JPS6223740B2 - - Google Patents
Info
- Publication number
- JPS6223740B2 JPS6223740B2 JP54122175A JP12217579A JPS6223740B2 JP S6223740 B2 JPS6223740 B2 JP S6223740B2 JP 54122175 A JP54122175 A JP 54122175A JP 12217579 A JP12217579 A JP 12217579A JP S6223740 B2 JPS6223740 B2 JP S6223740B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- optical
- hydrogen 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
- 150000001875 compounds Chemical class 0.000 claims description 42
- 125000005843 halogen group Chemical group 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 230000003287 optical effect Effects 0.000 claims description 16
- 125000003342 alkenyl group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000001188 haloalkyl group Chemical group 0.000 claims description 12
- 239000002917 insecticide Substances 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000002728 pyrethroid Substances 0.000 claims description 2
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 9
- 239000002671 adjuvant Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- -1 alkali metal salts Chemical class 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 14
- 230000000749 insecticidal effect Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 241000255925 Diptera Species 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000004480 active ingredient Substances 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 125000004494 ethyl ester group Chemical group 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 241000607479 Yersinia pestis Species 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 5
- 239000012267 brine Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229960005235 piperonyl butoxide Drugs 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- 229940024113 allethrin Drugs 0.000 description 4
- 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 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010438 heat treatment Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GXUQMKBQDGPMKZ-UHFFFAOYSA-N 2-hydroxy-2-(3-phenoxyphenyl)acetonitrile Chemical compound N#CC(O)C1=CC=CC(OC=2C=CC=CC=2)=C1 GXUQMKBQDGPMKZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241001674044 Blattodea Species 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229960005199 tetramethrin Drugs 0.000 description 3
- CXBMCYHAMVGWJQ-UHFFFAOYSA-N tetramethrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OCN1C(=O)C(CCCC2)=C2C1=O CXBMCYHAMVGWJQ-UHFFFAOYSA-N 0.000 description 3
- 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
- 241001124076 Aphididae Species 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 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
- 241000257226 Muscidae Species 0.000 description 2
- 241001477931 Mythimna unipuncta Species 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 241000320508 Pentatomidae Species 0.000 description 2
- 241001454295 Tetranychidae Species 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 238000003958 fumigation Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 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
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- SBNFWQZLDJGRLK-RTWAWAEBSA-N (1R)-trans-phenothrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 SBNFWQZLDJGRLK-RTWAWAEBSA-N 0.000 description 1
- KGANAERDZBAECK-UHFFFAOYSA-N (3-phenoxyphenyl)methanol Chemical compound OCC1=CC=CC(OC=2C=CC=CC=2)=C1 KGANAERDZBAECK-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
- QUYVTGFWFHQVRO-UHFFFAOYSA-N 1-(chloromethyl)-3-phenoxybenzene Chemical compound ClCC1=CC=CC(OC=2C=CC=CC=2)=C1 QUYVTGFWFHQVRO-UHFFFAOYSA-N 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- DSQFSFBBPSALMS-UHFFFAOYSA-N 2-bromo-2-(3-phenoxyphenyl)acetonitrile Chemical compound N#CC(Br)C1=CC=CC(OC=2C=CC=CC=2)=C1 DSQFSFBBPSALMS-UHFFFAOYSA-N 0.000 description 1
- LAWCUGGFTNCCKX-UHFFFAOYSA-N 2-methoxycyclopropane-1-carboxylic acid Chemical compound COC1CC1C(O)=O LAWCUGGFTNCCKX-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-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
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 241001124134 Chrysomelidae Species 0.000 description 1
- 241001414720 Cicadellidae Species 0.000 description 1
- NENBAISIHCWPKP-UHFFFAOYSA-N Clofenamide Chemical compound NS(=O)(=O)C1=CC=C(Cl)C(S(N)(=O)=O)=C1 NENBAISIHCWPKP-UHFFFAOYSA-N 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
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000005916 Methomyl Substances 0.000 description 1
- 241000721621 Myzus persicae Species 0.000 description 1
- 241001556089 Nilaparvata lugens Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000500437 Plutella xylostella Species 0.000 description 1
- 241000500441 Plutellidae Species 0.000 description 1
- 241000283080 Proboscidea <mammal> Species 0.000 description 1
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 description 1
- 244000088415 Raphanus sativus Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- ISRUGXGCCGIOQO-UHFFFAOYSA-N Rhoden Chemical compound CNC(=O)OC1=CC=CC=C1OC(C)C ISRUGXGCCGIOQO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 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
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000007605 air drying Methods 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- XUHFBOUSHUEAQZ-UHFFFAOYSA-N bromobenzyl cyanide Chemical compound N#CC(Br)C1=CC=CC=C1 XUHFBOUSHUEAQZ-UHFFFAOYSA-N 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- IRUJZVNXZWPBMU-UHFFFAOYSA-N cartap Chemical compound NC(=O)SCC(N(C)C)CSC(N)=O IRUJZVNXZWPBMU-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000013339 cereals Nutrition 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
- YMGUBTXCNDTFJI-UHFFFAOYSA-M cyclopropanecarboxylate Chemical compound [O-]C(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-M 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 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
- 230000003247 decreasing effect Effects 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
- 244000013123 dwarf bean Species 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation 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
- 238000007429 general method Methods 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
- 125000004970 halomethyl group Chemical group 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000003898 horticulture Methods 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
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 231100000636 lethal dose Toxicity 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 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
- 239000001301 oxygen Substances 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
- 239000007787 solid Substances 0.000 description 1
- 238000009331 sowing Methods 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
- 150000003463 sulfur Chemical class 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 210000000115 thoracic cavity Anatomy 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は一般式
（式中、ＸはＯ，Ｓ，又はNH基を示し、Y1，
Y2，Y3は水素原子又はハロゲン原子を示す。た
だしY1，Y2，Y3の少なくとも１個はハロゲン原
子を表わす。R1は炭素数が１〜８の低級アルキ
ル基、低級アルケニル基、ハロアルキル基、ハロ
アルケニル基及び一般式（），（），（）で表
わされる基を示す。
The present invention is based on the general formula (In the formula, X represents O, S, or NH group, Y 1 ,
Y 2 and Y 3 represent a hydrogen atom or a halogen atom. However, at least one of Y 1 , Y 2 and Y 3 represents a halogen atom. R 1 represents a lower alkyl group having 1 to 8 carbon atoms, a lower alkenyl group, a haloalkyl group, a haloalkenyl group, and a group represented by the general formula (), (), or ().
