JPS6252722B2 - - Google Patents
Info
- Publication number
- JPS6252722B2 JPS6252722B2 JP54148754A JP14875479A JPS6252722B2 JP S6252722 B2 JPS6252722 B2 JP S6252722B2 JP 54148754 A JP54148754 A JP 54148754A JP 14875479 A JP14875479 A JP 14875479A JP S6252722 B2 JPS6252722 B2 JP S6252722B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- acid
- methyl
- ethynyl
- trimethyl
- 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
- -1 cyclopropanecarboxylic acid ester Chemical class 0.000 claims description 11
- 239000002917 insecticide Substances 0.000 claims description 10
- 230000005068 transpiration Effects 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000003958 fumigation Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000004970 halomethyl group Chemical group 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 230000000749 insecticidal effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- LRNSIQGHWOBGEL-UHFFFAOYSA-N 2-methoxy-2,3,3-trimethylcyclopropane-1-carboxylic acid Chemical compound COC1(C)C(C(O)=O)C1(C)C LRNSIQGHWOBGEL-UHFFFAOYSA-N 0.000 description 7
- 241000255925 Diptera Species 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 125000004494 ethyl ester group Chemical group 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000077 insect repellent Substances 0.000 description 5
- 238000000034 method Methods 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 241001465754 Metazoa Species 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
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 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
- 241000723353 Chrysanthemum Species 0.000 description 3
- 235000007516 Chrysanthemum Nutrition 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004821 distillation 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
- 229960005235 piperonyl butoxide Drugs 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 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
- 229960005199 tetramethrin Drugs 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
- KSJBHWGZQXGMNL-UHFFFAOYSA-N 1,2,2,3-tetramethylcyclopropane-1-carboxylic acid Chemical compound CC1C(C)(C)C1(C)C(O)=O KSJBHWGZQXGMNL-UHFFFAOYSA-N 0.000 description 2
- ZUZAETTVAMCNTO-UHFFFAOYSA-N 2,3-dibutylbenzene-1,4-diol Chemical compound CCCCC1=C(O)C=CC(O)=C1CCCC ZUZAETTVAMCNTO-UHFFFAOYSA-N 0.000 description 2
- QMSYFNBRKYPTKN-UHFFFAOYSA-N 4-methyloct-4-en-1,7-diyn-3-ol Chemical compound C#CC(O)C(C)=CCC#C QMSYFNBRKYPTKN-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000256054 Culex <genus> Species 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 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
- 241000607479 Yersinia pestis Species 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 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 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052742 iron Inorganic materials 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
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- NEJDKFPXHQRVMV-UHFFFAOYSA-N (E)-2-Methyl-2-buten-1-ol Natural products CC=C(C)CO NEJDKFPXHQRVMV-UHFFFAOYSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- ADFXKUOMJKEIND-UHFFFAOYSA-N 1,3-dicyclohexylurea Chemical compound C1CCCCC1NC(=O)NC1CCCCC1 ADFXKUOMJKEIND-UHFFFAOYSA-N 0.000 description 1
