JPS6121615B2 - - Google Patents
Info
- Publication number
- JPS6121615B2 JPS6121615B2 JP13037181A JP13037181A JPS6121615B2 JP S6121615 B2 JPS6121615 B2 JP S6121615B2 JP 13037181 A JP13037181 A JP 13037181A JP 13037181 A JP13037181 A JP 13037181A JP S6121615 B2 JPS6121615 B2 JP S6121615B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- ethoxyphenyl
- water
- compound
- 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 46
- 239000002917 insecticide Substances 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000000895 acaricidal effect Effects 0.000 claims description 12
- 239000000642 acaricide Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- YREQHYQNNWYQCJ-UHFFFAOYSA-N etofenprox Chemical compound C1=CC(OCC)=CC=C1C(C)(C)COCC1=CC=CC(OC=2C=CC=CC=2)=C1 YREQHYQNNWYQCJ-UHFFFAOYSA-N 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 238000012360 testing method Methods 0.000 description 31
- -1 3-phenoxybenzyl Chemical group 0.000 description 27
- 239000000203 mixture Substances 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 241000607479 Yersinia pestis Species 0.000 description 22
- 241000251468 Actinopterygii Species 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 241000238631 Hexapoda Species 0.000 description 13
- 238000009472 formulation Methods 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000003814 drug Substances 0.000 description 11
- 229940079593 drug Drugs 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 241001414720 Cicadellidae Species 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000749 insecticidal effect Effects 0.000 description 9
- 231100000053 low toxicity Toxicity 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 231100000419 toxicity Toxicity 0.000 description 9
- 230000001988 toxicity Effects 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 150000004820 halides Chemical class 0.000 description 7
- 241000255925 Diptera Species 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 241000256248 Spodoptera Species 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 238000006266 etherification reaction Methods 0.000 description 6
- 239000000284 extract Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 240000007594 Oryza sativa Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 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 5
- 239000000839 emulsion Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 241000238657 Blattella germanica Species 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 241000721621 Myzus persicae Species 0.000 description 4
- 241000500437 Plutella xylostella Species 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 241001454293 Tetranychus urticae Species 0.000 description 4
- 239000003905 agrochemical Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 231100000820 toxicity test Toxicity 0.000 description 4
- LDOMMNCPNTZTQW-UHFFFAOYSA-N 2-(4-ethoxyphenyl)-2-methylpropanoic acid Chemical compound CCOC1=CC=C(C(C)(C)C(O)=O)C=C1 LDOMMNCPNTZTQW-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 241000084475 Delia antiqua Species 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- 241000699670 Mus sp. Species 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 241000254234 Xyeloidea Species 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 3
- 230000037396 body weight Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000012280 lithium aluminium hydride Substances 0.000 description 3
- VOEYXMAFNDNNED-UHFFFAOYSA-N metolcarb Chemical compound CNC(=O)OC1=CC=CC(C)=C1 VOEYXMAFNDNNED-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 150000003459 sulfonic acid esters Chemical class 0.000 description 3
- 239000012485 toluene extract Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- UJUNUASMYSTBSK-UHFFFAOYSA-N 1-(bromomethyl)-3-phenoxybenzene Chemical compound BrCC1=CC=CC(OC=2C=CC=CC=2)=C1 UJUNUASMYSTBSK-UHFFFAOYSA-N 0.000 description 2
- YDUREWJTLPKYER-UHFFFAOYSA-N 1-ethoxy-4-[1-[1-(4-ethoxyphenyl)-2-methylpropoxy]-2-methylpropyl]benzene Chemical compound C(C)OC1=CC=C(C=C1)C(C(C)C)OC(C(C)C)C1=CC=C(C=C1)OCC YDUREWJTLPKYER-UHFFFAOYSA-N 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- PKWJQJIGITWZKH-UHFFFAOYSA-N 2-(4-ethoxyphenyl)propanenitrile Chemical compound CCOC1=CC=C(C(C)C#N)C=C1 PKWJQJIGITWZKH-UHFFFAOYSA-N 0.000 description 2
- 241000256118 Aedes aegypti Species 0.000 description 2
- 241000218475 Agrotis segetum Species 0.000 description 2
- 241000519879 Anomala cuprea Species 0.000 description 2
- 241001177135 Anthrenus verbasci Species 0.000 description 2
- 241001600408 Aphis gossypii Species 0.000 description 2
- 241000459392 Apoderus erythrogaster Species 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 241000776777 Cacopsylla mali Species 0.000 description 2
- 241001182720 Cacopsylla pyrisuga Species 0.000 description 2
- 241000426497 Chilo suppressalis Species 0.000 description 2
- 241001374606 Chlorops oryzae Species 0.000 description 2
- 241001498622 Cixius wagneri Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 241000490513 Ctenocephalides canis Species 0.000 description 2
- 241000252233 Cyprinus carpio Species 0.000 description 2
- 241001609607 Delia platura Species 0.000 description 2
- 241001205778 Dialeurodes citri Species 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 241001486250 Etiella zinckenella Species 0.000 description 2
- 241000785585 Gryllotalpa africana Species 0.000 description 2
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- 241001477931 Mythimna unipuncta Species 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
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- 239000000073 carbamate insecticide Substances 0.000 description 2
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
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- PUPKPAZSFZOLOR-UHFFFAOYSA-N n,n-dimethylformamide;toluene Chemical compound CN(C)C=O.CC1=CC=CC=C1 PUPKPAZSFZOLOR-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 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 2
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- 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 2
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- 238000005406 washing Methods 0.000 description 2
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- 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 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
- KEUPLGRNURQXAR-UHFFFAOYSA-N (4-chlorophenyl) acetate Chemical compound CC(=O)OC1=CC=C(Cl)C=C1 KEUPLGRNURQXAR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GNEPLYVYORHREW-UHFFFAOYSA-N 1,1,3,3,6-pentamethyl-7-nitro-2h-inden-5-amine Chemical compound CC1=C(N)C=C2C(C)(C)CC(C)(C)C2=C1[N+]([O-])=O GNEPLYVYORHREW-UHFFFAOYSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- RRRWFPNXBFBFDT-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)pentan-2-ol 5-[2-(2-butoxyethoxy)ethoxymethyl]-6-propyl-1,3-benzodioxole Chemical compound CCCC(O)CC1=CC=C2OCOC2=C1.C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 RRRWFPNXBFBFDT-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
- XBFQMHMBSZKUSY-UHFFFAOYSA-N 1-ethoxy-4-[1-[2-(4-ethoxyphenyl)-2-methylpropoxy]-2-methylpropan-2-yl]benzene Chemical compound C1=CC(OCC)=CC=C1C(C)(C)COCC(C)(C)C1=CC=C(OCC)C=C1 XBFQMHMBSZKUSY-UHFFFAOYSA-N 0.000 description 1
- 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 1
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Landscapes
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Description