ここにｍは１〜３の整数、ｎは２〜５の整数
を、R3は水素原子、低級アルキル基、低級アル
ケニル基、ハロゲン原子、ハロアルキル基又はア
ルコキシル基を示す。R2は水素原子、シアノ基
又はトリフルオロメチル基を表わす。）で表わさ
れる新規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
しても従来のピレスロイド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、ＸはＯ，Ｓ，又はNH基を示し、Y1，
Y2，Y3は水素原子又はハロゲン原子を示す。た
だしY1，Y2，Y3の少なくとも１個はハロゲン原
子を表わす。R1は炭素数が１〜８の低級アルキ
ル基、低級アルケニル基、ハロアルキル基、ハロ
アルケニル基及び一般式（），（），（）で表
わされる基を示す。 Here, m is an integer of 1 to 3, n is an integer of 2 to 5, and R 3 is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a haloalkyl group, or an alkoxyl group. R 2 represents a hydrogen atom, a cyano group or a trifluoromethyl group. ), its optical and geometrical isomers, its production method, and an insecticide 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 as an insecticidal ingredient against various sanitary pests and agricultural and horticultural pests, and has extremely low toxicity to warm-blooded animals. We learned that it is much more stable against light than conventional pyrethroids. As described above, the compound represented by the above formula () overcomes the drawback of conventional pyrethroids such as 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 above formula () used as an active ingredient in the present invention
The compound represented by has the general formula according to the general method for ester production. (In the formula, X represents O, S, or NH group, Y 1 ,
Y 2 and Y 3 represent a hydrogen atom or a halogen atom. However, at least one of Y 1 , Y 2 and Y 3 represents a halogen atom. R 1 represents a lower alkyl group having 1 to 8 carbon atoms, a lower alkenyl group, a haloalkyl group, a haloalkenyl group, and a group represented by the general formula (), (), or ().
ここにｍは１〜３の整数、ｎは２〜５の整数
を、R3は水素原子、低級アルキル基、低級アル
ケニル基、ハロゲン原子、ハロアルキル基又はア
ルコキシル基を示す。）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
（ここにR2は水素原子、シアノ基又はトリフ
ルオロメチル基を示す。）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。
なお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。次に代表
例（光学異性体ならびに幾何異性体の混合物とし
て示す。）を示すが本発明はもちろんこれらのみ
に限定されるものではない。 Here, m is an integer of 1 to 3, n is an integer of 2 to 5, and R 3 is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a haloalkyl group, or an alkoxyl group. ) or its reactive derivative and the general formula (R 2 here represents a hydrogen atom, a cyano group, or a trifluoromethyl 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. 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.
Although what is obtained by a normal production method is a mixture of optical isomers, all of the esters of each isomer constituting this are also included in the present invention. Next, representative examples (shown as a mixture of optical isomers and geometric isomers) are shown, but the present invention is of course not limited to these.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
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。本発明の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、
ダニ類等の防除にきわめて有用である。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。また本発明の化合物の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、植物生長調整剤、肥
料その他の農薬を混合することによつて効果のす
ぐれた多目的組成物が得られ、労力の省力化、薬
剤間の相乗効果も充分期待しえるものである。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に次に効果の試
験成績を示す。
試験例１ 散布による殺虫試験
本発明化合物の0.2％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。[Table] 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. Also, when used as a so-called electric mosquito repellent by dissolving this active ingredient in an appropriate organic solvent and soaking it in a mount, or dissolving it in an appropriate solvent and heating and evaporating it with an appropriate heating element, it is as good as a mosquito coil. Show effectiveness. The compound of the present invention is more stable to light than conventional pyrethroids, has a broader insecticidal spectrum, is less toxic, and is cheaper, so it can be used in agriculture and horticulture as an alternative to conventional organophosphorus agents and organochlorine insecticides. It can be used as an 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 moths, diamondback moths, tobacco moths, bean weevils, nocturnal moths, and cabbage moths. , agricultural pests such as chestnut beetles, leaf beetles, aphids, and scale insects, grain storage pests such as brown elephants,
It is extremely useful for controlling mites, etc. 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, other insecticides of the compounds of the present invention, such as organophosphorus agents such as fenitrothion, DDVP, diazinon, propaphos, and pyridafentione,
Carbamates such as NAC, MTMC, BPMC, PHC, conventional pyrethroid insecticides such as pyrethrin, allethrin, phthalthrin, flamethrin, phenothrin, permethrin, cypermethrin, decametrin, fuenvalerate, fuenpropanate, cartap, chlorphenamide Insecticides or acaricides such as gin and methomyl,
By mixing fungicides, nematicides, herbicides, plant growth regulators, fertilizers, and other agricultural chemicals, highly effective multipurpose compositions can be obtained, saving labor and providing sufficient synergy between the drugs. It's something to look forward to. In order to make it clearer that the composition provided by the present invention is excellent, the results of the efficacy test are shown below. 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 rate of houseflies was 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 calculated ratio is as follows.