- AZJLZOVPJNPLGE-UHFFFAOYSA-N 1-(4-methylphenyl)-2-phenylethanamine Chemical compound C1=CC(C)=CC=C1C(N)CC1=CC=CC=C1 AZJLZOVPJNPLGE-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
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- UTMFMZALCNUPDJ-UHFFFAOYSA-N 2-(chloromethyl)cyclopropane-1-carboxylic acid Chemical compound OC(=O)C1CC1CCl UTMFMZALCNUPDJ-UHFFFAOYSA-N 0.000 description 1
- NEJDKFPXHQRVMV-HWKANZROSA-N 2-Methyl-2-buten-1-ol Chemical compound C\C=C(/C)CO NEJDKFPXHQRVMV-HWKANZROSA-N 0.000 description 1
- QTOUODMKMGNHCN-UHFFFAOYSA-N 2-ethoxy-2,3,3-trimethylcyclopropane-1-carboxylic acid Chemical compound CCOC1(C)C(C(O)=O)C1(C)C QTOUODMKMGNHCN-UHFFFAOYSA-N 0.000 description 1
- FJULGNKJYQQBJU-UHFFFAOYSA-N 2-methoxy-2,3,3-trimethylcyclopropane-1-carbonyl chloride Chemical compound COC1(C)C(C(Cl)=O)C1(C)C FJULGNKJYQQBJU-UHFFFAOYSA-N 0.000 description 1
- CNGPUXZHOOHVHJ-UHFFFAOYSA-N 4-methylhept-4-en-1-yn-3-ol Chemical compound CCC=C(C)C(O)C#C CNGPUXZHOOHVHJ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 241000257226 Muscidae Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 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
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Chemical class 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst 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
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 1
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-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
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 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
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 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
- 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
- 238000002156 mixing Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229960003536 phenothrin Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 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
- 239000002728 pyrethroid Substances 0.000 description 1
- 229940048383 pyrethrum extract Drugs 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 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
- 235000011121 sodium hydroxide Nutrition 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 Chemical class 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 210000002268 wool Anatomy 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、R1はメチル基又はハロメチル基であ
り、R2は炭素数が１〜３のアルキル基、アルケ
ニル基、ハロアルキル基又はハロアルケニル基を
表わす。R3は水素原子又はエチニル基であり、
R4は水素原子又はメチル基を、R5は炭素数が１
〜３のアルキル基、アリル基又はプロパルギル基
を示す。）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
性体を有効成分として含有することを特徴とする
燻蒸用及び蒸散用殺虫剤に関する。
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、例えば蚊取線香、電気蚊取の
ような燻蒸用、蒸散用殺虫剤としてはアレスリ
ン、フラメトリンが広く実用に供されている。最
近酸成分についての研究が盛んになり、光安定性
に優れたジハロビニル菊酸や、揮散性の高いテト
ラメチルシクロプロパンカルボン酸等が開発され
るに至つた。このテトラメチルシクロプロパンカ
ルボン酸と一般式（）のアルコールとのエステ
ルは、高い揮散性と殺虫活性を有するにもかかわ
らず、従来のピレスロイドに比べて温血動物に対
する毒性が強く、安全性志向の現状から、家庭用
としては必ずしも優れているとはいいがたい。と
ころでアルコキシ基が温血動物体内で代謝をうけ
やすいことはDDT、BHC関連物質の研究からも
広く知られており、発明者は研究を重ねた結果、
菊酸の側鎖をアルコキシ基で置換することが有用
であることを見出し、一般式（）で示されるア
ルコキシシクロプロパンカルボン酸エステルが殺
虫成分として種々の衛生害虫、農園芸用害虫に極
めて優れた殺虫効果を奏する一方、温血動物に対
する毒性が低く又揮散性にも優れていることを発
見した。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はメチル基又はハロメチル基であ
り、R2は炭素数が１〜３のアルキル基、アルケ
ニル基、ハロアルキル基又はハロアルケニル基を
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
（式中、R3は水素原子又はエチニル基であ
り、R4は水素原子又はメチル基を、R5は炭素数