本発明は新規な2−アリールプロピルエーテ
ル、その製造法および該化合物を含有する低毒性
の殺虫、殺ダニ剤に関するものである。
さらに詳しくは、本発明の1つは3−フエノキ
シベンジル 2−(4−エトキシフエニル)−2−
メチルプロピルエーテルに関する。
本発明の1つは一般式〔〕で表わされる化合
物を一般式〔〕
〔式中、基Aおよび基Bはその一方の基がハロゲ
ン原子を表わし、他方の基が−O−M基(式中、
Mは水素原子またはアルカリあるいはアルカリ土
類金属原子を表わす)を表わすか、または共にヒ
ドロキシル基を表わす〕で表わされる化合物と反
応させることを特徴とする3−フエノキシベンジ
ル 2−(4−エトキシフエニル)−2−メチルプ
ロピルエーテルの製造法に関する。
本発明の1つは3−フエノキシベンジル 2−
(4−エトキシフエニル)−2−メチルプロピルエ
ーテルを含有することを特徴とする殺虫、殺ダニ
剤に関する。
殺虫剤が農業生産性向上に果した役割は極めて
高く、有機合成農薬の登場は人類の食糧事情を一
変させ、虫により媒介される伝染病を予防するな
どの面で多大の恩恵をもたらした。
しかしながら、有機塩素系殺虫剤DDTやBHC
は使用後長く環境中に残留してしまうなどの点で
その使用が制限されており、またこれらに変つて
登場した有機リン系殺虫剤やカーバメート系殺虫
剤が広範囲に使用されているが、種々の害虫でこ
れらの殺虫剤に対する抵抗性問題が生じてきてい
る。また、一部地域では難防除害虫の出現を見て
おり、今後、ますます薬剤抵抗性害虫等の問題は
広がり深刻化していくことと思われる。
今日まで人類がその文明を礎き上げ、また今後
さらに発展させしめる上で食糧の充分な供給を続
けていこうとするとき、よりすぐれた殺虫活性を
もつた薬剤の出現が急がれているのである。
近年、こうした背景の中に合成ピレスロイド系
殺虫剤が脚光をあびてきた。これはその優れた殺
虫力とともに有機リン剤あるいはカーバメート剤
抵抗性の害虫に対して卓効を示し、人畜に対して
比較的低毒性である点が特長である。しかし、こ
の合成ピレスロイド系殺虫剤の致命的な欠点は極
めて魚毒性が高く、その使用範囲が限定されるこ
とである。そしてまた、従来開発されてきた殺虫
剤に比べ高価なことである。
今後望まれる農薬は上に述べてきたような欠点
を解決するようなものでなければならない。つま
り安全性が高く、残留することなく、すみやかに
分解し環境を汚染しない、現在問題となつている
薬剤抵抵抗性をもつた難防除害虫に高い活性をも
つていること、そして安価に製造できることが望
まれるのである。
本発明者らは低毒性で、低魚毒性であり、かつ
殺虫力の強い、殺虫、殺ダニ剤の開発を企画し、
研究に鋭意努めた結果、3−フエノキシベンジル
2−(4−エトキシフエニル)−2−メチルプロ
ピルエーテルが、極めて高い殺虫、殺ダニ活性を
有し、速効性および残効性においてすぐれた特徴
を有することを見出し、人畜に対しては勿論のこ
と、魚類に対しても比較的毒性が低く、比較的安
価に実用に供し得ることを見出し本発明を完成し
た。
本発明化合物は従来の農薬とは異なる活性構造
を有し、衛生害虫であるハエ、蚊、ゴキブリ等の
ほか、ウンカ類、ヨコバイ類、ヨトウ類、コナ
ガ、ハマキ類、アブラムシ類、メイ虫類、ハダニ
類等の農業害虫、特にツマグロヨコバイに卓効を
示し、コナダニ、ノシメコクガ、コクゾウ等の貯
穀害虫、動物寄生性のシラミ、ダニの防除にもき
わめて有効であり、その他の害虫にも有効であ
る。さらに本発明化合物は速効性、残効性にすぐ
れ、フラツシング効果も有する。本発明化合物は
単に害虫をノツクダウンさせ、死にいたらせるば
かりでなく、忌避性を有し、害虫をホストから、
忌避させる効果も有しており、合成ピレスロイド
の代表の一つでありフエンバレレートのようなナ
ス科植物に対する薬害もないという大きな利点を
有する。加えて哺乳動物に対する毒性が低い、本
発明化合物は低濃度で殺虫効力が高いので魚類に
対しても実質的に安全性が高い状態で使用でき、
水田における害虫駆除にも好適であるばかりでな
く、蚊、ブユ等の幼虫等の水性害虫駆除あるいは
湖、沼、池、河川などの点在する広い地域での航
空機散布による害虫駆除に供する場合にも、そこ
に生息する魚類を殺滅する危険なく用いることが
できる。
したがつて本発明化合物を含有する殺虫、殺ダ
ニ剤はその適用場面は極めて広範で、農園芸害
虫、貯穀害虫、衛生害虫、家屋害虫、森林害虫、
水生害虫などの殺虫、殺ダニ剤として活性が高
く、きわめて安全で、かつ安価に各種剤型で実用
に供し得るものである。
本発明の3−フエノキシベンジル 2−(4−
エトキシフエニル)−2−メチルプロピルエーテ
ルは新規化合物である。
本発明の製造方法をさらに詳しく述べると次の
とおりである。すなわち、一般式〔〕〔式中、
基Aが−O−H基を表わす場合〕のアルコールと
一般式〔〕(式中、基Bがハロゲン原子を表わ
す場合)のハライドを反応させる場合は脱酸剤と
しての塩基の存在下、適当な溶媒中、室温ないし
加熱下、反応させて目的の3−フエノキシベンジ
ル 2−(4−エトキシフエニル)−2−メチルプ
ロピルエーテルを得ることができる。ここに云う
塩基とは水酸化アルカリ金属、水酸化アルカリ土
類金属、水素化アルカリ金属、アルカリ金属アル
コラート、アルカリ金属酸化物、アルカリ金属炭
酸塩、ナトリウムアミド、トリエチルアミンなど
をさし、また脱酸剤として酸化銀を使用すること
もできる。また溶媒としては水をはじめ、ベンゼ
ン、トルエン、キシレン等の芳香族炭化水素、ヘ
キサン、ヘプタン、石油ベンゼン等の脂肪族炭化
水素、クロロホルム、ジクロロメタン等のハロゲ
ン化炭化水素、ジメチルホルムアミド、ジメチル
スルホキシド等の非プロトン供与性極性溶媒、メ
タノール、エタノール等の低級アルコール類、ジ
イソプロピルエーテル、ジエチルエーテル、1・
2−ジメトキシエタン、テトラヒドロフラン、ジ
オキサン等のエーテル類、アセトニトリル、プロ
ピオニトリルなどのニトリル類、アセトン、ジイ
ソプロピルケトンなどのケトン類等を用いること
ができる。さらに触媒として、テトラ−n−ブチ
ルアンモニウムブロマイドまたはトリエチルベン
ジルアンモニウムブロマイド等で代表される相間
移動触媒を用いることによつても目的とする3−
フエノキシベンジル 2−(4−エトキシフエニ
ル)−2−メチルプロピルエーテルを好収率で得
ることができる。
一般式〔〕〔式中、基Aが−O−M基(式
中、Mが水素原子でない場合)を表わす場合〕の
アルコラートと一般式〔〕〔式中、基Bはハロ
ゲン原子を表わす〕のハライドとを反応させる場
合は前記溶媒中、室温ないし加熱下、反応を行な
い、3−フエノキシベンジル 2−(4−エトキ
シフエニル)−2−メチルプロピルエーテルを得
ることができる。反応性の悪い場合はヨウ化カリ
ウム、ヨウ化銅などを触媒量加えることも好適で
ある。
一般式〔〕〔式中、基Aがハロゲン原子を表
わす場合〕のハライドと一般式〔〕〔式中、基
Bが−O−M基(式中、Mは前記の意味を表わ
す)である場合〕のアルコールまたはアルコラー
トと反応させる場合は前記同様に実施することが
できる。特に一般式〔〕〔式中、基Aがハロゲ
ン原子を表わす場合〕のハライドと一般式〔〕
(式中、基Bは−O−Hを表わす場合)のアルコ
ールを反応させる場合は、非プロトン性極性溶
媒、好ましくはジメチルスルホキシドまたはスル
ホランの存在下、脱酸剤としての塩基の存在下、
加熱下、反応させて目的の3−フエノキシベンジ
ル 2−(4−エトキシフエニル)−2−メチルプ
ロピルエーテルを好収率で得ることができる。
一般式〔〕〔式中、基Aがヒドロキシル基で
ある場合〕のアルコールと一般式〔〕〔式中、
基Bがヒドロキシル基である場合〕のアルコール
とを反応させる場合は触媒の存在下に脱水反応を
行い3−フエノキシベンジル 2−(4−エトキ
シフエニル)−2−メチルプロピルエーテルを得
ることができる。触媒としては硫酸、塩酸、芳香
族スルホン酸およびスルホン酸クロリド、三フツ
化ホウ素、塩化アルミニウムなどの酸触媒を用い
ることができる。ヨウ素、固体酸触媒(アルミナ
−酸化チタンなど)、ジメチルスルホキシド、ア
ルミナ、スルフアミド、イオン交換樹脂なども脱
水触媒として使用できる。必要ならばベンゼン、
トルエンなどの水と共沸する不活性溶媒中で還流
下に生成水を除去しながら反応を行うのが好適で
ある。
また、一般式〔〕〔式中、基Aがヒドロキシ
ル基を表わす場合〕のアルコールを脱水剤の存在
下、必要ならば触媒の存在下、一般式〔〕〔式
中、基Bがヒドロキシル基を表わす場合〕のアル
コールとを反応させて3−フエノキシベンジル
2−(4−エトキシフエニル)−2−メチルプロピ
ルエーテルを得ることもできる。脱水剤として
は、例えば、N・N−置換カルボジイミド特に
N・N−ジシクロヘキシルカルボジイミドが好ま
しく、触媒としては、例えば、塩化第一銅が好ま
しい。反応は適当な不活性溶媒または希釈剤の存
在下、室温または加熱下に実施される。適当な溶
媒または希釈剤としては、例えば、1・2−ジメ
トキシエタン、ジオキサン、テトラヒドロフラン
などのエーテル類、ジメチルホルムアミド、ヘキ
サメチルホスホン酸トリアミド、ジメチルスルホ
キシドなどの非プロトン供与性極性溶媒、アセト
ン、メチルエチルケトン、シクロヘキサノンなど
のケトン類等が挙げられる。
その他、3−フエノキシベンジル 2−(4−
エトキシフエニル)−2−メチルプロピルエーテ
ルの製造法としては、一般式〔〕〔式中、基A
がヒドロキシル基を表わす場合〕のアルコールの
金属アルコラートあるいはスルホン酸エステルと
一般式〔〕〔式中、基Bがヒドロキシル基であ
る場合〕のアルコールを反応させる方法、一般式
〔〕〔式中、基Aがヒドロキシル基である場合〕
のアルコールと一般式〔〕〔式中、基Bがヒド
ロキシル基である場合〕のアルコールの金属アル
コラートまたはスルホン酸エステルを反応させる
方法等があるが収率的には不利である。
一般式〔〕で表わされる出発物質は文献に記
載された公知方法と類似の方法で製造される。す
なわち、一般式〔〕〔式中、基Aがヒドロキシ
ル基を表わす場合〕で表わされるアルコールは、
例えば、対応する4−エトキシフエニルアセトニ
トリルをハロゲン化メチルでアルキル化、次いで
得られたニトリルを加水分解して対応するカルボ
ン酸に変換し、該カルボン酸を還元して得られ
る。また4−エトキシベンゼンにメタリルハライ
ドを付加して得られるハロゲン化物〔一般式
〔〕中、基Aがハロゲン原子を表わす場合〕を
アルコールに変換して得る。
以下に製造経路例を図式に示す。
参考文献Roczniki Chem.、39(9)、1223
(1965)(Pol)〔Chemical Abstract 64、
12595、h(1966)〕
以下(1)の経路に従つて製造する。
〔式〔〕中、基Aがハロゲン原子〕
参考文献Chem、Ber.、94、2609(1961)
参考文献J.Am.Chem.Soc.、65、1469(1943)
また、一般式〔〕〔式中、基Aがヒドロキシ
ル基である場合〕のアルコールはHelvetica
Chimica Acta、54、868(1971)記載の方法によ
つても製造することができる。
一般式〔〕〔式中、基Aが−O−M基を表わ
し、Mが水素原子でない場合〕の金属アルコラー
トは常法により、例えば、水素化ナトリウムのよ
うな金属水素化物と一般式〔〕〔式中、基Aが
−O−M基を表わし、Mが水素原子である場合〕
のアルコールを反応させることにより容易に得る
ことができる。
一般式〔〕〔式中、基Bがヒドロキシル基で
ある場合〕のアルコールは合成ピレスロイドのア
ルコール成分として公知である。
次に本発明の3−フエノキシベンジル 2−
(4−エトキシフエニル)−2−メチルプロピルエ
ーテルの製造法について以下合成実施例を挙げて
さらに詳細に説明する。
合成実施例 1
(エーテル化法A)
乾燥アセトニトリル20mlに水素化ナトリウム
(60%in oil)0.90gを加え、次いで2−(4−エ
トキシフエニル)−2−メチルプロピルアルコー
ル3.0g/10ml乾燥アセトニトリル溶液を50℃で
滴下した。
30分間加熱還流したのち、3−フエノキシベン
ジルブロマイド4.8g/10ml乾燥アセトニトリル
溶液を10分間で滴下し、さらに、1時間加熱還流
した。室温まで冷却後、水に注ぎ込みトルエンに
て抽出した。トルエン抽出液を飽和食塩水にて洗
浄後、無水硫酸ナトリウムで乾燥した。減圧下に
トルエンを留去して得られた粗エーテルをシリカ
ゲル150gのカラムクロマトグラフイー〔展開溶
媒:ベンゼン:n−ヘキサン(2:3)〕により
精製し3−フエノキシベンジル 2−(4−エト
キシフエニル)−2−メチルプロピルエーテル4.2
gを得た。
n20.2 D1.5732
νfilm nax1595、1525、1495、1260、1225、1195
、
1110、1055、830、700cm-1
δCCl4 TMS(ppm)1.29(s.6H)、1.37(t、J
=6.9
Hz、3H)、3.32(s、2H)、3.93(q、J=6.9
Hz、2H)、4.38(s、2H)、6.6〜7.35(m、
13H)
元素分析結果
C25H28O3
計算値(%)C;79.76、H;7.50
実測値(%)C;79.97、H;7.34
上記で得た3−フエノキシベンジル 2−(4
−エトキシフエニル)−2−メチルプロピルエー
テルを室温で長期間放置したら固化した。融点は
35〜38℃であつた。
これをメタノールでスラツジし、濾過、洗浄、
乾燥し、さらにn−ヘキサンでスラツジし、濾
過、洗浄、乾燥すると融点36.4〜38℃の白色結晶
が得られた。
合成実施例 2
(エーテル化法B)
トルエン20mlに水素化ナトリウム(60%in
oil)0.63gを加えた後、これに2−(4−エトキ
シフエニル)−2−メチルプロピルアルコール2.0
g/25%DMF−トルエン10ml溶液を加熱還流下
15分間で滴下した。このまま10分間撹拌を続けた
のち、3−フエノキシベンジルブロマイド3.3
g/25%DMF−トルエン10ml溶液を20分間で滴
下した。さらに、1時間加熱還流したのち、反応
混合物を室温まで冷却し水に注ぎ込んだ。
トルエンにて抽出し、トルエン抽出液を水洗し
たのち、無水硫酸ナトリウムにて乾燥した。減圧
下にトルエンを留去して得られた油状物をカラム
クロマトグラフイー〔シリカゲル100ml、ベンゼ
ン:n−ヘキサン(2:3)〕により精製し目的
とした精エーテル3.0gを得た。
合成実施例 3
(エーテル化法C)
50%NaOH水溶液30g、2−(4−エトキシフ
エニル)−2メチルプロピルアルコール6.3g、3
−フエノキシベンジルクロライド7.6gおよびテ
トラブチルアンモニウムブロマイド1.1gを加
え、80℃にて1時間加熱撹拌した。反応混合物を
室温まで冷却後、水を加え、トルエンにて抽出し
水洗した。トルエン抽出液を無水硫酸ナトリウム
にて乾燥後、減圧下トルエンを留去し得られた粗
エーテルをカラムクロマトグラフイー〔シリカゲ
ル展開溶媒:ベンゼン:n−ヘキサン(2:
3)〕により精製し目的としたエーテル10.0gを
得た。
合成実施例 4
(エーテル化法D)
トルエン50mlにp−トルエンスルホン酸0.50
g、3−フエノキシベンジルアルコール2.5g、
2−(4−エトキシフエニル)−2−メチルプロピ
ルアルコール2.5gを加え、6時間加熱還流した
(生成した水は水分離器により系外に除去した)。
室温まで冷却した後、水を加え、トルエン層を分
離し、水洗、乾燥した。減圧下にトルエンを留去
して得られた粗エーテルをカラムクロマトグラフ
イー〔シリカゲル、展開溶媒:ベンゼン:n−ヘ
キサン(2:3)〕により精製し目的としたエー
テルを得た。
合成実施例 5
(エーテル化法E)
2−(4−エトキシフエニル)−2−メチルプロ
ピルアルコール1.8g、3−フエノキシベンジル
クロライド2.4g、50%NaOH20g、トリエチル
ベンジルアンモニウムブロマイド0.3gの混合液
を50℃で2時間撹拌した。反応混合物を室温まで
冷却後、水を加え、ベンゼンにて抽出した。ベン
ゼン抽出液を希塩酸で、洗つた後、水洗し乾燥し
た。減圧下ベンゼンを留去して得られた粗エーテ
ルをカラムクロマトグラフイー(シリカゲル80
g、展開溶媒:ベンゼン−n−ヘキサン、2:
3)により精製し目的としたエーテル2.8gを得
た。
合成実施例 6
(エーテル化法F)
4−エトキシネオフイルクロライド8.9g、3
−フエノキシベンジルアルコール8.5g、45%カ
セイソーダ3.9gおよびジメチルスルホキサイド
48gを140℃で3時間加熱撹拌した。45%カセイ
ソーダ1.8gを追加し、さらに4時間同温度で反
応した。反応液を室温まで冷却後水に注ぎ込み、
ベンゼンにて抽出し、ベンゼン抽出液を水洗した
のち、乾燥した。減圧下にベンゼンを留去して得
られた粗エーテルをカラムクロマトグラフイー
(シリカゲル300g、展開溶媒:ベンゼン:n−ヘ
キサン2:3)により分離精製し、目的とするエ
ーテル10.3gを得た。
以下に出発原料〔〕のアルコールおよびハラ