【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 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 Insect Control Science Volume 16 (1951).
The relative effectiveness of the incense stick was calculated according to the method of Nagasawa, Katsuta et al., p. 176, and the results were as follows. The sample drug number is the same as that of the active ingredient example above.
【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
ピペロニルブトキサイド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ピペロニルブトキサイドによ
る共力効果を調べたところ次の如くである。[Table] Test Example 3 Insecticidal test by micro-dropping method Each of allethrin and the compound of the present invention and piperonyl butoxide were added to each of them as active ingredients.
An acetone solution with a predetermined concentration was added in twice the amount and applied to the thoracic dorsal plate of adult house flies using a microsyringe, and the mortality rate after 24 hours was determined from the relative insecticidal efficacy against allethrin and the synergistic effect with piperonyl butoxide. I investigated and found the following.
【表】
次に本発明化合物製造法について合成実施例を
あげて詳しく説明する。
合成実施例 １
２，２―ジメチル―３―トリフルオロメチル―
３―メトキシシクロプロパンカルボン酸4.3ｇを
アセトン50mlに溶解し、これに３―フエノキシ―
α―シアノベンジルブロマイド5.7ｇ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′―
フエノキシ―α―シアノベンジル２，２―ジメチ
ル―３―トリフルオロメチル―３―メトキシシク
ロプロパンカルボキシレート7.4ｇを得た。
合成実施例 ２
２，２―ジメチル―３―フルオロメチル―３―
（２―メチル―３―ブロモアリルチオ）シクロプ
ロパンカルボン酸6.3ｇと３―フエノキシ―α―
トリフルオロメチルベンジルアルコール4.8ｇと
を50mlの乾燥ベンゼンに溶解し、6.2ｇのジシク
ロヘキシルカルボジイミドを添加して一晩密栓放
置した。翌日、４時間加熱還流して反応を完結さ
せ、冷却後析出したジシクロヘキシル尿素をろ別
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3′―フエノキシ
―α′―トリフルオロメチルベンジル ２，２―
ジメチル―３―フルオロメチル―３―（２―メチ
ル―３―ブロモアリルチオ）シクロプロパンカル
ボキシレート8.8ｇを得た。
合成実施例 ３
２，２―ジメチル―３―トリフルオロメチル―
３―（２―クロロ―４―トリフルオロメチルアニ
リノ）シクロプロパンカルボン酸のナトリウム塩
8.0ｇと３―フエノキシベンジルクロライド4.5ｇ
をベンゼン50mlに溶解し、還流下に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
をろ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に留去して3′―フエノキシ
ベンジル ２，２―ジメチル―３―トリフルオロ
メチル―３―（２―クロロ―４―トリフルオロメ
チルアニリノ）シクロプロパンカルボキシレート
9.6ｇを得た。
合成実施例 ４
２，２―ジメチル―３―ブロモメチル―３―シ
クロヘキシルオキシシクロプロパンカルボン酸ク
ロライド6.3ｇを乾燥ベンゼン15mlに溶解し、こ
れに３―フエノキシ―α―シアノベンジルアルコ
ール4.5ｇ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が析出する。密栓して室
温で一夜放置後、ピリジン塩酸塩の結晶を別し
た後、ベンゼン溶液をぼう硝で乾燥しベンゼンを
減圧下に留去して3′―フエノキシ―α′―シアノ
ベンジル ２，２―ジメチル―３ブロモメチル―
３―シクロヘキシルオキシシクロプロパンカルボ
キシレート8.4ｇを得た。
合成実施例 ５
２，２―ジメチル―３―フルオロクロロメチル
―３―ブロモメトキシシクロプロパンカルボン酸
のメチルエステル6.1ｇと３―フエノキシベンジ
ルアルコール4.2ｇ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を加え理論量の
メタノールを得るまで温度を150℃前後に保ち前
記操作を繰返し行なう。ついで混合物を冷却し、
エーテルに溶解しエーテル溶液を希塩酸、重曹
水、食塩水で洗浄後ぼう硝で乾燥しエーテルを減
圧下に留去して3′―フエノキシベンジル ２，２
―ジメチル―３―フルオロクロロメチル―３―ブ
ロモメトキシシクロプロパンカルボキシレート
8.1ｇを得た。
合成実施例 ６
２，２―ジメチル―３―フルオロメチル―３―
メチルチオシクロプロパンカルボン酸無水物7.4
ｇと３―フエノキシ―α―シアノベンジルアルコ
ール4.5ｇとを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の氷中
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20
ml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20
ｇのカラムを流下させて3′―フエノキシ―α′―
シアノベンジル ２，２―ジメチル―３―フルオ
ロメチル―３―メチルチオシクロプロパンカルボ
キシレート6.5ｇを得た。
合成実施例 ７
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ｄ―
シス、トランス―２，２―ジメチル―３―トリフ
ルオロメチル―３―エトキシシクロプロパンカル
ボン酸のエチルエステル13.0ｇ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、ｄ―トラン
ス―２，２―ジメチル―３―トリフルオロメチル
―３―エ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120〜125℃／30mmHgの留分）
9.6ｇを得た。
このエチルエステル5.2ｇ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4.7ｇを合成実施例２の方法に従い、３―フ
エノキシ―α―シアノベンジルアルコール4.5ｇ
と反応させて3′―フエノキシ―α′―シアノベン
ジル ｄ―トランス―２，２―ジメチル―３―
トリフルオロメチル―３―エトキシシクロプロパ
ンカルボキシレート7.3ｇ（ｎ２０ Ｄ 1.5381）を得
た。
合成実施例 ８
ｄ―シス、トランス―２，２―ジメチル―３