が１〜３のアルキル基、アリル基又はプロパルギ
ル基を示す。）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。
通常の製法で得られるものは光学異性体の混合
物であるが、これを構成する各異性体のエステル
のそれぞれも全て本発明に含まれる。
上記式（）で示され、燻蒸用あるいは蒸散用
殺虫剤として好ましい化合物の代表例（光学異性
体ならびに幾何異性体の混合物として示す）を示
せば次の通りであるが本発明はこれらのみに限定
されるものではない。
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−メトキ
シシクロプロパンカルボキシレート ｎ２０ Ｄ 1.5026
1′−エチニル−2′−メチル−3′−プロパルギル
−2′−プロペン−1′−イル ２，２，３−トリメ
チル−３−メトキシシクロプロパンカルボキシレ
ート
ｎ２０ Ｄ 1.5075
2′，5′−ヘキサジエン−1′−イル ２，２，３
−トリメチル−３−（１−フルオロ−２−クロロ
ビニルオキシ）シクロプロパンカルボキシレート
ｎ２０ Ｄ 1.5285
1′−エチニル−2′−メチル−2′−ペンテン−
1′−イル ２，２−ジメチル−３−トリフルオロ
メチル−３−クロロメトキシシクロプロパンカル
ボキシレート
ｎ２０ Ｄ 1.5146
2′−メチル−2′−ヘキセン−1′−イル ２，
２，３−トリメチル−３−エトキシシクロプロパ
ンカルボキシレート
ｎ２０ Ｄ 1.5133
1′−エチニル−3′−プロパルギル−2′−プロペ
ン−1′−イル ２，２−ジメチル−３−フルオロ
メチル−３−アリルオキシシクロプロパンカルボ
キシレート
ｎ２０ Ｄ 1.5031
2′−メチル−2′−ブテン−1′−イル ２，２−
ジメチル−３−クロロメチル−３−プロポキシシ
クロプロパンカルボキシレート
ｎ２０ Ｄ 1.5147
次に代表例について合成例を示すが他の本発明
化合物も同様の傾向を示すものである。なお化合
物名は前記有効成分例のものと同一である。
合成例 １
２，２，３−トリメチル−３−メトキシシクロ
プロパンカルボン酸クロライド3.6ｇを乾燥ベン
ゼン15mlに溶解し、これに１−エチニル−２−メ
チル−２−ペンテン−１−オール2.5ｇ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−メトキ
シシクロプロパンカルボキシレート4.4ｇを得
た。
合成例 ２
２，２−ジメチル−３−トリフルオロメチル−
３−クロロメチルシクロプロパンカルボン酸4.7
ｇと１−エチニル−２−メチル−２−ペンテン−
１−オール2.5ｇをベンゼン50mlに溶解し、6.2ｇ
のジシクロヘキシルカルボキシイミドを添加して
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1′−
エチニル−2′−メチル−2′−ペンテン−1′−イル
２，２−ジメチル−３−トリフルオロメチル−
３−クロロメチルシクロプロパンカルボキシレー
ト5.5ｇを得た。
合成例 ３
２，２，３−トリメチル−３−メトキシシクロ
プロパンカルボン酸のナトリウム塩4.2ｇと１−
エチニル−２−メチル−３−プロパルギル−２−
プロペン−１−クロライド3.3ｇをベンゼン50ml
に懸濁し、環流下に３時間窒素気流中で反応させ
た後反応液を冷却し析出する食塩を別したのち
食塩水で充分洗浄後ぼう硝で乾燥し、ベンゼンを
減圧下で留去して1′−エチニル−2′−メチル−
3′−プロパルギル−2′−プロペン−1′−イル
２，２，３−トリメチル−３−メトキシシクロプ
ロパンカルボキシレート5.4ｇを得た。
合成例 ４
２，２−ジメチル−３−クロロメチル−３−プ
ロポキシシクロプロパンカルボン酸のメチルエス
テル4.7ｇと２−メチル−２−ブテン−１−オー
ル1.8ｇ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更に
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
2′−メチル−2′−ブテン−1′−イル ２，２−ジ
メチル−３−クロロメチル−３−プロポキシシク
ロプロパンカルボキシレート4.8ｇを得た。
合成例 ５
金属ナトリウム1.5ｇを無水エタノール50mlに
溶解させ、これに無水トルエン100mlを加える。
窒素気流中で減圧下にエタノール、トルエンを
除去し、析出したナトリウムエトキサイドに１，
２−ジメトキシエタン100mlを加え、更にdl−シ
ス，トランス−２，２，３−トリメチル−３−メ
トキシシクロプロパンカルボン酸のエチルエステ
ル11.0ｇを加えて12時間加熱還流する。異性化終
了後、１，２−ジメトキシエタンを減圧下に留去
し、残留分に水100mlを加えてエーテル抽出を行
なう。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、エーテルを留去後蒸
留により、dl−トランス−２，２，３−トリメチ
ル−３−メトキシシクロプロパンカルボン酸のエ
チルエステル（沸点115〜118℃／25mmHgの留
分）9.1ｇを得た。
このエチルエステル4.5ｇを酢酸20ml及び35％
臭酸水溶液20ml中で加水分解し、得られたカルボ
ン酸3.7ｇを合成例２の方法に従い、１−エチニ
ル−２−メチル−３−プロパルギル−２−プロペ
ン−１−オール2.8ｇと反応させて1′−エチニル
−2′−メチル−3′−プロパルギル−2′−プロペン
−1′−イル dl−トランス−２，２，３−トリメ
チル−３−メトキシシクロプロパンカルボキシレ
ート（ｎ２０ Ｄ 1.5087）4.5ｇを得た。
合成例 ６
dl−シス，トランス−２，２，３−トリメチル
−３−メトキシシクロプロパンカルボン酸のエチ
ルエステル15.0ｇについて精密蒸留を繰返し、dl
−トランス−２，２，３−トリメチル−３−メト
キシシクロプロパンカルボン酸のエチルエステル
（沸点76℃／17mmHgの留分）5.9ｇとdl−シス−
２，２，３−トリメチル−３−メトキシシクロプ
ロパンカルボン酸のエチルエステル（沸点81℃／
13mmHgの留分）1.6ｇを得た。
後者のエチルエステルを合成例５と同様に処理
して1′−エチニル−2′−メチル−3′−プロパルギ
ル−2′−プロペン−1′−イル dl−シス−２，
２，３−トリメチル−３−メトキシシクロプロパ
ンカルボキシレート（ｎ２０ Ｄ 1.5029）を得た。
以後、前記化合物番号の後にＡの記号をつけて
酸部分がdl−トランス体であることを、又Ｂの記
号をつけてdl−シス体であることを表わす。
合成例 ７
合成例５で得られたdl−トランス−２，２，３
−トリメチル−３−メトキシシクロプロパンカル
ボン酸3.9ｇをメタノール50mlに50℃で溶解し、
これにｌ−（４−トリル）−２−フエネチルアミン
5.2ｇをメタノール25mlに溶かした液を加え、塩
を生成さす。室温まで冷却して２時間放置し、析
出した結晶を取する。この結晶を更にメタノー
ルで再結して3.2ｇの結晶を得る。この結晶に10
％カセイソーダ水溶液を20mlを加えて懸濁後、エ
ーテル抽出によりｌ−（４−トリル）−２−フエネ
チルアミンを回収する。水層を塩酸で酸性にして
塩化メチレンで抽出後、溶媒を留去してｌ−トラ
ンス−２，２，３−トリメチル−３−メトキシシ
クロプロパンカルボン酸1.3ｇを得た。
〔α〕２０ Ｄ−44゜（クロロホルム）光学純度92％
このカルボン酸1.1ｇを合成例２の方法に従
い、１−エチニル−２−メチル−３−プロパルギ
ル−２−プロペン−１−オール1.3ｇと反応させ
て、1′−エチニル−2′−メチル−3′−プロパルギ
ル−2′−プロペン−1′−イル ｌ−トランス−