イドの製造法について合成参考例により詳細に説
明する。
合成参考例 1
2−(4−エトキシフエニル)−2−メチルプロ
ピルアルコール(4−エトキシネオフイルアル
コール)の合成
次の順序に従い合成した。
(1) 2−(4−エトキシフエニル)−2メチルプロ
ピオニトリルの合成
4−エトキシベンジルニトリル280g、トリ
エチルベンジルアンモニウムブロマイド80g、
水酸化カリウム750g、水750gを2セパラブ
ルフラスコに装入し、撹拌を開始すると内温が
約85〜90゜に上昇した。これにヨウ化メチル
180ml(約410g)を1.5時間で滴下した。次い
で80〜90℃にて更に7時間撹拌を継続した。反
応液を室温迄冷却後、ベンゼン500mlで抽出
し、ベンゼン抽出液を希塩酸、水の順で洗つた
後、無水硫酸ナトリウムで乾燥した。減圧下に
ベンゼンを留去し、粗2−(4−エトキシフエ
ニル)プロピオニトリル311gを得た。
上記で得た粗2−(4−エトキシフエニル)
プロピオニトリル311g、トリエチルベンジル
アンモニウムブロマイド110g、水酸化カリウ
ム800g、水800gを2セパラブルフラスコに
装入撹拌した。次いで85〜90℃にてヨウ化メチ
ル180ml(約410g)を1.5時間にて滴下した。
滴下終了後3.5時間経過した後、水酸化カリウ
ム300gを追加装入した。更に5時間経過後ヨ
ウ化メチル50ml(約114g)を追加した。更に
同温度で2時間反応した。以下2−(4−エト
キシフエニル)プロピオニトリル合成の際と同
様に処理し粗2−(4−エトキシフエニル)−2
−メチルプロピオニトリル340gを得た。減圧
下に蒸留精製し、目的物を275g得た。(111〜
112℃/0.60〜0.55mmHg)。
(2) 2−(4−エトキシフエニル)−2−メチルプ
ロピオン酸の合成
2−(4−エトキシフエニル)−2−メチルプ
ロプオニトリル275g、水酸化カリウム850g、
水700ml、エチレングリコール2000mlを撹拌し
ながら121〜126℃で還流下8時間反応した。反
応混合物を室温迄冷却後、2〜3の水中に注
ぎ込み、ベンゼンにて中性部を除去した。水層
を濃塩酸にてPHを2以下とし、ベンゼンで抽出
した。ベンゼン抽出液は水洗後、無水硫酸ナト
リウムで乾燥し、ベンゼンを留去後、n−ヘキ
サンから再結晶した。m.p.80.5〜82.5℃の2−
(4−エトキシフエニル)−2−メチルプロピオ
ン酸240gを得た。
(3) 2−(4−エトキシフエニル)−2−メチルプ
ロピオン酸エチルの合成
(2)で得たカルボン酸240gをベンゼン400ml、
エタノール200mlに溶解後、濃硫酸25mlを加え
還流下ベンゼン−エタノール−水の共沸混合物
を系外に除去する。この時ベンゼン400ml、エ
タノール200mlの混合溶液を反応器に6時間を
要して滴下した。反応物を室温まで、冷却後水
を加え、ベンゼン層を分離した。得られたベン
ゼン溶液を中性となるまで水洗した後乾燥し
た。減圧下にベンゼンを留去し、目的のエステ
ル264gを得た。
(4) 2−(4−エトキシフエニル)−2−メチルプ
ロピルアルコールの合成
乾燥テトラヒドロフラン400mlに水素化リチ
ウムアルミニウム35gを加えた系に撹拌下に(3)
で得たエステル264gを温度を30℃以下に保ち
ながら滴下した。
エステルの滴下終了後30分間還流した。次いで
過剰の水素化リチウムアルミニウムを分解するた
め、氷冷下で酢酸エチル30mlを滴下した。発熱お
よび発泡が認められなくなつた所で水を加え、完
全に水素化リチウムアルミニウムを分解した。生
成した沈殿物を減圧過で除去した後、テトラヒ
ドロフランを減圧下留去した。ベンゼン300mlで
抽出し、抽出液を水洗後乾燥した。減圧下ベンゼ
ンを留去し、2−(4−エトキシフエニル)−2−
メチルプロピルアルコール213gを得た。
m.p.;42.0〜43.5℃
νKBr nax;3400、1620、1520、1255、1195、1050
、
830cm-1
合成参考例 2
4−エトキシネオフイルクロライドの合成
撹拌機、ジムロート、温度計および滴下斗付
500mlフラスコに濃硫酸120gを加えた後、5℃を
保ちながらフエネトール200gを滴下した。0℃
〜10℃を保ちながらメタリルクロライド90g/フ
エネトール165g混合溶液を10時間で滴下した。
次いで25℃に15時間保つた後、氷水にそそぎ込ん
だ。有機層を分離後、希水酸化ナトリウム水溶
液、水の順に充分洗滌した。無水硫酸ナトリウム
で乾燥後減圧蒸留(100cm充てん塔)にて粗4−
エトキシネオフイルクロライド16gを得た(114
℃/2.0mmHg〜116.5℃/1.7mmHg)。
δCCl4(ppm)1.39(s、6H)、1.3〜1.6(m、
3H)、3.51(s、2H)、4.05(q、J=6.9Hz、
2H)、4.05(q、J=6.9Hz、2H)、6.6〜7.3
(m、4H)
参考文献;Chem、Ber.、94、2609(1961)
次に本発明の殺虫、殺ダニ剤の適用できる具体
的な害虫名をあげる〔学名−(和名)−英名〕。
1 Hemiptera(半翅目)
Nephotettix cincticeps Uhler(ツマグロヨ
コバイ)Green rice leafhopper
Sogata furcifera Horva′th(セジロウン
カ)White−backed rice planthopper
Nilaparvata lugens Sta゜l(トビイロウン
カ)Brown rice planthopper
Laodelphax striatellus Falle′n(ヒメトビ
ウンカ)Small brown planthopper
Eurydema rugosum Motschulsky(ナガ
メ)Cabbage bug
Eysarcoris parvus Uhler(トゲシラホシカ
メムシ)Whitespotted spined bug
Halyomorpha mista Uhler(クサギカメム
シ)Brown−marmorated stink bug
Lagynotomus elongatus Dallas(イネカメ
ムシ)Rice stink bug
Nezara viridula Linne′(ミナミアオカメム
シ)Southern green stink bug
Cletus trigonns Thunberg′(ヒメハリカメ
ムシ)Slender rice bug
Stephanitis nashi Esaki et、Takeya(ナ
シグンバイ)Japanese pear lace bug
Stephanitis pyrioides Scott(ツツジグンバ
イ)Azalea lace bug
Psylla pyrisuga Fo¨rster(ナシキジラミ)
Pear sucker
Psylla mali Schmidberger(リンゴキジラ
ミ)Apple sucker
Aleurolobus taonabae Kuwana(ブトウコ
ナジラミ)Grape whitefly
Dialeurodes citri Ashmead(ミカンノコナ
ジラミ)Citrus whitefly
Trialeurodes vaporariorum Westwood(オ
ンシツコナジラミ)Greenhouse whitefly
Aphis gossypii Glover(ワタアブラムシ)
Cotton aphid
Brevicoryne、brassicae Linne′(ダイコン
アブラムシ)Cabbage aphid
Myzus persicae Sulzer(モモアカアブラム
シ)Green peach aphid
Rhopalosiphum maidis Fitch(キビクビレ
アブラムシ)Corn leaf aphid
Icerya purchasi Maskell(イセリヤカイガ
ラムシ)Cottonycushion scale
Planococcus citri Risso(ミカンコナカイガ
ラムシ)citrus mealybug
Unaspis yanonensis Kuwana(ヤノネカイ
ガラムシ)arrowhead scale
2 Lepidoptera(鱗翅目)
Canephora asiatica Staudinger(ミノガ)
Mulberry bagworm
Spu´lerina astaurcta Meyrick(ナシホソ
ガ)Pear bark miner
Phyllonorycter ringoneella Matsumura(キ
ンモンホソガ)Apple leafminer
Plutella xylostella Linne′(コナガ)
Diamond back moth
Promalactis inopisema Butler(ワタミガ)
Cotton seedworm
Adoxophyes orana Fischer von
Ro¨slerstamm(コカクモンハマキ)Smaller
tea tortrix
Bactra furfurana Haworth(イグサシンム
シガ)Mat rush worm
Leguminivora glycinivorella Matsumura
(マメシンクイガ)Soybean pod borer
Cnaphalocrocis medinalis Guene′e(コブノ
メイガ)Rice leaf roller
Etiella zinckenella Treitschke(シロイチ
モジマダラメイガ)Lima−bean pod borer
Ostrinia furnacalis Gueue′e(アワノメイ
ガ)Oriental corn borer
Pleuroptya derogata Fabricius(ワタノメ
イガ)Cotton leaf roller
Hyphantria cunea Drury(アメリカシロヒ
トリ)Fall webworm
Abraxas miranda Butler(ユウマダラエダ
シヤク)Magpie moth
Lymantria dispar japonica Motschulsky
(マイマイガ)Gypsy moth
Phalera fiavescens Bremer etGrey(モン
クロシヤチホコ)Cherry caterpiller
Agrotis segetum Denis et Schiffer mu¨ller
(カブラヤガ)Cutworm
Helicoverpa armigera Hu¨bner(オオタバコ
ガ)Cotton、boll worm
Pseudaletia separata Walker(アワヨト
ウ)Armyworm
Mamestra brassicae Linne′(ヨトウガ)
Cabbage armyworm
Plusia nigrisigna Walker(タマナギンウワ
バ)Beet semi−looper
Spodoptera litura Fablicius(ハスモンヨト
ウ)Common cutworm
Parnara guttata Bremer et Grey(イネツ
トムシ)Rice skipper
Pieris rapae crucivora Boisduval(モンシ
ロチヨウ)Common cabbageworm
Chilo suppressalis Walker(ニカメイガ)
Rice stem borer
3 Coleoptera(鞘翅目)
Melanotus fortnumi Cande′ze(マルクビク
シコメツキ)Sweetpotato wirewerm
Anthrenus verbasci Linne′(ヒメマルカツ
オブシムシ)Varied carpet beetle
Tenebroides mauritanicus Linne′(コクヌ
スト)Cadelle
Lyctus brunneus Stephens(ヒラタキクイ
ムシ)powder post beetle
Henosepilachna vigintioctopunctata
Fablicius(ニジユウヤホシテントウ)28−
spotted lady beetle
Monochamus alternatus Hope(マツノマダ
ラカミキリ)Japanese pine sawyer
Xylotrechus pyrrhoderus Bates(ブドウト
ラカミキリ)Grape borer
Aulacophora femoralis Motschulsky(ウリ
ハムシ)Cucurbit leaf beetle
Oulema oryzae Kuwayama(イネドロオイ
ムシ)Rice、leaf beetle
Phyllotreta striolata Fablicius(キスジノ
ミハムシ)Striped flea beetle
Callosobruchus chinensis Linne′(アズキ
ゾウムシ)Azuki bean、weevil
Echinocnemis squameus Billberg(イネゾ
ウムシ)Rice plant weevil
Sitophilus oryzae Linne′(ココクゾウ)
Rice weevil
Apoderus erythrogaster Vollenhoven(ヒ
メクロオトシブミ)Small black leaf−cut
weevil
Rhynchites heros Roelofs(モモチヨツキリ
ゾウムシ)Peach curculio
Anomala cuprea Hope(ドウガネブイブ
イ)Cupreous chafer
Popillia japonica Newman(マメコガネ)
Japanese beetle
4 Hymenoptera(膜翅目)
Athalia rosae japonensis Rohwer(カブラ
ハバチ)Cabbage sawfly
Arge similis Vollenhoven(ルリチユウレン
ジ)Azalea argid sawfly
Arge pagana Panzer(チユウレンジバチ)
Rose argid sawfly
5 Diptera(双翅目)
Tipura aino Alexander(キリウジガガン
ボ)Rice crane fly
Culex pipiens fatigans Wiedemann(ネツ
タイイエカ)House mosquito
Aedes aegypti Linne′(ネツタイシマカ)
Yellow−fever mosquito
Asphondylia sp.(ダイズサヤタマバエ)
Soybean pod gall midge
Hylemya antiqua Meigen(タマネギバエ)
Onion maggot
Hylemya platura Meigen(タマバエ)Seed
corn maggot
Musca domestica vicina Macquart(イエ
バエ)House fly
Dacus cucurbitae Coquillett(ウリミバ
エ)Melon fly
Chlorops oryzae Matsumura(イネカラバ
エ)Rice stem maggot
Agromyza oryzae Munakata(イネハモグ
リバエ)Rice leafmier
6 Siphonaptera(隠翅目)
Pulex irritans Linne′(ヒトノミ)Human
flea
Xenopsylla cheopis Rothschild(ケオブス
ネズミノミ)Tropical rat flea
Ctenocephalides canis Curtis(イヌノミ)
Dog flea
7 Thysanoptera(総翅目)
Scirtothrips dorsalis Hood(チヤノキイロ
アザミウマ)、Yellow tea thrips
Thrips tabaci Lindeman(ネギアザミウ
マ)Onion thrips
Chloethrips oryzae Williams(イネアザミ
ウマ)Rice thrips
8 Anoplura(シラミ目)
Pediculus humanus corporis De Geer(コ
ロモジラミ)Body louse
Phthirus pubis Linne′(ケジラミ)Crab
louseHaematopinus eurysternus Nitzsh(ウ
シジラミ))Short−nosed cattle louce
9 Psocoptera(チヤタテムシ目)
Trogium pulsatsrium Linne′(コチヤタ
テ)larger pale booklouse
Liposcelis bostrychophilus Badonnel(ヒ
ラタチヤタテ)Flattened booklice
10 Orthoptera(直翅目)
Gryllotalpa africana palisot de Beauvois
(ケラ)African mole cricket
Locusta migratoria danica Linne′(トノサ
マバツタ)Asiatic locust
Oxya yezoensis Shiraki(コバネイナゴ)
Short−winged rice grass hopper
11 Dictyoptera(網翅目)
Blattella germanica Linne′(チヤバネゴキ