―トリフルオロメチル―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16.0ｇについて
精密蒸留を繰返し、ｄ―トランス―２，２―ジ
メチル―３―トリフルオロメチル―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75℃／15mmHg）5.9ｇとｄ―シス―２，２―
ジメチル―３―トリフルオロメチル―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実施例７と同様に
処理して3′―フエノキシ―α′―シアノベンジル
ｄ―シス―２，２―ジメチル―３―トリフル
オロメチル―３―メトキシシクロプロパンカルボ
キシレート（ｎ２０ Ｄ 1.5306）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ｄ―トランス体であることを、又Ｂの
記号をつけてｄ―シス体であることを表わす。
合成実施例 ９
合成実施例７で得られたｄ―トランス―２，
２―ジメチル―３―トリフルオロメチル―３―エ
トキシシクロプロパンカルボン酸4.2ｇをメタノ
ール50mlに50℃で溶解し、これに―（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20mlを加えて懸濁後、エーテル抽出により―
（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―トランス―２，２―ジメ
チル―３―トリフルオロメチル―３―エトキシシ
クロプロパンカルボン酸1.4ｇを得た。
〔α〕２０ Ｄ−45゜（クロロホルム）光学純度93％
このカルボン酸1.3ｇを合成実施例１の方法に
従い、３―フエノキシ―α―シアノベンジルブロ
マイド1.5ｇと反応させて3′―フエノキシ―α′―
シアノベンジル ―トランス―２，２―ジメチ
ル―３―トリフルオロメチル―３―エトキシシク
ロプロパンカルボキシレート2.0ｇ（ｎ２０ Ｄ
1.5374）を得た。
なお、この化合物はｄ―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―トランス体であることを表わす。
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(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。
参考例 ３
本発明化合物(4)20部にソルポールSM―200（東
邦化学商標名）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(10)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(17)0.5部、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99.0
ｇ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(34)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(45)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
参考例３に準じて得られた下記本発明化合物お
よび対照化合物の乳剤の水による所定濃度の稀釈
液にイネ茎（長さ約12cm）を１分間浸漬した。風
乾後、試験管にイネ茎を入れヒメトビウンカ成虫
を10頭放ち、１日後に生死を調査し、LC50値
（50％致死濃度）から本発明化合物の対照化合物
（）に対する相対殺虫効力を求めたところ次の
如くである。
対照化合物（）…引例１の化合物
対照化合物（）…引例２の化合物
[Table] Next, the method for producing the compound of the present invention will be explained in detail by giving synthesis examples. Synthesis Example 1 2,2-dimethyl-3-trifluoromethyl-
Dissolve 4.3 g of 3-methoxycyclopropanecarboxylic acid in 50 ml of acetone, and add 3-phenoxy-
Add 5.7 g of α-cyanobenzyl bromide.
Add 4 ml of triethylamine under stirring, react at 60-80°C for 3 hours, dissolve in ether, wash the ether solution thoroughly with diluted hydrochloric acid, aqueous sodium bicarbonate, and brine, dry over sulfuric acid, and distill off the ether under reduced pressure. te, 3′-
7.4 g of phenoxy-α-cyanobenzyl 2,2-dimethyl-3-trifluoromethyl-3-methoxycyclopropanecarboxylate was obtained. Synthesis Example 2 2,2-dimethyl-3-fluoromethyl-3-
(2-Methyl-3-bromoallylthio)cyclopropanecarboxylic acid 6.3g and 3-phenoxy-α-
4.8 g of trifluoromethylbenzyl alcohol was dissolved in 50 ml of dry benzene, 6.2 g of dicyclohexylcarbodiimide was added, and the mixture was left sealed overnight. The next day, the reaction was completed by heating under reflux for 4 hours, and after cooling, the precipitated dicyclohexyl urea was filtered off. 100g of the oily substance obtained by concentrating the filtrate
3′-phenoxy-α′-trifluoromethylbenzyl 2,2-
8.8 g of dimethyl-3-fluoromethyl-3-(2-methyl-3-bromoallylthio)cyclopropanecarboxylate was obtained. Synthesis Example 3 2,2-dimethyl-3-trifluoromethyl-
Sodium salt of 3-(2-chloro-4-trifluoromethylanilino)cyclopropanecarboxylic acid
8.0g and 4.5g of 3-phenoxybenzyl chloride
was dissolved in 50 ml of benzene, reacted under reflux for 3 hours in a nitrogen stream, cooled the reaction solution, filtered out the precipitated salt, washed thoroughly with brine, dried over sulfur salt, and removed the benzene under reduced pressure. Distill to give 3'-phenoxybenzyl 2,2-dimethyl-3-trifluoromethyl-3-(2-chloro-4-trifluoromethylanilino)cyclopropanecarboxylate.