２，２，３−トリメチル−３−メトキシシクロプ
ロパンカルボキシレート（ｎ２０ Ｄ 1.5037）1.4ｇを
得た。
なお、この化合物はdl−トランス体のエステル
に較べて約２倍の殺虫活性を示した。
以後前記化合物番号の後にＣの記号をつけて、
酸部分がｌ−トランス体であることを表わす。
本発明の化合物は常温で固体または液体であ
り、有機溶剤一般に易溶である。これらの化合物
は従来のピレスロイドに比べて揮散性が高いとい
う特徴を有しており、燻蒸用、及び蒸散用殺虫剤
として好適に使用される。なお、油剤、乳剤、エ
アゾール剤など従来の散布用殺虫剤に調製したも
のを、適当な媒体に散布、噴霧し、前記目的のた
めに使用してももちろんかまわないが、例えば、
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場合や、この有効成
分を適当な加熱体や蒸散促進助剤によりあるいは
常温下に揮散させるいわゆる蒸散用殺虫剤として
使用する場合に特にすぐれた効果が得られる。こ
こでいう適当な加熱体としては電気ヒーターや化
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、これらに水ある
いは空気を接触させることによつて発熱がおこ
る。）があげられ、蒸散促進助剤としてはアダマ
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があげられる。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、２，６−ジターシヤリ−ブチル−４
−メチルフエノール（BHT）、２，６−ジターシ
ヤリ−ブチルフエノール等のフエノール系又はア
ミン系等の酸化防止剤を添加することによつて本
発明化合物の安定性を一層増大することができ
る。又、他の殺虫剤例えばフエニトロチオン、
DDVP、ダイアジノンなどの有機リン剤、NAC、
MTMC、BPMC、PHCなどのカーバメート剤、
ピレトリン、アレスリン、フラメトリン、フター
ルスリン、フエノトリン、ペルメトリンなどの従
来のピレスロイド系殺虫剤を混合することによつ
て効力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。
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次に実施例
及び効果の試験成績を示す。
実施例 １
本発明化合物(1)0.2物に白灯油を加えて全体を
100部として0.2％油剤を得る。
実施例 ２
本発明化合物(2)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。
実施例 ３
本発明化合物(3)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。
実施例 ４
本発明化合物(4)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。
実施例 ５
本発明化合物(5)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。
実施例 ６
本発明化合物(6)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。
実施例 ７
本発明化合物(7)0.03ｇ、サイネピリン500 0.1
ｇ、ジブチルハイドロキノン（DBHQ）0.01ｇを
厚さ２mm、たて35mm、横22mmの厚紙シートに浸み
込ませて、電気蚊取用マツトを得る。
実施例 ８
本発明化合物(2)−A0.3ｇ、香料0.01ｇを厚さ１
mm、たて60mm、横80mmの厚紙シートに浸み込ませ
て衣料用防虫マツトを得る。
試験例 １
散布による殺虫試験
本発明化合物の0.2％の白灯溶液(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。
The present invention is based on the general formula (In the formula, R 1 is a methyl group or a halomethyl group, and R 2 is an alkyl group, alkenyl group, haloalkyl group, or haloalkenyl group having 1 to 3 carbon atoms. R 3 is a hydrogen atom or an ethynyl group. ,
R 4 is a hydrogen atom or a methyl group, R 5 has 1 carbon number
-3 represents an alkyl group, an allyl group or a propargyl group. The present invention relates to an insecticide for fumigation and transpiration, characterized by containing a novel cyclopropanecarboxylic acid ester derivative shown in ) and its optical and geometric isomers as active ingredients. Various alcohol components of chrysanthemum acid esters have been studied, and for example, allethrin and flamethrin are widely used as insecticides for fumigation and transpiration such as mosquito coils and electric mosquito repellents. Recently, research on acid components has become active, and dihalobinyl chrysanthemum acid, which has excellent photostability, and tetramethylcyclopropanecarboxylic acid, which has high volatility, have been developed. Although this ester of tetramethylcyclopropanecarboxylic acid and alcohol of the general formula () has high volatility and insecticidal activity, it is more toxic to warm-blooded animals than conventional pyrethroids, and is a safety-oriented ester. From the current situation, it is difficult to say that it is necessarily excellent for home use. By the way, it is widely known from research on DDT and BHC-related substances that alkoxy groups are easily metabolized in the bodies of warm-blooded animals, and as a result of repeated research, the inventors found that