ブリ)German cockroach
Periplaneta fuliginosa Serville(クロゴキ
ブリ)Smoky−brown cockroach
12 Acarina(ダニ目)
Boophilus microplus Canestrini(オウシマ
ダニ)Bull tick
Polyphagotarsonemus latus Banks(チヤ
ノホコリダニ)Broad mite
Panonychus citri McGregor(ミカンハダ
ニ)Citrus red mite
Tetranychus cinnabarinus Boisduval(ニ
セナミハダニ)Carmine Spider mite
Tetranychus urticae Koch(ナミハダニ)
Two−spotted spider mite
Rhizoglyphus enhinophus Fumouze et
Robin(ネダニ)Bulb mite
本発明化合物を実際に施用する場合には、他の
成分を加えずに単味の形でも使用できるが、防除
薬剤として使いやすくするため担体を配合して製
剤とし、これを必要に応じ希釈するなどして適用
するのが一般的である。本発明化合物の製剤化に
あたつては、何らの特別の条件を必要とせず、一
般農薬に準じて当業技術の熟知する方法につつて
乳剤、水和剤、粉剤、粒剤、微粒剤、油剤、エア
ゾール、加熱燻蒸剤(蚊取線香、電気蚊取等)、
フオツキング等の煙霧剤、非加熱燻蒸剤、毒餌等
の任意の剤型に調製でき、これらそれぞれの目的
に応じた各種用途に供しうる。
さらに他の生理活性物質、例えばアレスリン
〔d・l−(3−アリル−2−メチル−2−シクロ
ペンテン−4−オン−1−イル)クリサンセメー
ト〕、N−(クリサンセモイルメチル)−3・4・
5・6−テトラハイドロフタルイミド、5−ベン
ジル−3−フリルメチルクリサンセメート、3−
フエノキシベンジルクリサンセメート、5−プロ
パルギルフルフリルクリサンセメート、その他既
知のシクロプロパンカルボン酸エステル、3−フ
エノキシベンジル 3−(2・2−ジクロロビニ
ル)−2・2−ジメチルシクロプロパン−1−カ
ルボキシレート、3−フエノキシ−α−シアノベ
ンジル 3−(2・2−ジクロロビニル)−2・2
−ジメチルシクロプロパン−1−カルボキシレー
ト、3−フエノキシ−α−シアノベンジル 3−
(2・2−ジブロモビニル)−2・2−ジメチルシ
クロプロパン−1−カルボキシレート、3−フエ
ノキシ−α−シアノベンジルα−イソプロピル−
4−クロルフエニルアセテートなどの合成ピレス
ロイドおよびこれらの各種異性体あるいは除虫菌
エキス、o・o−ジエチル−o−(3−オキソ−
2−フエニル−2H−ピリダジン−6−イル)ホ
スホロチオエート(三井東圧化学登録商標オフナ
ツク)、o・o−ジメチル−o−(2・2−ジクロ
ロビニル)−ホスフエート(DDVP)、o・o−ジ
メチル−o−(3−メチル−4−ニトロフエニ
ル)ホスホロチオエート、ダイアジノン、o・o
−ジメチル−o−4−シアノフエニルホスホロチ
オエート、o・o−ジメチル−s−〔α−(エトキ
シカルボニル)ベンジル〕ホスホロジチオエー
ト、2−メトキシ−4H−1・3・2−ベンゾジ
オキサホスホリン−2−スルフイド、o−エチル
−o−4−シアノフエニルフエニルホスホノチオ
エートなどの有機リン系殺虫剤、1−ナフチル−
N−メチルカーバメート(NAC)、m−トリル−
N−メチルカーバメート(MTMC)、2−ジメチ
ルアミノ−5・6−ジメチルピリミジン−4−イ
ル−ジメチルカーバメート(ピリマー)、3・4
−ジメチルフエニルN−メチルカーバメート、2
−イソプロポキシフエニルN−メチルカーバメー
トなどのカーバメート系殺虫剤、その他の殺虫
剤、殺ダニ剤あるいは殺菌剤、殺線虫剤、除草
剤、植物生長調整剤、肥料、BT剤、昆虫ホルモ
ン剤、その他の農薬等と混合することによりさら
に効力のすぐれた多目的組成物をつくることもで
き、また相乗効果も期待できる。
さらに、例えばα−〔2−(2−ブトキシエトキ
シ)エトキシ〕−4・5−メチレンジオキシ−2
−プロピルトルエン{ピペロニルブトキサイ
ド}、1・2−メチレンジオキシ−4−〔2−(オ
クチルサルフイニル)プロピル〕ベンゼン{サル
ホキサイド}、4−(3・4−メチレンジオキシフ
エニル)−5−メチル−1・3−ジオキサン{サ
フロキサン}、N−(2−エチルヘキシル)−ピシ
クロ(2・2・1)ヘプタ−5−エン−2・3−
ジカルボキシイミド{MGK−264}、オクタクロ
ロジプロピルエーテル{s−421}、イソボルニー
ルチオシアノアセテート{サーナイト}などのピ
レスロイド用共力剤として知られるものを加える
ことによりその効力を数倍にすることもできる。
なお、本発明化合物は光、熱、酸化等に安定性
が高いが、必要に応じ酸化防止剤あるいは紫外線
吸収剤、例えばBHT(2・6−ジ−tert−ブチル
−4−メチルフエノール)、BHA(ブチル−ヒド
ロキシアニソール)のようなフエノール誘導体、
ビス・フエノール誘導体、またフエニル−α−ナ
フチルアミン、フエニル−β−ナフチルアミン、
フエネチジンとアセトンの縮合物等のアリールア
ミン類あるいはベンゾフエノン系化合物類を安定
剤として適量加えることによつて、より効果の安
定した組成物を得ることができる。
本発明化合物の殺虫、殺ダニ剤は該化合物を
0.0001〜99重量%、好ましくは0.001〜50重量%
含有させる。
次に本発明化合物を殺虫、殺ダニ剤として用い
る場合の製剤例を若干示すが、本発明はこれらの
みに限定されるものではない。「部」はすべて重
量部を示す。
製剤例 1
本発明化合物20部、ソルポールSM−100(非イ
オン性界面活性剤とアニオン性界面活性剤との混
合物、東邦化学株式会社商品名)20部、キシロー
ル60部を撹拌混合して乳剤とする。
製剤例 2
本発明化合物1部をアセトン10部に溶解、粉剤
用クレー99部を加えたのちアセトンを蒸発せしめ
粉剤とする。
製剤例 3
本発明化合物20部に界面活性剤5部を加え、よ
く混合した後ケイソウ土75部を加え、ライカイ機
中にて撹拌混合して水和剤とする。
製剤例 4
本発明化合物0.2部にメタ・トリルNメチルカ
ーバメート2部を加え、さらに各々PAP(イソ
プロピルアシドホスフエート、日本化学工業株式
会社登録商標名、物性改良剤)0.2部を加えアセ
トン10部に溶解し、粉剤用クレーを97.6部を加え
ライカイ器中で撹拌混合し、アセトンを蒸発させ
れば粉剤となる。
製剤例 5
本発明化合物0.2部にオフナツク(前出)2部
を加え、さらにPAP(前出)0.2部を加え、アセ
トン10部に溶解し、粉剤用クレーを97.6部を加え
ライカイ器中で撹拌混合し、アセトンを蒸発させ
れば粉剤となる。
製剤例 6
本発明化合物0.1部にピペロニルブトキサイド
(前出)0.5部を加え白灯油に溶解し、全体を100
部とすれば油剤となる。
製剤例 7
本発明化合物0.5部、オフナツク(前出)5部
にソルポールSM−200(前出のソルポールSM−
100に同じ)を5部加え、キシロール89.5部に溶
解すれば乳剤となる。
製剤例 8
本発明化合物、0.4部、ピペロニルブトキサイ
ド(前出)20部、キシロール6部、脱臭灯油7.6
部を混合溶解し、エアゾール容器に充てんし、バ
ルブ部分を取り付け後、バルブ部分を通じて噴射
剤(液化石油ガス)84部を加圧充てんすればエア
ゾールとなる。
製剤例 9
本発明化合物0.05gを適量のクロロホルムに溶
解し、2.5cm×1.5cm厚さ0.3mmの石綿の表面に均等
に吸着させると熱板上加熱繊維燻蒸殺虫組成物と
なる。
製剤例 10
本発明化合物0.5gを20mlのメタノールに溶解
し、線香用担体(タブ粉:粕粉;木粉を3:5:
1の割合で混合)を99.5部と均一に撹拌混合し、
メタノールを蒸発させた後、水150mlを加えて充
分練り合わせたものを成型乾燥すれば蚊取線香と
なる。
製剤例 11
本発明化合物1部オフナツク(前出)3部、セ
ロゲン7A(カルボキシメチルセルローズ、第一
工業製薬株式会社商品名)2部、サンエキス(リ
グニンスルホン酸−Na塩、山陽国策パルプ株式
会社商品名)2部にクレー92部を混合し、加水し
て造粒、最適な粒径に整粒すれば粒剤となる。
本発明化合物を施用する場合の施用量は有効成
分で一般的には10アールあたり300g〜1g、の
ぞましくは100g〜2gである。
次に本発明化合物がすぐれた殺虫、殺ダニ効力
を有し、かつ温血動物に対して低毒性で、魚類に
対しても比較的低毒性であることを明確にするた
めに以下に試験例を示す。
試料:本発明化合物の20部とソルボールSM−
200(東邦化学登録商標名)20部にキシロール60
部を加え、これらをよく撹拌混合した。乳剤を蒸
留水で各供試濃度に希釈して用いる。魚毒性試験
は、供試化合物原体をアセトンに溶解して1%液
とし、水中に所定量加える。
マウスに対する毒性試験は原体をコーンオイル
に溶解または懸濁させて用いる。
なお対照化合物は以下に示す(a)〜(i)の比較
化合物を用い、本発明化合物と同様にして試験に
供した。
(公知Japan Pesticid Information No.33、、13
(1977))
(公知米国特許4073812)
(c) ピレトリン
(d) オフナツク(前出)
(e) MTMC(前出)
(f) メソミル(s−メチルN−(メチルカルバモ
イルオキシ)チオアセトアミデート)
(g) DDVP(前出)
(h) オルトラン(o・s−ジメチルN−アセチル
ホスホロアミドチオレート)
(i) ペルメトリン〔3−フエノキシベンジル2・
2−ジメチル−3−(2・2−ジクロロビニ
ル)−シクロプロパン−1−カルボキシレー
ト〕
試験例 1
ハスモンヨトウに対する効果
製剤例1によつて調製した各供試化合物の乳剤
を100および20ppm濃度に調製する。各薬液にサ
ツマイモ葉を10秒間浸漬し、風乾後径10cmのブラ
スチツクカツプに入れ、ハスモンヨトウの2令幼
虫を放ち、25℃の恒温室に静置した。処理24時間
後生死虫数を調査し、死虫率を算出した。結果は
3連制の平均値で示した。
The present invention relates to a novel 2-arylpropyl ether, a method for producing the same, and a low-toxicity insecticide and acaricide containing the compound. More specifically, one of the inventions provides 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-
Concerning methyl propyl ether. One of the aspects of the present invention is to convert a compound represented by the general formula [] into a compound represented by the general formula [] [In the formula, one group of group A and group B represents a halogen atom, and the other group represents an -O-M group (in the formula,
M represents a hydrogen atom, an alkali or alkaline earth metal atom), or both represent a hydroxyl group. The present invention relates to a method for producing (phenyl)-2-methylpropyl ether. One of the present invention is 3-phenoxybenzyl 2-
The present invention relates to an insecticide and acaricide containing (4-ethoxyphenyl)-2-methylpropyl ether. Pesticides have played an extremely important role in improving agricultural productivity, and the appearance of synthetic organic pesticides has completely changed the food situation for humankind, bringing great benefits in terms of preventing infectious diseases transmitted by insects. However, organochlorine insecticides DDT and BHC
Their use is limited because they remain in the environment for a long time after use, and organophosphorus insecticides and carbamate insecticides, which have replaced these insecticides, are widely used. Problems of resistance to these insecticides have arisen in several insect pests. In addition, difficult-to-control pests are appearing in some areas, and it is thought that problems such as drug-resistant pests will continue to spread and become more serious in the future. To this day, humans have built up their civilization, and as we seek to maintain an adequate supply of food for further development in the future, there is an urgent need for the emergence of drugs with superior insecticidal activity. be. In recent years, synthetic pyrethroid insecticides have been in the spotlight against this background. It has excellent insecticidal power and is highly effective against pests resistant to organic phosphorus agents or carbamate agents, and is characterized by relatively low toxicity to humans and livestock. However, the fatal drawback of this synthetic pyrethroid insecticide is that it is extremely toxic to fish, which limits its range of use. Furthermore, they are more expensive than conventionally developed insecticides. Agrochemicals that are desired in the future must be ones that solve the above-mentioned drawbacks. In other words, it is highly safe, does not leave any residue, decomposes quickly and does not pollute the environment, has high activity against the current problem of chemically resistant pests that are difficult to control, and can be manufactured at low cost. is desired. The present inventors planned to develop an insecticide and acaricide that is low toxicity, low toxicity to fish, and has strong insecticidal power.