9.6g was obtained. Synthesis Example 4 6.3 g of 2,2-dimethyl-3-bromomethyl-3-cyclohexyloxycyclopropanecarboxylic acid chloride was dissolved in 15 ml of dry benzene, and 4.5 g of 3-phenoxy-α-cyanobenzyl alcohol was dissolved in 20 ml of dry benzene. When 3 ml of dry pyridine is added as a condensation aid, pyridine hydrochloride is precipitated. After sealing the cap and leaving it overnight at room temperature, after separating the crystals of pyridine hydrochloride, the benzene solution was dried with sulfuric acid, and the benzene was distilled off under reduced pressure to produce 3'-phenoxy-α'-cyanobenzyl 2,2- Dimethyl-3bromomethyl-
8.4 g of 3-cyclohexyloxycyclopropane carboxylate was obtained. Synthesis Example 5 6.1 g of methyl ester of 2,2-dimethyl-3-fluorochloromethyl-3-bromomethoxycyclopropanecarboxylic acid and 4.2 g of 3-phenoxybenzyl alcohol are heated 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, 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 is then cooled and
Dissolve in ether, wash the ether solution with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dry with sulfuric acid, and distill off the ether under reduced pressure to obtain 3'-phenoxybenzyl 2,2.
-dimethyl-3-fluorochloromethyl-3-bromomethoxycyclopropanecarboxylate
8.1g was obtained. Synthesis Example 6 2,2-dimethyl-3-fluoromethyl-3-
Methylthiocyclopropanecarboxylic anhydride 7.4
g and 4.5 g of 3-phenoxy-α-cyanobenzyl alcohol were 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 and extracted three times with 20 ml of ether. Combine the ether layers and add 5% sodium hydroxide aqueous solution 20
ml was used to remove by-product carboxylic acid. The ether layer was further washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over sulfuric acid, and the ether was removed under reduced pressure to obtain a crude ester, which was injected into activated alumina 20.
3′-phenoxy-α′-
6.5 g of cyanobenzyl 2,2-dimethyl-3-fluoromethyl-3-methylthiocyclopropanecarboxylate was obtained. Synthesis Example 7 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 100ml of 2-dimethoxyethane and add d-
Add 13.0 g of ethyl ester of cis,trans-2,2-dimethyl-3-trifluoromethyl-3-ethoxycyclopropanecarboxylic 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 sulfuric acid, distilled off the ether, and then distilled to give d-trans-2,2-dimethyl-3-trifluoromethyl-3-ethoxycyclopropanecarboxylic acid. Ethyl ester of acid (boiling point 120-125℃/30mmHg fraction)
9.6g was obtained. Add 5.2 g of this ethyl ester to 20 ml of acetic acid and 35%
4.7 g of the obtained carboxylic acid was hydrolyzed in 20 ml of an aqueous solution of hydrochloric acid, and 4.5 g of 3-phenoxy-α-cyanobenzyl alcohol was added according to the method of Synthesis Example 2.
3′-phenoxy-α′-cyanobenzyl d-trans-2,2-dimethyl-3-
7.3 g of trifluoromethyl-3-ethoxycyclopropanecarboxylate (n 20 D 1.5381) were obtained. Synthesis Example 8 d-cis,trans-2,2-dimethyl-3
16.0 g of ethyl ester of trifluoromethyl-3-methoxycyclopropanecarboxylic acid was subjected to repeated precision distillation to obtain ethyl ester of d-trans-2,2-dimethyl-3-trifluoromethyl-3-methoxycyclopropanecarboxylic acid ( Boiling point 75℃/15mmHg) 5.9g and d-cis-2,2-
1.6 g of ethyl ester of dimethyl-3-trifluoromethyl-3-methoxycyclopropanecarboxylic acid (a fraction with a boiling point of 81° C./13 mmHg) was obtained. The latter ethyl ester was treated in the same manner as in Synthesis Example 7 to obtain 3'-phenoxy-α'-cyanobenzyl d-cis-2,2-dimethyl-3-trifluoromethyl-3-methoxycyclopropanecarboxylate (n 20D 1.5306 ) was obtained. Hereinafter, the symbol A will be added after the compound number to indicate that the acid moiety is the d-trans form, and the symbol B will be added to indicate that the acid moiety is the d-cis form. Synthesis Example 9 d-trans-2 obtained in Synthesis Example 7,
4.2 g of 2-dimethyl-3-trifluoromethyl-3-ethoxycyclopropanecarboxylic acid was dissolved in 50 ml of methanol at 50°C, and 5.2 g of -(4-tolyl)-2-phenethylamine was dissolved in methanol.
Add the dissolved solution to 25ml to generate salt. Cool to room temperature, leave for 2 hours, and collect precipitated crystals. This crystal was further re-crystallized with methanol to give 3.2g
Obtain the crystals. After adding 20ml of 10% caustic soda aqueous solution to these crystals and suspending them, by ether extraction -
(4-Tolyl)-2-phenethylamine is recovered. The aqueous layer was acidified with hydrochloric acid, extracted with methylene chloride, and the solvent was distilled off to obtain 1.4 g of -trans-2,2-dimethyl-3-trifluoromethyl-3-ethoxycyclopropanecarboxylic acid. [α] 20 D -45° (Chloroform) Optical purity 93% 1.3 g of this carboxylic acid was reacted with 1.5 g of 3-phenoxy-α-cyanobenzyl bromide according to the method of Synthesis Example 1 to obtain 3'-phenoxy-α. ′-
Cyanobenzyl-trans-2,2-dimethyl-3-trifluoromethyl-3-ethoxycyclopropanecarboxylate 2.0 g (n 20 D
1.5374) was obtained. This compound exhibited approximately twice the insecticidal activity as compared to the d-trans ester. Hereinafter, add the symbol C after the compound number,
Indicates that the acid moiety is -trans form. 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 compound of the present invention (2) 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 of the present invention (4), 10 parts of Solpol SM-200 (trade name of Toho Chemical) and 70 parts of xylol were added and mixed and dissolved with stirring to obtain a 20% emulsion. Reference Example 4 0.4 parts of the present compound (10), 0.1 parts of resmethrin, and 1.5 parts of octachlorodipropyl ether were added to refined kerosene.