It was discovered that it was useful to substitute the side chain of chrysanthemum acid with an alkoxy group, and the alkoxycyclopropanecarboxylic acid ester represented by the general formula () was found to be extremely effective as an insecticidal ingredient against various sanitary pests and agricultural and horticultural pests. It was discovered that while it has an insecticidal effect, it has low toxicity to warm-blooded animals and has excellent volatility. 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 is a methyl group or a halomethyl group, and R 2 represents an alkyl group, alkenyl group, haloalkyl group, or haloalkenyl group having 1 to 3 carbon atoms.) or its reactivity Derivatives and general formulas (In the formula, R 3 is a hydrogen atom or an ethynyl group, R 4 is a hydrogen atom or a methyl group, and R 5 is an alkyl group having 1 to 3 carbon atoms, an allyl group, or a propargyl group.) It can be prepared by reacting with an alcohol 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. 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. What is obtained by a normal production method is a mixture of optical isomers, and the present invention includes all of the esters of each isomer constituting this mixture. Typical examples (shown as a mixture of optical isomers and geometric isomers) of the compound represented by the above formula () and preferred as an insecticide for fumigation or transpiration are as follows; however, the present invention is limited only to these. It is not something that will be done. 1'-ethynyl-2'-methyl-2'-pentene-
1'-yl 2,2,3-trimethyl-3-methoxycyclopropanecarboxylate n 20 D 1.5026 1'-ethynyl-2'-methyl-3'-propargyl-2'-propen-1'-yl 2,2,3-trimethyl-3-methoxycyclopropanecarboxylate n 20 D 1.5075 2',5'-hexadien-1'-yl 2,2,3
-Trimethyl-3-(1-fluoro-2-chlorovinyloxy)cyclopropanecarboxylate n 20 D 1.5285 1'-ethynyl-2'-methyl-2'-pentene-
1'-yl 2,2-dimethyl-3-trifluoromethyl-3-chloromethoxycyclopropanecarboxylate n 20 D 1.5146 2'-methyl-2'-hexen-1'-yl 2,
2,3-trimethyl-3-ethoxycyclopropanecarboxylate n 20 D 1.5133 1'-ethynyl-3'-propargyl-2'-propen-1'-yl 2,2-dimethyl-3-fluoromethyl-3-allyloxycyclopropanecarboxylate n 20 D 1.5031 2'-Methyl-2'-buten-1'-yl 2,2-
Dimethyl-3-chloromethyl-3-propoxycyclopropanecarboxylate n 20 D 1.5147 Next, a synthesis example will be shown for a typical example, but other compounds of the present invention also show a similar tendency. The compound names are the same as those in the active ingredient examples above. Synthesis Example 1 3.6 g of 2,2,3-trimethyl-3-methoxycyclopropanecarboxylic acid chloride was dissolved in 15 ml of dry benzene, and 2.5 g of 1-ethynyl-2-methyl-2-penten-1-ol was dried therein. When a solution of 20 ml of benzene is added and 3 ml of dry pyridine is added as a condensation aid, crystals of pyridine hydrochloride are precipitated. 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 1'-ethynyl-2'-methyl-2'-pentene-
4.4 g of 1'-yl 2,2,3-trimethyl-3-methoxycyclopropanecarboxylate was obtained. Synthesis example 2 2,2-dimethyl-3-trifluoromethyl-
3-chloromethylcyclopropanecarboxylic acid 4.7
g and 1-ethynyl-2-methyl-2-pentene-
Dissolve 2.5g of 1-ol in 50ml of benzene to obtain 6.2g
of dicyclohexylcarboximide 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.