As a result of intensive research, we have discovered that 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether has extremely high insecticidal and acaricidal activity, and has excellent immediate and residual effects. The present invention was completed based on the discovery that it has relatively low toxicity not only to humans and livestock, but also to fish, and that it can be put to practical use at a relatively low cost. The compound of the present invention has an active structure different from that of conventional agricultural chemicals, and is effective against sanitary pests such as flies, mosquitoes, and cockroaches, as well as planthoppers, leafhoppers, armyworms, diamondback moths, leafhoppers, aphids, and caterpillars. It is highly effective against agricultural pests such as spider mites, especially the black leafhopper, and is also extremely effective against grain storage pests such as the white mite, white-spotted moth, and brown elephant, animal-parasitic lice, and mites, and is also effective against other pests. Furthermore, the compound of the present invention has excellent rapid action and residual action, and also has a flushing effect. The compound of the present invention not only knocks down and kills pests, but also has repellent properties and removes pests from the host.
It also has a repellent effect, is one of the representative synthetic pyrethroids, and has the great advantage of not causing any phytotoxicity to plants of the Solanaceae family, such as fuenvalerate. In addition, the compound of the present invention has low toxicity to mammals and has high insecticidal efficacy at low concentrations, so it can be used with substantially high safety for fish.
Not only is it suitable for exterminating pests in rice fields, but it is also suitable for exterminating aquatic pests such as the larvae of mosquitoes and black flies, or for exterminating pests by aircraft spraying in large areas dotted with lakes, marshes, ponds, rivers, etc. can also be used without the risk of killing the fish that live there. Therefore, the insecticides and acaricides containing the compounds of the present invention can be applied to a wide range of fields, including agricultural and horticultural pests, grain storage pests, sanitary pests, house pests, forest pests,
It is highly active as an insecticide and acaricide for aquatic pests, etc., is extremely safe, and can be put to practical use in various dosage forms at low cost. 3-phenoxybenzyl 2-(4-
Ethoxyphenyl)-2-methylpropyl ether is a new compound. The manufacturing method of the present invention will be described in more detail as follows. That is, the general formula [] [in the formula,
When the alcohol of the group A represents an -O-H group] is reacted with the halide of the general formula The desired 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether can be obtained by reaction in a suitable solvent at room temperature to heating. The bases mentioned here refer to alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal hydrides, alkali metal alcoholates, alkali metal oxides, alkali metal carbonates, sodium amide, triethylamine, etc., and also deoxidizing agents. Silver oxide can also be used as a metal. Examples of solvents include water, aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane, heptane, and petroleum benzene, halogenated hydrocarbons such as chloroform and dichloromethane, and dimethylformamide and dimethyl sulfoxide. Non-proton-donating polar solvents, lower alcohols such as methanol and ethanol, diisopropyl ether, diethyl ether, 1.
Ethers such as 2-dimethoxyethane, tetrahydrofuran, and dioxane, nitriles such as acetonitrile and propionitrile, and ketones such as acetone and diisopropyl ketone can be used. Furthermore, the desired 3-
Phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether can be obtained in good yield. Alcoholate of the general formula [] [where the group A represents a -OM group (in the formula, M is not a hydrogen atom]] and the general formula [] [where the group B represents a halogen atom] When reacting with a halide, 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether can be obtained by carrying out the reaction in the above-mentioned solvent at room temperature or under heating. If the reactivity is poor, it is also suitable to add a catalytic amount of potassium iodide, copper iodide, etc. A halide of the general formula [] [where group A represents a halogen atom] and a halide of the general formula [] [where the group B represents a -OM group (in the formula, M represents the above meaning)] When reacting with an alcohol or an alcoholate in [case], it can be carried out in the same manner as described above. In particular, the halide of the general formula [] [in the formula, when group A represents a halogen atom] and the general formula []
(wherein the group B represents -OH) is reacted in the presence of an aprotic polar solvent, preferably dimethyl sulfoxide or sulfolane, and in the presence of a base as a deoxidizing agent.
The desired 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether can be obtained in good yield by the reaction under heating. Alcohol of general formula [] [in the formula, when group A is a hydroxyl group] and general formula [] [in the formula,
When group B is a hydroxyl group], a dehydration reaction is carried out in the presence of a catalyst to obtain 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether. I can do it. As the catalyst, acid catalysts such as sulfuric acid, hydrochloric acid, aromatic sulfonic acid, sulfonic acid chloride, boron trifluoride, and aluminum chloride can be used. Iodine, solid acid catalysts (alumina-titanium oxide, etc.), dimethyl sulfoxide, alumina, sulfamide, ion exchange resins, etc. can also be used as dehydration catalysts. Benzene if necessary
It is preferable to carry out the reaction in an inert solvent that is azeotropic with water, such as toluene, while removing the produced water under reflux. In addition, an alcohol of the general formula [] [where the group A represents a hydroxyl group] is added to the alcohol of the general formula [] [where the group A represents a hydroxyl group] in the presence of a dehydrating agent and, if necessary, a catalyst. 3-phenoxybenzyl by reacting with alcohol]
2-(4-ethoxyphenyl)-2-methylpropyl ether can also be obtained. As the dehydrating agent, for example, N.N-substituted carbodiimide, especially N.N-dicyclohexylcarbodiimide is preferable, and as the catalyst, for example, cuprous chloride is preferable. The reaction is carried out in the presence of a suitable inert solvent or diluent at room temperature or under heat. Suitable solvents or diluents include, for example, ethers such as 1,2-dimethoxyethane, dioxane, and tetrahydrofuran, aproton-donating polar solvents such as dimethylformamide, hexamethylphosphonic acid triamide, and dimethyl sulfoxide, acetone, methyl ethyl ketone, and cyclohexanone. Examples include ketones such as. Others, 3-phenoxybenzyl 2-(4-
As a method for producing ethoxyphenyl)-2-methylpropyl ether, the general formula [ ] [wherein the group A
A method of reacting a metal alcoholate or sulfonic acid ester of an alcohol with a metal alcoholate or a sulfonic acid ester of the alcohol represented by the general formula [] [in which the group B represents a hydroxyl group], When A is a hydroxyl group]
There is a method of reacting the alcohol with the metal alcoholate or sulfonic acid ester of the alcohol of the general formula [ ] (where group B is a hydroxyl group), but this method is disadvantageous in terms of yield. The starting materials of the general formula [] are prepared analogously to known methods described in the literature. That is, the alcohol represented by the general formula [] [where the group A represents a hydroxyl group] is
For example, it can be obtained by alkylating the corresponding 4-ethoxyphenylacetonitrile with methyl halide, then hydrolyzing the obtained nitrile to convert it into the corresponding carboxylic acid, and reducing the carboxylic acid. It is also obtained by converting a halide obtained by adding methallyl halide to 4-ethoxybenzene (in the case where group A represents a halogen atom in the general formula []) into an alcohol. An example manufacturing route is shown diagrammatically below. References Roczniki Chem., 39 (9), 1223
(1965) (Pol) [Chemical Abstract 64 ,
12595, h (1966)] Produced according to the route (1) below. [In formula [], group A is a halogen atom] References Chem, Ber., 94 , 2609 (1961) Reference J.Am.Chem.Soc., 65 , 1469 (1943) Also, the alcohol of the general formula [] [where the group A is a hydroxyl group] is Helvetica
It can also be produced by the method described in Chimica Acta, 54 , 868 (1971). The metal alcoholate of the general formula [] [where the group A represents an -OM group and M is not a hydrogen atom] can be prepared by a conventional method, for example, with a metal hydride such as sodium hydride and the general formula [] [In the formula, when group A represents an -OM group and M is a hydrogen atom]
It can be easily obtained by reacting alcohol. Alcohols of the general formula [] [where group B is a hydroxyl group] are known as alcohol components of synthetic pyrethroids. Next, the 3-phenoxybenzyl 2- of the present invention
The method for producing (4-ethoxyphenyl)-2-methylpropyl ether will be described in more detail below with reference to synthesis examples. Synthesis Example 1 (Etherification Method A) Add 0.90 g of sodium hydride (60% in oil) to 20 ml of dry acetonitrile, then add 3.0 g of 2-(4-ethoxyphenyl)-2-methylpropyl alcohol/10 ml of dry acetonitrile. The solution was added dropwise at 50°C. After heating under reflux for 30 minutes, a solution of 4.8 g of 3-phenoxybenzyl bromide/10 ml of dry acetonitrile was added dropwise over 10 minutes, and the mixture was further heated under reflux for 1 hour. After cooling to room temperature, it was poured into water and extracted with toluene. The toluene extract was washed with saturated brine and dried over anhydrous sodium sulfate. The crude ether obtained by distilling toluene off under reduced pressure was purified by column chromatography on 150 g of silica gel [developing solvent: benzene:n-hexane (2:3)] to obtain 3-phenoxybenzyl 2-(4). -ethoxyphenyl)-2-methylpropyl ether 4.2
I got g. n20 . 2 D 1.5732 ν film nax 1595, 1525, 1495, 1260, 1225, 1195
,
1110, 1055, 830, 700cm -1 δ CCl4 TMS (ppm) 1.29 (s.6H), 1.37 (t, J
=6.9
Hz, 3H), 3.32 (s, 2H), 3.93 (q, J=6.9
Hz, 2H), 4.38 (s, 2H), 6.6-7.35 (m,
13H) Elemental analysis results C 25 H 28 O 3 Calculated value (%) C; 79.76, H; 7.50 Actual value (%) C; 79.97, H; 7.34 3-Phenoxybenzyl 2-(4) obtained above
-ethoxyphenyl)-2-methylpropyl ether solidified upon standing at room temperature for an extended period of time. The melting point is
The temperature was 35-38℃. Sludge this with methanol, filter, wash,
After drying, sludge with n-hexane, filtration, washing and drying, white crystals with a melting point of 36.4-38°C were obtained. Synthesis Example 2 (Etherification Method B) Sodium hydride (60% in
After adding 0.63 g of 2-(4-ethoxyphenyl)-2-methylpropyl alcohol to this
g/25% DMF-Toluene 10ml solution was heated under reflux.
It was added dropwise over 15 minutes. After continuing stirring for 10 minutes, 3-phenoxybenzyl bromide 3.3
g/25% DMF-toluene 10ml solution was added dropwise over 20 minutes. After further heating under reflux for 1 hour, the reaction mixture was cooled to room temperature and poured into water. After extraction with toluene and washing the toluene extract with water, it was dried over anhydrous sodium sulfate. The oil obtained by distilling toluene off under reduced pressure was purified by column chromatography [100 ml of silica gel, benzene:n-hexane (2:3)] to obtain 3.0 g of the desired pure ether. Synthesis Example 3 (Etherification Method C) 30g of 50% NaOH aqueous solution, 6.3g of 2-(4-ethoxyphenyl)-2methylpropyl alcohol, 3
-7.6 g of phenoxybenzyl chloride and 1.1 g of tetrabutylammonium bromide were added, and the mixture was heated and stirred at 80°C for 1 hour. After cooling the reaction mixture to room temperature, water was added, extracted with toluene, and washed with water. After drying the toluene extract over anhydrous sodium sulfate, the toluene was distilled off under reduced pressure, and the resulting crude ether was subjected to column chromatography [silica gel developing solvent: benzene: n-hexane (2:
3)] to obtain 10.0 g of the desired ether. Synthesis Example 4 (Etherification method D) 0.50 p-toluenesulfonic acid in 50 ml of toluene
g, 2.5 g of 3-phenoxybenzyl alcohol,
2.5 g of 2-(4-ethoxyphenyl)-2-methylpropyl alcohol was added and heated under reflux for 6 hours (produced water was removed from the system using a water separator).