After dissolving the solution 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 parts of the compound of the present invention (17) and 0.5 g of BHT were added to a base material for mosquito coils such as pyrethrum extract powder, wood flour, starch powder, etc.99.0
g to obtain a mosquito coil by a known method. Reference Example 6 0.4 g of the compound (26) of the present invention and 1.0 g of MGK-5026 are 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 (34) of the present invention and 97 parts of clay were thoroughly ground and mixed to obtain a 3% powder. Reference example 8 40 parts of the present compound (45), 35 parts of diatomaceous earth, 20 parts of clay
1 part, 3 parts of lauryl sulfonate, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder. Test Example 4 Rice stems (about 12 cm in length) were immersed for 1 minute in a water dilution of an emulsion of the present invention compound and a control compound obtained according to Reference Example 3 at a predetermined concentration. After air-drying, rice stems were placed in test tubes and 10 adult brown planthoppers were released. After 1 day, they were examined for survival and death, and the relative insecticidal efficacy of the compound of the present invention relative to the control compound () was determined from the LC 50 value (50% lethal concentration). The situation is as follows. Control compound ()... Compound of Reference 1 Control compound ()... Compound of Reference 2
【表】【table】
【表】【table】
【表】
試験の結果、シクロプロパン環の３位の位置に
ハロメチル基を有する本発明化合物の有用性が認
められた。
試験例 ５
モモアカ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(1)，(4)，(7)，(12)，(19)，(23)，
(28)，(32)，(37)，(41)，(8)―Ａ，(14)―Ｃ，(29)
―Ｂおよび(42)―Ｂ(44)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 ６
参考例３で得られた乳剤のうち本発明化合物
(2)，(4)，(5)，(10)，(14)，(17)，(24)，(29)，(33)
，
(38)，(42)，(8)―Ａ，(21)―Ｃ，(30)―Ｂおよび(3
９）―A2000倍希釈液にかんらん生葉を薬液中に約
５秒間浸漬し、薬液乾燥後シヤーレに入れヨトウ
ムシの健全幼虫10頭を放飼した。その供試虫の放
飼は生葉浸漬当日、５日後の２回行ない24時間後
の死虫率を求めた。[Table] As a result of the test, the usefulness of the compound of the present invention having a halomethyl group at the 3-position of the cyclopropane ring was confirmed. Test Example 5 5 to 6 of a surface where a large number of green peach aphids appeared
Among the emulsions obtained in Reference Example 3 in the radish field at the leaf stage, compounds of the present invention (1), (4), (7), (12), (19), (23),
(28), (32), (37), (41), (8)-A, (14)-C, (29)
A 1000-fold dilution of each emulsion containing -B and (42)-B(44) with water was applied at a rate of 100/per plate.
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 6 Compound of the present invention among the emulsions obtained in Reference Example 3
(2), (4), (5), (10), (14), (17), (24), (29), (33)
，
(38), (42), (8)-A, (21)-C, (30)-B and (3
9) - A fresh leaf was immersed in the 2000 times diluted solution for about 5 seconds, and after the solution had dried, it was placed in a shear dish and 10 healthy larvae of armyworm were released. The test insects were released twice, once on the day of soaking the fresh leaves, and once 5 days later, and the mortality rate after 24 hours was determined.
【表】【table】
【表】
試験例 ７
針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
(3)，(6)，(9)，(16)，(20)，(26)，(31)，(35)，(3
９），(45)および(48)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 ８
参考例７によつて得られた(1)，(5)，(8)，(12)，(1
８），(22)，(29)，(34)，(36)，(41)、および(47)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 ９
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
れた乳剤の本発明化合物(2)，(4)，(11)，(18)，(2
５），(30)，(34)，(39)，(43)および(48)を水で有
効成分100ppmに希釈した薬液をターンテーブル
上で１鉢あたり10ml散布した。10日後植物上のニ
セナミハダニの調査ではいずれにおいても寄生数
は10頭以下であつた。[Table] Test Example 7 One day before applying the insecticidal active ingredient to needle-planted fava beans, each tree was infested with approximately 200 aphids. Among the hydrating agents obtained by Reference Example 8
(3), (6), (9), (16), (20), (26), (31), (35), (3
9), (45) and (48) diluted 4000 times were sprayed on leaves infested with compressed air at 10 ml/pot, 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 8 (1), (5), (8), (12), (1) obtained by Reference Example 7
8), (22), (29), (34), (36), (41), and (47) were uniformly sprinkled on the bottom of a tall 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. If adult German cockroaches were released into the container in groups of 10, and the cockroaches were left in contact for 30 minutes and then transferred to a new container, more than 80% of the cockroaches could be killed by either powder after three days. Test Example 9 1 for 4 leaves of potted green beans 5 days after sowing
Infested with 10 female adult spider mites per leaf.
Store in a constant temperature room at 27℃. After 6 days, compounds of the present invention (2), (4), (11), (18), (2) of the emulsion obtained in Reference Example 3 were added.