Ethynyl-2'-methyl-2'-penten-1'-yl 2,2-dimethyl-3-trifluoromethyl-
5.5 g of 3-chloromethylcyclopropanecarboxylate was obtained. Synthesis Example 3 4.2 g of sodium salt of 2,2,3-trimethyl-3-methoxycyclopropanecarboxylic acid and 1-
Ethynyl-2-methyl-3-propargyl-2-
3.3g of propene-1-chloride in 50ml of benzene
After reacting under reflux for 3 hours in a nitrogen stream, the reaction solution was cooled and the precipitated salt was separated, thoroughly washed with brine and dried over sulfuric acid, and the benzene was distilled off under reduced pressure. 1'-ethynyl-2'-methyl-
3′-propargyl-2′-propen-1′-yl
5.4 g of 2,2,3-trimethyl-3-methoxycyclopropanecarboxylate was obtained. Synthesis Example 4 4.7 g of methyl ester of 2,2-dimethyl-3-chloromethyl-3-propoxycyclopropanecarboxylic acid and 1.8 g of 2-methyl-2-buten-1-ol are heated to 150°C. When the temperature reaches 150°C, add 0.25 g of sodium and start distilling off methanol. When the distillation of methanol has stopped, 0.25 g of sodium is further 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 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.
4.8 g of 2'-methyl-2'-buten-1'-yl 2,2-dimethyl-3-chloromethyl-3-propoxycyclopropanecarboxylate was obtained. Synthesis Example 5 1.5 g of sodium metal is dissolved in 50 ml of absolute ethanol, and 100 ml of anhydrous toluene is added thereto. Ethanol and toluene were removed under reduced pressure in a nitrogen stream, and 1,
Add 100 ml of 2-dimethoxyethane, and further add 11.0 g of ethyl ester of dl-cis,trans-2,2,3-trimethyl-3-methoxycyclopropanecarboxylic acid, and heat under reflux for 12 hours. After the isomerization is completed, 1,2-dimethoxyethane is distilled off under reduced pressure, and 100 ml of water is added to the residue for ether extraction. The ether solution was thoroughly washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over nitric acid, the ether was distilled off, and the ethyl ester of dl-trans-2,2,3-trimethyl-3-methoxycyclopropanecarboxylic acid was obtained by distillation. (9.1 g of a fraction with a boiling point of 115-118°C/25 mmHg) was obtained. Add 4.5 g of this ethyl ester to 20 ml of acetic acid and 35%
3.7 g of the carboxylic acid obtained by hydrolysis in 20 ml of aqueous hydrochloric acid solution was reacted with 2.8 g of 1-ethynyl-2-methyl-3-propargyl-2-propen-1-ol according to the method of Synthesis Example 2. 1'-ethynyl-2'-methyl-3'-propargyl-2'-propen-1'-yl dl-trans-2,2,3-trimethyl-3-methoxycyclopropanecarboxylate (n 20 D 1.5087) 4.5 I got g. Synthesis Example 6 Repeat precision distillation on 15.0 g of ethyl ester of dl-cis,trans-2,2,3-trimethyl-3-methoxycyclopropanecarboxylic acid to obtain dl
- 5.9 g of ethyl ester of trans-2,2,3-trimethyl-3-methoxycyclopropanecarboxylic acid (boiling point 76°C/17 mmHg fraction) and dl-cis-
Ethyl ester of 2,2,3-trimethyl-3-methoxycyclopropanecarboxylic acid (boiling point 81℃/
1.6 g of 13 mmHg fraction) was obtained. The latter ethyl ester was treated in the same manner as in Synthesis Example 5 to obtain 1'-ethynyl-2'-methyl-3'-propargyl-2'-propen-1'-yl dl-cis-2,
2,3-trimethyl-3-methoxycyclopropanecarboxylate ( n20D 1.5029 ) was obtained. Hereinafter, the symbol A will be added after the compound number to indicate that the acid moiety is the dl-trans form, and the symbol B will be added to indicate the dl-cis form. Synthesis Example 7 dl-trans-2,2,3 obtained in Synthesis Example 5
-Dissolve 3.9 g of trimethyl-3-methoxycyclopropanecarboxylic acid in 50 ml of methanol at 50°C,
To this, l-(4-tolyl)-2-phenethylamine
Add a solution of 5.2g dissolved in 25ml of methanol to generate salt. Cool to room temperature, leave for 2 hours, and collect precipitated crystals. The crystals were further recrystallized with methanol to obtain 3.2 g of crystals. 10 to this crystal
After adding 20 ml of % caustic soda aqueous solution and suspending, 1-(4-tolyl)-2-phenethylamine is recovered by ether extraction. The aqueous layer was acidified with hydrochloric acid, extracted with methylene chloride, and the solvent was distilled off to obtain 1.3 g of l-trans-2,2,3-trimethyl-3-methoxycyclopropanecarboxylic acid. [α] 20 D -44° (Chloroform) Optical purity 92% 1.1 g of this carboxylic acid was mixed with 1.3 g of 1-ethynyl-2-methyl-3-propargyl-2-propen-1-ol according to the method of Synthesis Example 2. 1'-ethynyl-2'-methyl-3'-propargyl-2'-propen-1'-yl l-trans-
1.4 g of 2,2,3-trimethyl-3-methoxycyclopropanecarboxylate (n 20 D 1.5037) was obtained. This compound exhibited approximately twice the insecticidal activity as compared to the dl-trans ester. Hereinafter, add the symbol C after the compound number,