After cooling to room temperature, water was added, and the toluene layer was separated, washed with water, and dried. The crude ether obtained by distilling toluene off under reduced pressure was purified by column chromatography [silica gel, developing solvent: benzene:n-hexane (2:3)] to obtain the desired ether. Synthesis Example 5 (Etherification Method E) Mixing of 1.8 g of 2-(4-ethoxyphenyl)-2-methylpropyl alcohol, 2.4 g of 3-phenoxybenzyl chloride, 20 g of 50% NaOH, and 0.3 g of triethylbenzylammonium bromide. The liquid was stirred at 50°C for 2 hours. After the reaction mixture was cooled to room temperature, water was added and extracted with benzene. The benzene extract was washed with dilute hydrochloric acid, then water, and dried. The crude ether obtained by distilling off benzene under reduced pressure was subjected to column chromatography (silica gel 80
g, developing solvent: benzene-n-hexane, 2:
3) to obtain 2.8 g of the desired ether. Synthesis Example 6 (Etherification Method F) 4-ethoxyneofyl chloride 8.9g, 3
- 8.5 g of phenoxybenzyl alcohol, 3.9 g of 45% caustic soda and dimethyl sulfoxide
48g was heated and stirred at 140°C for 3 hours. 1.8 g of 45% caustic soda was added, and the reaction was continued at the same temperature for an additional 4 hours. After cooling the reaction solution to room temperature, pour it into water.
After extraction with benzene, the benzene extract was washed with water and then dried. The crude ether obtained by distilling off benzene under reduced pressure was separated and purified by column chromatography (300 g of silica gel, developing solvent: benzene:n-hexane 2:3) to obtain 10.3 g of the desired ether. The method for producing alcohol and halide as starting materials [] will be explained in detail below using synthetic reference examples. Synthesis Reference Example 1 Synthesis of 2-(4-ethoxyphenyl)-2-methylpropyl alcohol (4-ethoxyneofyl alcohol) Synthesis was performed according to the following sequence. (1) Synthesis of 2-(4-ethoxyphenyl)-2methylpropionitrile 280 g of 4-ethoxybenzyl nitrile, 80 g of triethylbenzylammonium bromide,
When 750 g of potassium hydroxide and 750 g of water were charged into two separable flasks and stirring was started, the internal temperature rose to about 85-90°. This includes methyl iodide
180 ml (approximately 410 g) was added dropwise over 1.5 hours. Stirring was then continued for an additional 7 hours at 80-90°C. After cooling the reaction solution to room temperature, it was extracted with 500 ml of benzene, and the benzene extract was washed with dilute hydrochloric acid and water in that order, and then dried over anhydrous sodium sulfate. Benzene was distilled off under reduced pressure to obtain 311 g of crude 2-(4-ethoxyphenyl)propionitrile. Crude 2-(4-ethoxyphenyl) obtained above
311 g of propionitrile, 110 g of triethylbenzylammonium bromide, 800 g of potassium hydroxide, and 800 g of water were charged into two separable flasks and stirred. Next, 180 ml (approximately 410 g) of methyl iodide was added dropwise at 85 to 90° C. over 1.5 hours.
After 3.5 hours had passed after the completion of the dropping, 300 g of potassium hydroxide was additionally charged. After a further 5 hours, 50 ml (approximately 114 g) of methyl iodide was added. The reaction was further continued at the same temperature for 2 hours. The crude 2-(4-ethoxyphenyl)-2 was then treated in the same manner as in the synthesis of 2-(4-ethoxyphenyl)propionitrile.
-340 g of methylpropionitrile were obtained. The product was purified by distillation under reduced pressure to obtain 275 g of the desired product. (111~
112℃/0.60~0.55mmHg). (2) Synthesis of 2-(4-ethoxyphenyl)-2-methylpropionic acid 275 g of 2-(4-ethoxyphenyl)-2-methylpropionic acid, 850 g of potassium hydroxide,
700 ml of water and 2000 ml of ethylene glycol were reacted for 8 hours under reflux at 121 to 126° C. with stirring. After the reaction mixture was cooled to room temperature, it was poured into 2 to 3 portions of water, and the neutral portion was removed with benzene. The aqueous layer was adjusted to pH 2 or less with concentrated hydrochloric acid and extracted with benzene. The benzene extract was washed with water, dried over anhydrous sodium sulfate, and after distilling off the benzene, it was recrystallized from n-hexane. mp80.5~82.5℃ 2-
240 g of (4-ethoxyphenyl)-2-methylpropionic acid was obtained. (3) Synthesis of ethyl 2-(4-ethoxyphenyl)-2-methylpropionate 240 g of the carboxylic acid obtained in (2) was mixed with 400 ml of benzene,
After dissolving in 200 ml of ethanol, 25 ml of concentrated sulfuric acid is added and the azeotrope of benzene-ethanol-water is removed from the system under reflux. At this time, a mixed solution of 400 ml of benzene and 200 ml of ethanol was added dropwise to the reactor over a period of 6 hours. After cooling the reaction mixture to room temperature, water was added and the benzene layer was separated. The obtained benzene solution was washed with water until it became neutral, and then dried. Benzene was distilled off under reduced pressure to obtain 264 g of the desired ester. (4) Synthesis of 2-(4-ethoxyphenyl)-2-methylpropyl alcohol Add 35 g of lithium aluminum hydride to 400 ml of dry tetrahydrofuran and add (3)
264 g of the ester obtained above was added dropwise while keeping the temperature below 30°C. After the completion of dropping the ester, the mixture was refluxed for 30 minutes. Next, in order to decompose excess lithium aluminum hydride, 30 ml of ethyl acetate was added dropwise under ice cooling. When heat generation and foaming were no longer observed, water was added to completely decompose the lithium aluminum hydride. After removing the generated precipitate under reduced pressure, tetrahydrofuran was distilled off under reduced pressure. Extraction was performed with 300 ml of benzene, and the extract was washed with water and dried. Benzene was distilled off under reduced pressure, and 2-(4-ethoxyphenyl)-2-
213 g of methylpropyl alcohol was obtained. mp; 42.0-43.5℃ ν KBr nax ; 3400, 1620, 1520, 1255, 1195, 1050
,
830cm -1 Synthesis reference example 2 Synthesis of 4-ethoxyneofyl chloride Equipped with stirrer, Dimroth, thermometer and dropping funnel
After adding 120 g of concentrated sulfuric acid to a 500 ml flask, 200 g of phenetol was added dropwise while maintaining the temperature at 5°C. 0℃
While maintaining the temperature at ~10°C, a mixed solution of 90 g of methallyl chloride/165 g of phenetol was added dropwise over 10 hours.
Then, after keeping at 25°C for 15 hours, it was poured into ice water. After separating the organic layer, it was thoroughly washed in the order of dilute aqueous sodium hydroxide solution and water. After drying with anhydrous sodium sulfate, crude 4-
16 g of ethoxyneofyl chloride was obtained (114
℃/2.0mmHg to 116.5℃/1.7mmHg). δ CCl4 (ppm) 1.39 (s, 6H), 1.3-1.6 (m,
3H), 3.51 (s, 2H), 4.05 (q, J=6.9Hz,
2H), 4.05 (q, J=6.9Hz, 2H), 6.6-7.3
(m, 4H) Reference: Chem, Ber., 94, 2609 (1961) Next, the names of specific pests to which the insecticide and acaricide of the present invention can be applied are listed [scientific name - (Japanese name) - English name]. 1 Hemiptera Nephotettix cincticeps Uhler Green rice leafhopper Sogata furcifera Horva'th White-backed rice planthopper Nilaparvata lugens Sta゜l Brown rice planthopper Laodelphax striatellus Falle'n Small brown planthopper Eurydema rugosum Motschulsky Cabbage bug Eysarcoris parvus Uhler Whitespotted spined bug Halyomorpha mista Uhler Brown-marmorated stink bug Lagynotomus elongatus Dallas Rice stink bug Nezara viridula Linne′ Southern green stink bug Cletus trigonns Thunberg′ Slender rice bug Stephanitis nashi Esaki et, Takeya Japanese pear lace bug Stephanitis pyrioides Scott Azalea lace bug Psylla pyrisuga Fo¨rster
Pear sucker Psylla mali Schmidberger Apple sucker Aleurolobus taonabae Kuwana Grape whitefly Dialeurodes citri Ashmead Citrus whitefly Trialeurodes vaporariorum Westwood Greenhouse whitefly Aphis gossypii Glover
Cotton aphid Brevicoryne, brassicae Linne′ Cabbage aphid Myzus persicae Sulzer Green peach aphid Rhopalosiphum maidis Fitch Corn leaf aphid Icerya purchasi Maskell Cottonycushion scale Planococcus citri Risso citrus mealybug Unaspis yanonensis Kuwana arrowhead scale 2 Lepidoptera Canephora asiatica Staudinger
Mulberry bagworm Spu´lerina astaurcta Meyrick Pear bark miner Phyllonorycter ringoneella Matsumura Apple leafminer Plutella xylostella Linne′
Diamond back moth Promalactis inopisema Butler
Cotton seedworm Adoxophyes orana Fischer von
Ro¨slerstamm Smaller
tea tortrix Bactra furfurana Haworth Mat rush worm Leguminivora glycinivorella Matsumura
Soybean pod borer Cnaphalocrocis medinalis Guene′e Rice leaf roller Etiella zinckenella Treitschke Lima-bean pod borer Ostrinia furnacalis Gueue′e Oriental corn borer Pleuroptya derogata Fabricius Cotton leaf roller Hyphantria cunea DruryFall webworm Abraxas miranda ButlerMagpie moth Lymantria dispar japonica Motschulsky
Gypsy moth Phalera fiavescens Bremer etGreyCherry caterpiller Agrotis segetum Denis et Schiffer mu¨ller
Cutworm Helicoverpa armigera Hu¨bner Cotton, boll worm Pseudaletia separata Walker Armyworm Mamestra brassicae Linne′
Cabbage armyworm Plusia nigrisigna Walker Beet semi-looper Spodoptera litura Fablicius Common cutworm Parnara guttata Bremer et Gray Rice skipper Pieris rapae crucivora Boisduval Common cabbageworm Chilo suppressalis Walker
Rice stem borer 3 Coleoptera Melanotus fortnumi Cande'ze Sweetpotato wirewerm Anthrenus verbasci Linne' Varied carpet beetle Tenebroides mauritanicus Linne' Cadelle Lyctus brunneus Stephens powder post beetle Henosepilachna vigintioctopunctata
Fablicius 28−
spotted lady beetle Monochamus alternatus HopeJapanese pine sawyer Striped flea beetle Callosobruchus chinensis Linne′ Azuki bean, weevil Echinocnemis squameus Billberg Rice plant weevil Sitophilus oryzae Linne′
Rice weevil Apoderus erythrogaster Vollenhoven Small black leaf−cut
weevil Rhynchites heroes Roelofs Peach curculio Anomala cuprea Hope Cupreous chafer Popillia japonica Newman
Japanese beetle 4 Hymenoptera Athalia rosae japonensis Rohwer Cabbage sawfly Arge similis Vollenhoven Azalea argid sawfly Arge pagana Panzer
Rose argid sawfly 5 Diptera Tipura aino Alexander Rice crane fly Culex pipiens fatigans Wiedemann House mosquito Aedes aegypti Linne′
Yellow−fever mosquito Asphondylia sp.