5), (30), (34), (39), (43), and (48) were diluted with water to 100 ppm of active ingredients, and 10 ml of each pot was sprayed on a turntable. After 10 days, the number of parasitized spider mites on the plants was less than 10 in all cases.
Claims (1)
Y2，Y3は水素原子又はハロゲン原子を示す。た
だしY1，Y2，Y3の少なくとも１個はハロゲン原
子を表わす。R1は炭素数が１〜８の低級アルキ
ル基、低級アルケニル基、ハロアルキル基、ハロ
アルケニル基及び一般式（），（），（）で表
わされる基を示す。 【式】【式】 ここにｍは１〜３の整数、ｎは２〜５の整数
を、R3は水素原子、低級アルキル基、低級アル
ケニル基、ハロゲン原子、ハロアルキル基又はア
ルコキシル基を示す。R2は水素原子、シアノ基
又はトリフルオロメチル基を表わす。）で表わさ
れる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、Y1，Y2，Y3は水素原子又はハロゲン
原子を示す。ただしY1，Y2，Y3の少なくとも１
個はハロゲン原子を表わす。R1は炭素数が１〜
８の低級アルキル基、低級アルケニル基、ハロア
ルキル基、ハロアルケニル基及び一般式（），
（），（）で表わされる基を示す。 【式】【式】 ここにｍは１〜３の整数、ｎは２〜５の整数
を、R1は水素原子、低級アルキル基、低級アル
ケニル基、ハロゲン原子、ハロアルキル基又はア
ルコキシル基を示す。R2は水素原子、シアノ基
又はトリフルオロメチル基を表わす。）で表わさ
れる特許請求の範囲第１項記載のカルボン酸エス
テル誘導体及びその光学ならびに幾何異性体。 ３ 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２項記載の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。 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２項記載の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。 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２項記載の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。 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２項記載の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。 ７ 一般式 （式中、ＸはＯ，Ｓ，又はNH基を示し、Y1，
Y2，Y3は水素原子又はハロゲン原子を示す。た
だしY1，Y2，Y3の少なくとも１個はハロゲン原
子を表わす。R1は炭素数が１〜８の低級アルキ
ル基、低級アルケニル基、ハロアルキル基、ハロ
アルケニル基及び一般式（），（），（）で表
わされる基を示す。 【式】【式】 ここにｍは１〜３の整数、ｎは２〜５の整数
を、R3は水素原子、低級アルキル基、低級アル
ケニル基、ハロゲン原子、ハロアルキル基又はア
ルコキシル基を示す。）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 （ここにR2は水素原子、シアノ基又はトリフ
ルオロメチル基を示す。）で表わされるアルコー
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、Ｘ，Y1，Y2，Y3，R1，R2は前述と
同じ意味を表わす。）で示されるカルボン酸エス
テル誘導体及びその光学ならびに幾何異性体の製
造法。 ８ 一般式 （式中、ＸはＯ，Ｓ，又はNH基を示し、Y1，
Y2，Y3は水素原子又はハロゲン原子を示す。た
だしY1，Y2，Y3の少なくとも１個はハロゲン原
子を表わす。R1は炭素数が１〜８の低級アルキ
ル基、低級アルケニル基、ハロアルキル基、ハロ
アルケニル基及び一般式（），（），（）で表
わされる基を示す。 【式】【式】 ここにｍは１〜３の整数、ｎは２〜５の整数
を、R3は水素原子、低級アルキル基、低級アル
ケニル基、ハロゲン原子、ハロアルキル基又はア
ルコキシル基を示す。R2は水素原子、シアノ基
又はトリフルオロメチル基を表わす。）で表わさ
れる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殺虫
剤。 ９ 式 で示される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
る特許請求の範囲第８項記載の殺虫剤。 １０ 式 で示される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
る特許請求の範囲第８項記載の殺虫剤。 １１ 式 で示される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
る特許請求の範囲第８項記載の殺虫剤。 １２ 式 で示される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
る特許請求の範囲第８項記載の殺虫剤。 １３ 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８項記載
の殺虫剤。[Claims] 1. General formula (In the formula, X represents O, S, or NH group, Y 1 ,
Y 2 and Y 3 represent a hydrogen atom or a halogen atom. However, at least one of Y 1 , Y 2 and Y 3 represents a halogen atom. R 1 represents a lower alkyl group having 1 to 8 carbon atoms, a lower alkenyl group, a haloalkyl group, a haloalkenyl group, and a group represented by the general formula (), (), or (). [Formula] [Formula] Here, m is an integer of 1 to 3, n is an integer of 2 to 5, and R 3 is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a haloalkyl group, or an alkoxyl group. R 2 represents a hydrogen atom, a cyano group or a trifluoromethyl group. ) and its optical and geometric isomers. 2 General formula (In the formula, Y 1 , Y 2 , Y 3 represent hydrogen atoms or halogen atoms. However, at least one of Y 1 , Y 2 , Y 3
Each represents a halogen atom. R 1 has 1 or more carbon atoms
8 lower alkyl group, lower alkenyl group, haloalkyl group, haloalkenyl group and general formula (),
Indicates a group represented by () or (). [Formula] [Formula] Here, m is an integer of 1 to 3, n is an integer of 2 to 5, and R 1 is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a haloalkyl group, or an alkoxyl group. R 2 represents a hydrogen atom, a cyano group or a trifluoromethyl group. ) and its optical and geometric isomers. 3 formulas The carboxylic acid ester derivative and optical and geometrical isomers thereof according to claim 2, which are compounds represented by the following. 4 formula The carboxylic acid ester derivative and optical and geometrical isomers thereof according to claim 2, which are compounds represented by the following. 5 formula The carboxylic acid ester derivative and optical and geometrical isomers thereof according to claim 2, which are compounds represented by the following. 6 formula The carboxylic acid ester derivative and optical and geometrical isomers thereof according to claim 2, which are compounds represented by the following. 7 General formula (In the formula, X represents O, S, or NH group, Y 1 ,