Indicates that the acid moiety is l-trans form. The compound of the present invention is solid or liquid at room temperature and is generally easily soluble in organic solvents. These compounds are characterized by higher volatility than conventional pyrethroids, and are suitably used as fumigation and transpiration insecticides. It should be noted that it is of course possible to use a conventional sprayable insecticide such as an oil, emulsion, or aerosol by dispersing or spraying it onto a suitable medium and using it for the above purpose, but for example,
When mixed with wood flour or other suitable base material and used as a fumigating insecticide such as mosquito coils, or when the active ingredient is volatilized with a suitable heating element or transpiration accelerator or at room temperature, so-called transpiration insecticide. Particularly excellent effects can be obtained when used as an agent. Examples of suitable heating elements include electric heaters and chemical heating elements (for example, compositions made of sodium sulfide and carbon, compositions made of common salt, iron, and carbon, and hydrated salts of common salt, iron, carbon, and sodium metasilicate). (compositions, quicklime, etc., which generate heat when brought into contact with water or air), and transpiration-promoting agents include sublimable substances such as adamantane, cyclododecane, and trimethylene norbornane. It will be done. 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. In addition, 2,6-ditertiary-butyl-4
The stability of the compounds of the present invention can be further increased by adding phenolic or amine antioxidants such as -methylphenol (BHT) and 2,6-ditertiary-butylphenol. Also, other insecticides such as fenitrothion,
Organic phosphorus agents such as DDVP and diazinon, NAC,
Carbamate agents such as MTMC, BPMC, PHC,
By mixing conventional pyrethroid insecticides such as pyrethrin, allethrin, flamethrin, phthalthrin, phenothrin, and permethrin, a multipurpose composition with excellent efficacy can be obtained, and labor-saving and synergistic effects between drugs can be expected. It is something that can be taught. In order to make it clearer that the composition provided by the present invention is excellent, Examples and efficacy test results are shown below. Example 1 White kerosene was added to 0.2 of the compound of the present invention (1) and the whole was mixed.
Obtain 0.2% oil solution as 100 parts. Example 2 White kerosene was added to 0.2 parts of the compound (2) of the present invention and 0.8 parts of piperonyl butoxide to make a total of 100 parts to obtain an oil agent. Example 3 To 20 parts of the compound of the present invention (3), 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. Example 4 0.4 parts of the present compound (4), 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. Example 5 0.5 g of the present compound (5) 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. Example 6 0.4 g of the compound (6) of the present invention and 1.0 g of MGK-5026 were uniformly mixed with 98.6 g of a mosquito coil base material to obtain a mosquito coil by a known method. Example 7 Compound of the present invention (7) 0.03g, Cinepirin 500 0.1
g, 0.01 g of dibutylhydroquinone (DBHQ) is impregnated into a cardboard sheet with a thickness of 2 mm, a height of 35 mm, and a width of 22 mm to obtain an electric mosquito repellent mat. Example 8 0.3 g of the present compound (2)-A and 0.01 g of fragrance were added to a thickness of 1
Insect repellent mat for clothing is obtained by impregnating a cardboard sheet with a length of 60 mm and a width of 80 mm. Test Example 1 Insecticidal test by spraying A 0.2% white light solution of the compound of the present invention (A), 0.2% and a white light solution of 0.8% piperonyl butoxide (B), 0.1%
The falling and turning rates of houseflies were determined for a white light solution containing 0.1% phthalthrin (C), and a white light solution containing 0.2% each of allethrin and phthalthrin, and the relative effectiveness of the test agent was calculated. The ratio was calculated as follows. 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
実施例(5)より、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。この実験は防虫科学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 Based on Example (5), a mosquito coil containing 0.5% of the insecticidal ingredient was prepared, and its effectiveness in causing adult Culex mosquitoes to fall and roll over was tested. This experiment is insect control science 16
(1951), p. 176, the relative effectiveness of the incense sticks was calculated according to the method of Nagasawa, Katsuta et al. The sample drug number is the same as that of the active ingredient example above.