Soybean pod gall midge Hylemya antiqua Meigen (onion fly)
Onion maggot Hylemya platura Meigen Seed
corn maggot Musca domestica vicina Macquart House fly Dacus cucurbitae Coquillett Melon fly Chlorops oryzae Matsumura Rice stem maggot Agromyza oryzae Munakata Rice leafmier 6 Siphonaptera Pulex irritans Linne′ )Human
flea Xenopsylla cheopis Rothschild Tropical rat flea Ctenocephalides canis Curtis
Dog flea 7 Thysanoptera Scirtothrips dorsalis Hood, Yellow tea trips Thrips tabaci Lindeman Onion thrips Chloethrips oryzae Williams Rice thrips 8 Anoplura Pediculus humanus corporis De Geer Body louse Phthirus pubis Linne′ Crab
louseHaematopinus eurysternus Nitzsh) Short-nosed cattle louce 9 Psocoptera Trogium pulsatsrium Linne′ large pale booklouse Liposcelis bostrychophilus Badonnel Flattened booklice 10 Orthoptera Gryllotalpa africana palisot de Beauvois
(Mole cricket) African mole cricket Locusta migratoria danica Linne′ (Tonosama battuta) Asiatic locust Oxya yezoensis Shiraki (Kobanei locust)
Short-winged rice grass hopper 11 Dictyoptera Blattella germanica Linne′ German cockroach Periplaneta fuliginosa Serville Smoky-brown cockroach 12 Acarina Boophilus microplus Canestrini Bull tick Polyphagotarsonemus latus Banks Broad mite Panonychus citri McGregor Citrus red mite Tetranychus cinnabarinus Boisduval Carmine Spider mite Tetranychus urticae Koch
Two-spotted spider mite Rhizoglyphus enhinophus Fumouze et
Robin Bulb mite When actually applying the compound of the present invention, it can be used alone without adding other ingredients, but in order to make it easier to use as a pesticidal agent, it may be formulated with a carrier. It is common to dilute and apply as necessary. The compounds of the present invention can be formulated into emulsions, wettable powders, powders, granules, and fine granules using methods well known in the art in accordance with general agricultural chemicals, without requiring any special conditions. , oils, aerosols, heated fumigants (mosquito coils, electric mosquito repellents, etc.),
It can be prepared in any form such as a fogging agent for focking, a non-heating fumigant, a poisonous bait, etc., and can be used for various purposes depending on the purpose of each. Furthermore, other physiologically active substances, such as allethrin [d·l-(3-allyl-2-methyl-2-cyclopenten-4-one-1-yl)chrysanthemate], N-(chrysansemoylmethyl)-3・4・
5,6-tetrahydrophthalimide, 5-benzyl-3-furylmethyl chrysansemate, 3-
Phenoxybenzyl chrysanthemate, 5-propargyl furfuryl chrysanthemate, other known cyclopropane carboxylic acid esters, 3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane -1-carboxylate, 3-phenoxy-α-cyanobenzyl 3-(2,2-dichlorovinyl)-2,2
-dimethylcyclopropane-1-carboxylate, 3-phenoxy-α-cyanobenzyl 3-
(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylate, 3-phenoxy-α-cyanobenzyl α-isopropyl-
Synthetic pyrethroids such as 4-chlorophenylacetate and their various isomers or pyrethyl extracts, o.o-diethyl-o-(3-oxo-
2-phenyl-2H-pyridazin-6-yl) phosphorothioate (Mitsui Toatsu Chemical registered trademark Offnack), o・o-dimethyl-o-(2,2-dichlorovinyl)-phosphate (DDVP), o・o-dimethyl -o-(3-methyl-4-nitrophenyl)phosphorothioate, diazinon, o・o
-dimethyl-o-4-cyanophenyl phosphorothioate, o,o-dimethyl-s-[α-(ethoxycarbonyl)benzyl]phosphorodithioate, 2-methoxy-4H-1,3,2-benzodioxaphospho Organophosphorus insecticides such as phosphorus-2-sulfide, o-ethyl-o-4-cyanophenyl phenylphosphonothioate, 1-naphthyl-
N-methyl carbamate (NAC), m-tolyl-
N-Methyl carbamate (MTMC), 2-dimethylamino-5,6-dimethylpyrimidin-4-yl-dimethylcarbamate (pyrimer), 3,4
-dimethylphenyl N-methylcarbamate, 2
- Carbamate insecticides such as isopropoxyphenyl N-methyl carbamate, other insecticides, acaricides or fungicides, nematicides, herbicides, plant growth regulators, fertilizers, BT agents, insect hormone agents, By mixing it with other agricultural chemicals, etc., it is possible to create a multipurpose composition with even greater efficacy, and a synergistic effect can also be expected. Further, for example, α-[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2
-Propyltoluene {piperonyl butoxide}, 1,2-methylenedioxy-4-[2-(octylsulfinyl)propyl]benzene {sulfoxide}, 4-(3,4-methylenedioxyphenyl) -5-methyl-1,3-dioxane {safloxane}, N-(2-ethylhexyl)-picyclo(2,2,1)hept-5-ene-2,3-
By adding known synergists for pyrethroids, such as dicarboximide {MGK-264}, octachlorodipropyl ether {s-421}, and isobornyl thiocyanoacetate {Garnite}, its potency can be increased several times. You can also. The compound of the present invention has high stability against light, heat, oxidation, etc., but if necessary, antioxidants or ultraviolet absorbers such as BHT (2,6-di-tert-butyl-4-methylphenol), BHA Phenol derivatives such as (butyl-hydroxyanisole),
Bis-phenol derivatives, also phenyl-α-naphthylamine, phenyl-β-naphthylamine,
By adding an appropriate amount of arylamines such as a condensate of phenetidine and acetone or benzophenone compounds as a stabilizer, a composition with more stable effects can be obtained. The insecticide and acaricide of the compound of the present invention is
0.0001-99% by weight, preferably 0.001-50% by weight
Contain. Next, some examples of formulations in which the compound of the present invention is used as an insecticide or acaricide are shown, but the present invention is not limited to these. All "parts" indicate parts by weight. Formulation Example 1 20 parts of the compound of the present invention, 20 parts of Solpol SM-100 (a mixture of nonionic surfactant and anionic surfactant, trade name of Toho Chemical Co., Ltd.), and 60 parts of xylol were stirred and mixed to form an emulsion. do. Formulation Example 2 1 part of the compound of the present invention is dissolved in 10 parts of acetone, 99 parts of clay for powders are added, and the acetone is evaporated to form a powder. Formulation Example 3 Add 5 parts of a surfactant to 20 parts of the compound of the present invention, mix well, then add 75 parts of diatomaceous earth, and stir and mix in a Raikai machine to prepare a wettable powder. Formulation Example 4 Add 2 parts of meta-tolyl N-methyl carbamate to 0.2 parts of the compound of the present invention, and then add 0.2 parts of PAP (isopropyl acid phosphate, registered trademark of Nihon Kagaku Kogyo Co., Ltd., physical property improver) to 10 parts of acetone. Dissolve, add 97.6 parts of powder clay, stir and mix in a Raikai vessel, and evaporate the acetone to form a powder. Formulation Example 5 Add 2 parts of Offnack (mentioned above) to 0.2 parts of the compound of the present invention, further add 0.2 parts of PAP (mentioned above), dissolve in 10 parts of acetone, add 97.6 parts of powder clay, and stir in a Raikai vessel. Mix and evaporate the acetone to form a powder. Formulation Example 6 Add 0.5 parts of piperonyl butoxide (mentioned above) to 0.1 part of the compound of the present invention, dissolve in white kerosene, and add 0.1 part of the compound of the present invention to 100%
%, it becomes an oil agent. Formulation Example 7 Solpol SM-200 (Solpol SM-
Add 5 parts of (same as 100) and dissolve in 89.5 parts of xylene to form an emulsion. Formulation Example 8 Compound of the present invention, 0.4 parts, piperonyl butoxide (above) 20 parts, xylol 6 parts, deodorized kerosene 7.6 parts
After mixing and dissolving 84 parts of the propellant (liquefied petroleum gas) and filling it into an aerosol container, attaching the valve part and pressurizing 84 parts of propellant (liquefied petroleum gas) through the valve part, it becomes an aerosol. Formulation Example 9 When 0.05 g of the compound of the present invention is dissolved in an appropriate amount of chloroform and evenly adsorbed onto the surface of asbestos measuring 2.5 cm x 1.5 cm and 0.3 mm thick, a fiber fumigation insecticidal composition heated on a hot plate is obtained. Formulation Example 10 0.5 g of the compound of the present invention was dissolved in 20 ml of methanol, and a carrier for incense sticks (Tab flour: Leek flour; Wood flour: 3:5:
Stir and mix evenly with 99.5 parts of (mixed at a ratio of 1 part)
After evaporating the methanol, add 150 ml of water, mix well, mold and dry to make a mosquito coil. Formulation Example 11 1 part of the compound of the present invention, 3 parts of Offnatsu (mentioned above), 2 parts of Celogen 7A (carboxymethyl cellulose, trade name of Daiichi Kogyo Seiyaku Co., Ltd.), Sunextract (ligninsulfonic acid-Na salt, Sanyo Kokusaku Pulp Co., Ltd.) (Product name) 2 parts and 92 parts of clay are mixed, water is added and granulated, and the particles are sized to the optimum particle size to form granules. When applying the compound of the present invention, the amount of active ingredient to be applied is generally 300 g to 1 g, preferably 100 g to 2 g per 10 ares. Next, in order to clarify that the compound of the present invention has excellent insecticidal and acaricidal effects, has low toxicity to warm-blooded animals, and has relatively low toxicity to fish, test examples are provided below. shows. Sample: 20 parts of the compound of the present invention and Sorbol SM-
200 (Toho Chemical registered trademark name) 20 parts xylol 60
of the mixture were added, and these were thoroughly stirred and mixed. Dilute the emulsion with distilled water to each test concentration. For the fish toxicity test, the raw material of the test compound is dissolved in acetone to make a 1% solution, and a predetermined amount is added to water. For toxicity tests on mice, the drug substance is dissolved or suspended in corn oil. Note that the comparative compounds (a) to (i) shown below were used as control compounds and were subjected to the test in the same manner as the compounds of the present invention. (Publicly known Japan Pesticid Information No.33, 13
(1977)) (Known U.S. Pat. No. 4,073,812) (c) Pyrethrin (d) Ofnac (supra) (e) MTMC (supra) (f) Methomyl (s-methyl N-(methylcarbamoyloxy)thioacetamidate) (g) DDVP (Supra) (h) Ortolan (os-dimethyl N-acetyl phosphoramidothiolate) (i) Permethrin [3-phenoxybenzyl 2.
2-Dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-1-carboxylate] Test Example 1 Effect on Spodoptera spp. Emulsions of each test compound prepared according to Formulation Example 1 were adjusted to concentrations of 100 and 20 ppm. do. Sweet potato leaves were immersed in each chemical solution for 10 seconds, air-dried, placed in a plastic cup with a diameter of 10 cm, and the second instar larvae of Spodoptera japonica were released and left in a constant temperature room at 25°C. 24 hours after treatment, the number of live and dead insects was investigated, and the mortality rate was calculated. The results are shown as the average value of three consecutive results.
【表】
試験例 2
ハスモンヨトウ幼虫浸漬効果
試験例1同様に各供試化合物の100および
20ppm濃度の薬液を調製した。
ハスモンヨトウ2令幼虫および5令幼虫を上記
薬液に5秒間虫体浸漬し、ろ紙で余分な薬液を除
いたのち、あらかじめ用意したプラスチツクカツ
プに放ち、人工飼料を与え、25℃の恒温室に静置
した。処理24時間後、生死虫数を調査し、死虫率
を算出した。結果は3連の平均値で示した。[Table] Test Example 2 Effect of immersion in Spodoptera larvae Same as Test Example 1, 100 and 100% of each test compound
A drug solution with a concentration of 20 ppm was prepared. Spodoptera 2nd and 5th instar larvae were immersed in the above chemical solution for 5 seconds, and after removing excess chemical solution with filter paper, they were released into pre-prepared plastic cups, fed with artificial food, and left in a constant temperature room at 25℃. did. 24 hours after the treatment, the number of live and dead insects was investigated, and the mortality rate was calculated. The results are shown as the average value of three series.
【表】
試験例 3
ハスモンヨトウに対する局所施用効果
各供試化合物をアセトンに溶解し、ハスモンヨ
トウ3令幼虫に体重1g当たり0.25μgあて、微
量局所施用装置にて処理した。処理24時間後生死
虫数を調査した。結果は3連平均値で示した。[Table] Test Example 3 Effect of local application on Spodoptera trifoliata Each test compound was dissolved in acetone, and 0.25 μg/g of body weight was applied to 3rd instar larvae of Spodoptera pruriens using a micro-dose local application device. The number of live and dead insects was investigated 24 hours after treatment. The results are shown as the average value of three consecutive runs.
【表】
試験例 4
抵抗性ツマグロヨコバイおよび感受性ツマグロ
ヨコバイに対する効果
水稲稚苗(本葉2〜3枚)を径5cmのポツトに
水耕裁培し、試験例1同様に調製した各供試薬剤
の100および20ppm濃度の薬液を噴霧器にてそれ
ぞれ3ml/ポツト処理した。風乾後、苗を金網円
筒でおおい、抵抗性ツマグロヨコバイ(中川原
産)および感受性ツマグロヨコバイ(茅ケ崎産)
の各雌成虫をそれぞれポツト当り10頭放ち、ガラ
ス温室内に静置した。処理24時間後生死虫数を調
査し、死虫率を算出した。結果は3連平均値で示
した。[Table] Test Example 4 Effect on resistant leafhopper and susceptible leafhopper Rice seedlings (2 to 3 true leaves) were hydroponically cultured in pots with a diameter of 5 cm, and 100% of each test chemical prepared in the same manner as Test Example 1 was used. and 3 ml/pot of each drug solution with a concentration of 20 ppm was applied using a sprayer. After air-drying, the seedlings were covered with a wire mesh cylinder, and resistant leafhoppers (from Nakagawa) and susceptible leafhoppers (from Chigasaki) were isolated.
Ten female adults were released per pot and left in a glass greenhouse. 24 hours after treatment, the number of live and dead insects was investigated, and the mortality rate was calculated. The results are shown as the average value of three consecutive runs.