Y 2 and Y 3 represent a hydrogen atom or a halogen atom. However, at least one of Y 1 , Y 2 and Y 3 represents a halogen atom. R 1 represents a lower alkyl group having 1 to 8 carbon atoms, a lower alkenyl group, a haloalkyl group, a haloalkenyl group, and a group represented by the general formula (), (), or (). [Formula] [Formula] Here, m is an integer of 1 to 3, n is an integer of 2 to 5, and R 3 is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a haloalkyl group, or an alkoxyl group. ) or its reactive derivative and the general formula (Here, R 2 represents a hydrogen atom, a cyano group, or a trifluoromethyl group.) A general formula characterized by reacting with an alcohol or a reactive derivative thereof. (Here, X, Y 1 , Y 2 , Y 3 , R 1 , and R 2 have the same meanings as above.) A method for producing a carboxylic acid ester derivative and its optical and geometric isomers. 8 General formula (In the formula, X represents O, S, or NH group, Y 1 ,
Y 2 and Y 3 represent a hydrogen atom or a halogen atom. However, at least one of Y 1 , Y 2 and Y 3 represents a halogen atom. R 1 represents a lower alkyl group having 1 to 8 carbon atoms, a lower alkenyl group, a haloalkyl group, a haloalkenyl group, and a group represented by the general formula (), (), or (). [Formula] [Formula] Here, m is an integer of 1 to 3, n is an integer of 2 to 5, and R 3 is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a haloalkyl group, or an alkoxyl group. R 2 represents a hydrogen atom, a cyano group or a trifluoromethyl group. ) and its optical and geometric isomers. 9 formula 9. The insecticide according to claim 8, which contains a carboxylic acid ester derivative represented by: and its optical and geometrical isomers. 10 formula 9. The insecticide according to claim 8, which contains a carboxylic acid ester derivative represented by: and its optical and geometrical isomers. 11 formula 9. The insecticide according to claim 8, which contains a carboxylic acid ester derivative represented by: and its optical and geometrical isomers. 12 formula 9. The insecticide according to claim 8, which contains a carboxylic acid ester derivative represented by: and its optical and geometrical isomers. 13. The insecticide according to claim 8, which contains a pyrethroid synergist as an adjuvant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12217579A JPS5646843A (en) | 1979-09-23 | 1979-09-23 | Novel carboxylic acid ester derivative, preparation of novel carboxylic acid ester derivative, and insecticide containing novel carboxylic acid ester derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12217579A JPS5646843A (en) | 1979-09-23 | 1979-09-23 | Novel carboxylic acid ester derivative, preparation of novel carboxylic acid ester derivative, and insecticide containing novel carboxylic acid ester derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5646843A JPS5646843A (en) | 1981-04-28 |
| JPS6223740B2 true JPS6223740B2 (en) | 1987-05-25 |
Family
ID=14829422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12217579A Granted JPS5646843A (en) | 1979-09-23 | 1979-09-23 | Novel carboxylic acid ester derivative, preparation of novel carboxylic acid ester derivative, and insecticide containing novel carboxylic acid ester derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5646843A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0242836U (en) * | 1988-09-19 | 1990-03-23 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2515176A1 (en) * | 1981-10-23 | 1983-04-29 | Roussel Uclaf | NOVEL ESTERS OF AROMATIC OR HETEROAROMATIC ALCOHOLS, PROCESS FOR PREPARING THEM AND THEIR APPLICATION TO THE FIGHT AGAINST PESTS |
| JP4747866B2 (en) * | 2006-02-09 | 2011-08-17 | 株式会社デンソー | Temperature sensor mounting structure for high-pressure hydrogen containers |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54100348A (en) * | 1978-01-21 | 1979-08-08 | Yoshio Katsuta | Cyclopropane carboxylic acid ester derivative* its manufacture and insecticide containing it |
| JPS54117443A (en) * | 1978-03-01 | 1979-09-12 | Yoshio Katsuta | Cyclopropane carboxylic acid ester derivative* manufacture thereof and insecticide containing it |
| JPS54130532A (en) * | 1978-03-31 | 1979-10-09 | 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 |
| JPS5620547A (en) * | 1979-07-31 | 1981-02-26 | Yoshio Katsuta | Cyclopropanecarboxylic ester derivative, its preparation, and insecticide comprising the same |
-
1979
- 1979-09-23 JP JP12217579A patent/JPS5646843A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54100348A (en) * | 1978-01-21 | 1979-08-08 | Yoshio Katsuta | Cyclopropane carboxylic acid ester derivative* its manufacture and insecticide containing it |
| JPS54117443A (en) * | 1978-03-01 | 1979-09-12 | Yoshio Katsuta | Cyclopropane carboxylic acid ester derivative* manufacture thereof and insecticide containing it |
| JPS54130532A (en) * | 1978-03-31 | 1979-10-09 | 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 |
| JPS5620547A (en) * | 1979-07-31 | 1981-02-26 | Yoshio Katsuta | Cyclopropanecarboxylic ester derivative, its preparation, and insecticide comprising the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0242836U (en) * | 1988-09-19 | 1990-03-23 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5646843A (en) | 1981-04-28 |
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