: 7. The compound according to claim 1, wherein the absolute configuration of the cyclopropane ring is (1R, 3R) or (1R, 3S) when R 1 and R 2 in the general formula () are different. 8. The compound according to claim 2, wherein in the general formula (), R 5 is not a hydrogen atom, and the absolute configuration of the carbon atom to which R 5 is bonded is (S). 9 General formula (In the formula, R 1 represents a hydrogen atom, a methyl group, an ethyl group, a halogen atom, a halomethyl group, or a haloethyl group, and R 2 represents a halomethyl group or a haloethyl group. However, when R 1 is a hydrogen atom, R 2 represents a halomethyl group. carboxylic acid or its reactive derivative represented by the general formula HO-R...() (wherein R is the formula (), (), (), (),
Indicates a group represented by (). [Formula] [Formula] [Formula] -CH 2 -R 11 ... () -CH 2 -C≡C-CH 2 -R 12 () R 3 is a hydrogen atom or a methyl group, R 4 is an allyl group,
It represents a propargyl group, a benzyl group, or a 2,4-pentadienyl group. X is an oxygen atom, a sulfur atom, or a (-CH=CH-) group, and R 5 represents a hydrogen atom, a cyano group, an ethynyl group, a prohynyl group, or a trifluoromethyl group. R 6 is a hydrogen atom,
It represents a methyl group, a halogen atom or a trifluoromethyl group, and n represents an integer of 1 to 4. R 7 is a halogen atom, a lower alkyl group, a lower haloalkoxy group, a lower haloalkoxymethyl group, an allyl group, a propargyl group, a benzyl group, a benzoyl group, a phenoxy group, or one hydrogen atom of the benzene ring is substituted with a halogen atom. represents a phenoxy group or a dichlorovinyloxy group. Here, the case where R 6 and R 7 are bonded together at the terminal to form a trimethylene or tetramethylene chain, and the case where R 5 and R 6 are bonded at the terminal to form an ethylene or methyleneoxy chain are also included. R 8 is a hydrogen atom or an ethynyl group, and R 9 and R' 9 are a hydrogen atom, a methyl group, or a halogen atom. R 10 represents a phenyl group, a benzyl group, or an alkyl group having 2 to 4 carbon atoms, an alkenyl group, or an alkynyl group. R 11 represents a tetrahydrophthalimide group or a dialkylmaleimide group, and R 12 represents a phenyl group or a phenoxy group. ) A general formula characterized by reacting with an alcohol or its reactive derivative represented by (Here, R 1 , R 2 , and R have the same meanings as above.) A method for producing a cyclopropane carboxylic acid ester derivative. 10 General formula (In the formula, R 1 represents a hydrogen atom, a methyl group, an ethyl group, a halogen atom, a halomethyl group, or a haloethyl group, and R 2 represents a halomethyl group or a haloethyl group. However, when R 1 is a hydrogen atom, R 2 represents a halomethyl group. Represents a group. R represents a group represented by the formula (), (), (), (), (). [Formula] [Formula] [Formula] - CH 2 - R 11 ... () - CH 2 - C≡C—CH 2 —R 12 …() Here, R 3 is a hydrogen atom or a methyl group, and R 4 is an allyl group, propargyl group, benzyl group, or 2,4
- indicates a pentadienyl group. X is an oxygen atom, a sulfur atom or a (-CH=CH-) group,
R 5 represents a hydrogen atom, a cyano group, an ethynyl group, a propynyl group, or a trifluoromethyl group. R 6 represents a hydrogen atom, a methyl group, a halogen atom or a trifluoromethyl group, and n represents an integer of 1 to 4. R 7 is a halogen atom, a lower alkyl group, a lower haloalkoxy group, a lower haloalkoxymethyl group, an allyl group, a propargyl group, a benzyl group, a benzoyl group, a phenoxy group, or one hydrogen atom of the benzene ring is substituted with a halogen atom. represents a phenoxy group or a dichlorovinyloxy group. here
When R 6 and R 7 are combined at the ends to form a trimethylene or tetramethylene chain, and R 5 and R 6
This also includes the case where they are bonded at the terminal to form an ethylene or methyleneoxy chain. R 8 is a hydrogen atom or an ethynyl group, and R 9 and R' 9 are a hydrogen atom, a methyl group, or a halogen atom. R 10 represents a phenyl group, a benzyl group, or an alkyl group having 2 to 4 carbon atoms, an alkenyl group, or an alkynyl group. R 11 represents a tetrahydrophthalimide group or a dialkylmaleimide group, and R 12 represents a phenyl group or a phenoxy group. ) An insecticide and acaricide characterized by containing a cyclopropanecarboxylic acid ester derivative represented by: 11. The insecticide and acaricide according to claim 10, which contains a pyrethroid synergist as an adjuvant.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4723380A JPS56145244A (en) | 1980-04-10 | 1980-04-10 | Derivative of cyclopropanecarboxylic acid ester, its preparation, and insecticidal and tickicidal agent containing the same |
| AU70337/81A AU7033781A (en) | 1980-04-10 | 1981-04-10 | Cyclopropanecarboxylic acid ester derivatives, process for their preparation, and insecticidal and acaricidal composition containing such as effective ingredients |
| PCT/JP1981/000084 WO1981002892A1 (en) | 1980-04-10 | 1981-04-10 | Cyclopropanecarboxylic acid ester derivatives,process for their preparation,and insecticidal and acaricidal composition containing such as effective ingredients |
| US06/329,273 US4459305A (en) | 1980-04-10 | 1981-04-10 | Cyclopropanecarboxylic acid ester derivatives, a method of manufacturing them, and their uses |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4723380A JPS56145244A (en) | 1980-04-10 | 1980-04-10 | Derivative of cyclopropanecarboxylic acid ester, its preparation, and insecticidal and tickicidal agent containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56145244A JPS56145244A (en) | 1981-11-11 |
| JPS6250458B2 true JPS6250458B2 (en) | 1987-10-24 |
Family
ID=12769487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4723380A Granted JPS56145244A (en) | 1980-04-10 | 1980-04-10 | Derivative of cyclopropanecarboxylic acid ester, its preparation, and insecticidal and tickicidal agent containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56145244A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58121246A (en) * | 1982-01-14 | 1983-07-19 | Kuraray Co Ltd | Substituted benzyl ester and insecticide containing the same as active constituent |
-
1980
- 1980-04-10 JP JP4723380A patent/JPS56145244A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56145244A (en) | 1981-11-11 |
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