【表】
試験例 5
ツマグロヨコバイに対する水面施用効果
1/10000aポツトに3葉期の水稲を移植し活着
させた。水深を2cmに保ち各化合物の1%粒剤を
試作し、これを10a当り有効成分量で5gあて処
理した。ポツト金網円筒でおおい、ツマグロヨコ
バイ(茅ケ崎産)の雄成虫を放ち、24時間後生死
虫数を調査し、死虫率を求めた。結果は3連平均
値で示した。[Table] Test Example 5 Effect of water surface application on leafhopper Paddy rice at the 3-leaf stage was transplanted into a 1/10000a pot and allowed to take root. While keeping the water depth at 2 cm, 1% granules of each compound were prepared as a trial, and 5 g of the active ingredient was applied per 10 acres. The pot was covered with a wire mesh cylinder, and male adult leafhoppers (from Chigasaki) were released. After 24 hours, the number of living and dead insects was examined to determine the mortality rate. The results are shown as the average value of three consecutive runs.
【表】
試験例 6
コナガに対する効果
プラスチツクカツプにカンラン葉を敷き、コナ
ガ3令幼虫を10頭放つた。
試験例1と同様に調製した各供試薬剤の100お
よび20ppm濃度の薬液を散布塔にてカツプ当り
3ml散布した。
散布後カツプのふたをし、24時間後、生死虫数
を調査し、死虫率を算出した。結果は3連の平均
値で示した。[Table] Test Example 6 Effect on diamondback moth A plastic cup was covered with citrus leaves and 10 third instar diamondback moth larvae were released. 3 ml of each test chemical solution prepared in the same manner as in Test Example 1 at concentrations of 100 and 20 ppm was sprayed per cup using a spray tower. After spraying, the cup was covered, and 24 hours later, the number of live and dead insects was counted, and the mortality rate was calculated. The results are shown as the average value of three series.
【表】
試験例 7
モモアカアブラムシに対する効果
鉢植えのナスの稚苗(本葉3〜4枚)にモモア
カアブラムシを接種し増殖させた。虫数を測定
し、試験例1同様に調製した各供試薬剤の
100ppm、20ppmおよび4ppm濃度の薬液をスプ
レーガンにて鉢当り10ml処理した。処理後ガラス
温室内に静置し24時間後生虫数を調査し死虫率を
求めた。
なお結果は3連の平均死虫率95%以上はA、95
〜80%はB、80〜50%はC、50%以下をDで示し
た。[Table] Test Example 7 Effect on Green Peach Aphid Potted eggplant seedlings (3 to 4 true leaves) were inoculated with Green peach aphid and allowed to grow. The number of insects was measured, and each test drug prepared in the same manner as Test Example 1 was tested.
Each pot was treated with 10 ml of chemical solutions at concentrations of 100 ppm, 20 ppm, and 4 ppm using a spray gun. After treatment, the plants were left in a glass greenhouse, and the number of live insects was counted after 24 hours to determine the mortality rate. The results are A, 95 if the average mortality rate of three series is 95% or more.
~80% was designated as B, 80 to 50% was designated as C, and 50% or less was designated as D.
【表】
試験例 8
ナミハダニ成虫に対する効果
水で浸した脱脂綿(2cm×2cm)上にコルクボ
ーラー(径15mm)で打抜いたインゲン葉のリーフ
デイスクをのせナミハダニ成虫10頭を放飼した。
各供試薬剤の100ppm濃度の薬液を噴霧塔で3ml
あて処理した。
処理後25℃の恒温室に静置し、処理24時間後生
死虫数を調査し殺成虫率を求めた。結果は3連の
平均値で示した。[Table] Test Example 8 Effect on adult two-spotted spider mites Ten adult two-spotted spider mites were placed on water-soaked absorbent cotton (2 cm x 2 cm) with leaf discs of green bean leaves punched out with a cork borer (15 mm in diameter).
3ml of 100ppm concentration of each test drug in a spray tower
I dealt with it. After treatment, the specimens were left in a constant temperature room at 25°C, and the number of living and dead insects was investigated 24 hours after treatment to determine the adult killing rate. The results are shown as the average value of three series.
【表】
試験例 9
チヤバネゴキブリに対する効果
直径9cm高さ9cmの腰高シヤーレ底面に各供試
化合物を50mg/m2、10mg/m2、1mg/m2および0.5
mg/m2あて処理した。風乾後、チヤバネゴキブリ
雄成虫10頭/シヤーレづつ放ち25℃の恒温室内に
静置し、24時間後、苦悶死虫数を調査した。なお
虫の逃亡を防ぐためシヤーレ内壁はバターで処理
した。結果は2連の平均値で示した。[Table] Test Example 9 Effect on German cockroaches Each test compound was applied to the bottom of a waist-high shear dish with a diameter of 9 cm and a height of 9 cm at doses of 50 mg/m 2 , 10 mg/m 2 , 1 mg/m 2 and 0.5
treated with mg/ m2 . After air-drying, 10 male German cockroaches were released and left in a constant temperature room at 25°C, and after 24 hours, the number of dead insects was counted. The inner walls of the shear were treated with butter to prevent insects from escaping. The results are shown as the average value of two series.
【表】
試験例 10
魚毒性
横60cm、縦30cm、高さ40cmの水槽に水を入れ、
体長約5cmのコイの当才魚を10匹放ち順応させた
後、各供試薬剤を水中濃度で10.1、0.1ppm等に
なるように添加し、48時間後、生死数を調査し、
魚に対する影響をみた。[Table] Test example 10 Fish toxicity Fill a water tank with width 60cm, length 30cm, and height 40cm.
After releasing 10 common carp fish with a body length of about 5 cm and allowing them to acclimate, each test chemical was added to the water at a concentration of 10.1 ppm, 0.1 ppm, etc., and after 48 hours, the number of live and dead fish was investigated.
We looked at the effects on fish.
【表】
死亡する薬剤濃度
試験例 11
毒性試験
マウス雄(体重19〜23g)にコーンオイルに溶
解または懸濁させた原液(0.2ml/体重10g)を
所定量経口投与し、7日後死亡数を調査し、マウ
スに対する影響をみた。[Table] Example of drug concentration test that causes death 11 Toxicity test A prescribed amount of the stock solution (0.2 ml/10 g body weight) dissolved or suspended in corn oil was orally administered to male mice (body weight 19-23 g), and the number of deaths was calculated after 7 days. We investigated the effect on mice.
【表】
*供試動物数の半数が死亡
する薬量
本発明化合物が対象害虫に高い効果を保有し、
かつ比較的低魚毒性であることが明らかである
が、この特性をさらに明確にするために、魚毒並
びに殺虫試験の結果から魚毒安全係数を求めた。
魚毒安全係数=魚毒性(TLm48 ppm)/水中薬
量濃度(LC50ppm)
感受性ツマグロヨコバイ(茅ケ崎)の雌成虫に
ついて試験例4に従つて種々の濃度で試験し、
各々3連反復の死亡率より中央致死量
(LC50ppm値)を求める。散布LC50(ppm)値相
当の濃度液を水深5cmに湛水した水田に、10アー
ル当り100散布し、これが全て水中に混入した
と仮定して求めた水中濃度を基にする。
たとえば本発明化合物では水深5cm、10アール
の水量は50tになり、そこに10アール当り100
LC50(ppm)値の有効成分量を散布すれば、水
中の薬量濃度は0.0102ppmになる。一方コイに対
する魚毒性TLm48(ppm)は>0.1ppmであるこ
とから、魚毒性TLm48(ppm)を水中の薬量濃
度で割れば魚毒安全係数が算出される。この場合
の値は9.8以上となる。[Table] *Half of the animals tested died.
The amount of the compound of the present invention that is highly effective against target pests,
It is clear that it has relatively low toxicity to fish, but in order to further clarify this characteristic, a fish toxicity safety factor was determined from the results of fish toxicity and insecticidal tests. Fish toxicity safety factor = fish toxicity (TLm 48 ppm) / drug concentration in water (LC 50 ppm) Female adult susceptible leafhoppers (Chigasaki) were tested at various concentrations according to Test Example 4,
Determine the median lethal dose (LC 50 ppm value) from the mortality rate of each triplicate. The concentration in water is based on the assumption that a solution with a concentration equivalent to the sprayed LC 50 (ppm) value is sprayed at 100 times per 10 ares into a rice field flooded to a depth of 5 cm, and all of this is mixed into the water. For example, with the compound of the present invention, the amount of water in 10 ares at a depth of 5 cm is 50 tons, and there is 100 tons per 10 ares.
If the amount of active ingredient with LC 50 (ppm) value is sprayed, the drug concentration in water will be 0.0102 ppm. On the other hand, since the fish toxicity TLm 48 (ppm) for carp is >0.1 ppm, the fish toxicity safety factor can be calculated by dividing the fish toxicity TLm 48 (ppm) by the drug concentration in water. In this case, the value will be 9.8 or higher.
【表】
本発明化合物は比較化合物に比し70倍以上安全
である。
以上の薬効試験および毒性試験の結果からも明
らかなとおり、比較化合物に対し、本発明化合物
はすぐれた殺虫力を有し、しかも温血動物に対し
て極めて毒性が低く、魚類に対しても、合成ピレ
スロイドより低毒性で、実質的に安全である特性
を有するものである。[Table] The compound of the present invention is 70 times safer than the comparative compound. As is clear from the results of the above drug efficacy tests and toxicity tests, the compounds of the present invention have superior insecticidal activity compared to comparative compounds, are extremely low in toxicity to warm-blooded animals, and are also highly effective against fish. It has the characteristics of being less toxic and substantially safer than synthetic pyrethroids.
Claims (1)
シフエニル)−2−メチルプロピルエーテル。 2 一般式〔〕で表わされる化合物を一般式
〔〕で表わされる化合物 〔式中、基Aおよび基Bはその一方の基がハロゲ
ン原子を表わし、他方の基が−O−M基(式中、
Mは水素原子またはアルカリあるいはアルカリ土
類金属原子を表わす)を表わすか、または共にヒ
ドロキシル基を表わす〕で表わされる化合物と反
応させることを特徴とする3−フエノキシベンジ
ル 2−(4−エトキシフエニル)−2−メチルプ
ロピルエーテルの製造法。 3 一般式〔〕において、基Aが−O−M基
(式中、Mは前記の意味を表わす)であり、一般
式〔〕において、基Bがハロゲン原子であるこ
とを特徴とする前記特許請求範囲第2項記載の製
法。 4 一般式〔〕において、基Aがハロゲン原子
であり、一般式〔〕において、基Bがヒドロキ
シル基である場合において、ジメチルスルホキシ
ドまたはスルホランの存在下、一般式〔〕で表
わされる化合物と一般式〔〕で表わされる化合
物を反応させることを特徴とする前記特許請求の
範囲第2項記載の製法。 5 一般式〔〕および一般式〔〕において、
基Aおよび基Bが共にヒドロキシル基であること
を特徴とする前記特許請求の範囲第2項記載の製
造法。 6 3−フエノキシベンジル 2−(4−エトキ
シフエニル)−2−メチルプロピルエーテルを含
有することを特徴とする殺虫、殺ダニ剤。[Claims] 1 3-Phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether. 2 A compound represented by the general formula [] is a compound represented by the general formula [] [In the formula, one group of group A and group B represents a halogen atom, and the other group represents an -O-M group (in the formula,
M represents a hydrogen atom, an alkali or alkaline earth metal atom), or both represent a hydroxyl group. Method for producing phenyl)-2-methylpropyl ether. 3 In the general formula [], the group A is an -OM group (in the formula, M represents the above meaning), and in the general formula [], the group B is a halogen atom, The manufacturing method according to claim 2. 4 In general formula [], when group A is a halogen atom and in general formula [], group B is a hydroxyl group, in the presence of dimethyl sulfoxide or sulfolane, a compound represented by general formula [] and general formula The manufacturing method according to claim 2, characterized in that a compound represented by [ ] is reacted. 5 In general formula [] and general formula [],
3. The method according to claim 2, wherein both group A and group B are hydroxyl groups. 6 An insecticide and acaricide characterized by containing 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13037181A JPS5832840A (en) | 1981-08-21 | 1981-08-21 | 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether, its preparation, and insecticidal and miticidal agent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13037181A JPS5832840A (en) | 1981-08-21 | 1981-08-21 | 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether, its preparation, and insecticidal and miticidal agent |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20198382A Division JPH0232266B2 (en) | 1982-11-19 | 1982-11-19 | 22 * 44ETOKISHIFUENIRU ** 2MECHIRUPUROPIRUARUKOORUOYOBISONOSEIZOHO |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5832840A JPS5832840A (en) | 1983-02-25 |
JPS6121615B2 true JPS6121615B2 (en) | 1986-05-28 |
Family
ID=15032763
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13037181A Granted JPS5832840A (en) | 1981-08-21 | 1981-08-21 | 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether, its preparation, and insecticidal and miticidal agent |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5832840A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5890525A (en) * | 1981-10-30 | 1983-05-30 | Mitsui Toatsu Chem Inc | Preparation of benzyl propyl ether derivative |
JP2532245B2 (en) * | 1986-05-19 | 1996-09-11 | 武田薬品工業株式会社 | Agrochemical solid formulation |
-
1981
- 1981-08-21 JP JP13037181A patent/JPS5832840A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5832840A (en) | 1983-02-25 |
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