【表】【table】
【表】
試験例 ３
蒸散による殺虫試験〔〕
実施例７より調製した電気蚊取用マツトを市販
電気蚊取器で140℃に加熱する。６畳の部屋にお
いたアカイエカの仰転率からアレスリンに対する
相対有効度を経時的に調べたところ次の如くであ
る。[Table] Test Example 3 Insecticidal test by transpiration [] The electric mosquito repellent mat prepared in Example 7 was heated to 140°C using a commercially available electric mosquito repellent. The relative effectiveness of allethrin was examined over time based on the supination rate of Culex mosquitoes placed in a 6-tatami room, and the results were as follows.
【表】【table】
【表】
試験例 ４
蒸散による殺虫試験〔〕
実施例８により調製した衣料用殺虫マツトをプ
ラスチツクケースに収納し容積600のタンス内
につるした。
試験開始直後及び６ケ月後に、イガの１令幼虫
10匹を放飼した直径４cm、幅２cmのガラスリング
（両面を羊毛布でカバー）をタンス内に設置し、
１日後、２日後、７日後の死虫率を観察した。[Table] Test Example 4 Insecticidal test by transpiration [] The insecticidal mat for clothing prepared in Example 8 was housed in a plastic case and hung in a 600-volume chest of drawers. Immediately after the start of the test and after 6 months, the first instar larvae of the burr
A glass ring with a diameter of 4 cm and a width of 2 cm (covered on both sides with wool cloth) containing 10 animals was placed inside a chest of drawers.
The mortality rate of insects was observed after 1 day, 2 days, and 7 days.
Claims (1)
り、R2は炭素数が１〜３のアルキル基、アルケ
ニル基、ハロアルキル基又はハロアルケニル基を
表わす。R3は水素原子又はエチニル基であり、
R4は水素原子又はメチル基を、R5は炭素数が１
〜３のアルキル基、アリル基又はプロパルギル基
を示す。）で示されるシクロプロパンカルボン酸
エステル誘導体及びその光学ならびに幾何異性体
を含有することを特徴とする燻蒸用及び蒸散用殺
虫剤。[Claims] 1. General formula (In the formula, R 1 is a methyl group or a halomethyl group, and R 2 is an alkyl group, alkenyl group, haloalkyl group, or haloalkenyl group having 1 to 3 carbon atoms. R 3 is a hydrogen atom or an ethynyl group. ,
R 4 is a hydrogen atom or a methyl group, R 5 has 1 carbon number
-3 represents an alkyl group, an allyl group or a propargyl group. ) An insecticide for fumigation and transpiration, characterized by containing a cyclopropanecarboxylic acid ester derivative represented by () and its optical and geometric isomers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14875479A JPS5671044A (en) | 1979-11-15 | 1979-11-15 | Cyclopropanecarboxylate derivative, its preparation, and insecticide containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14875479A JPS5671044A (en) | 1979-11-15 | 1979-11-15 | Cyclopropanecarboxylate derivative, its preparation, and insecticide containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5671044A JPS5671044A (en) | 1981-06-13 |
| JPS6252722B2 true JPS6252722B2 (en) | 1987-11-06 |
Family
ID=15459879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14875479A Granted JPS5671044A (en) | 1979-11-15 | 1979-11-15 | Cyclopropanecarboxylate derivative, its preparation, and insecticide containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5671044A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54119437A (en) * | 1978-03-08 | 1979-09-17 | Yoshio Katsuta | Cyclopropane carboxylic acid ester derivative*its manufacture and insecticide containing it |
| JPS5553243A (en) * | 1978-10-12 | 1980-04-18 | Yoshio Katsuta | Cyclopropanecarboxylate derivative, its preparation, insecticide comprising it |
| JPS5557538A (en) * | 1978-10-24 | 1980-04-28 | Yoshio Katsuta | Cyclopropanecarboxylic acid ester derivative, its preparation, and insecticide containing the same |
-
1979
- 1979-11-15 JP JP14875479A patent/JPS5671044A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54119437A (en) * | 1978-03-08 | 1979-09-17 | Yoshio Katsuta | Cyclopropane carboxylic acid ester derivative*its manufacture and insecticide containing it |
| JPS5553243A (en) * | 1978-10-12 | 1980-04-18 | Yoshio Katsuta | Cyclopropanecarboxylate derivative, its preparation, insecticide comprising it |
| JPS5557538A (en) * | 1978-10-24 | 1980-04-28 | Yoshio Katsuta | Cyclopropanecarboxylic acid ester derivative, its preparation, and insecticide containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5671044A (en) | 1981-06-13 |
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