GB1579514A - Optionally substituted phenoxybenzyl esters of-haloalkenyl isovalenic acids and pesticidal compositions containing them - Google Patents
Optionally substituted phenoxybenzyl esters of-haloalkenyl isovalenic acids and pesticidal compositions containing them Download PDFInfo
- Publication number
- GB1579514A GB1579514A GB9425/78A GB942578A GB1579514A GB 1579514 A GB1579514 A GB 1579514A GB 9425/78 A GB9425/78 A GB 9425/78A GB 942578 A GB942578 A GB 942578A GB 1579514 A GB1579514 A GB 1579514A
- Authority
- GB
- United Kingdom
- Prior art keywords
- general formula
- phenoxybenzyl
- isovalerate
- compounds
- isovaleric acid
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 105
- 230000000361 pesticidal effect Effects 0.000 title claims abstract description 28
- -1 phenoxybenzyl esters Chemical class 0.000 title claims description 53
- 239000002253 acid Substances 0.000 title description 9
- 150000007513 acids Chemical class 0.000 title description 3
- 239000004480 active ingredient Substances 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 10
- 239000000460 chlorine Substances 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 125
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 108
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 claims description 93
- 238000000034 method Methods 0.000 claims description 53
- 238000012360 testing method Methods 0.000 claims description 32
- 238000009472 formulation Methods 0.000 claims description 29
- 230000000694 effects Effects 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 241000255925 Diptera Species 0.000 claims description 11
- 230000002147 killing effect Effects 0.000 claims description 11
- 230000034994 death Effects 0.000 claims description 10
- 231100000517 death Toxicity 0.000 claims description 10
- 241000257226 Muscidae Species 0.000 claims description 9
- 239000000443 aerosol Substances 0.000 claims description 6
- 239000003595 mist Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000004495 emulsifiable concentrate Substances 0.000 claims description 5
- 239000002316 fumigant Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 241000257159 Musca domestica Species 0.000 claims description 2
- 239000002775 capsule Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 59
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 44
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 34
- 239000000243 solution Substances 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 238000009835 boiling Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 21
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 21
- 239000011541 reaction mixture Substances 0.000 description 20
- 238000000921 elemental analysis Methods 0.000 description 19
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical class O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 13
- 241000607479 Yersinia pestis Species 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000000575 pesticide Substances 0.000 description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 241000358422 Nephotettix cincticeps Species 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 8
- KGANAERDZBAECK-UHFFFAOYSA-N (3-phenoxyphenyl)methanol Chemical compound OCC1=CC=CC(OC=2C=CC=CC=2)=C1 KGANAERDZBAECK-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- ISULZYQDGYXDFW-UHFFFAOYSA-N 3-methylbutanoyl chloride Chemical compound CC(C)CC(Cl)=O ISULZYQDGYXDFW-UHFFFAOYSA-N 0.000 description 6
- 241001674044 Blattodea Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000003350 kerosene Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 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 5
- 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 5
- 241000238631 Hexapoda Species 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 229940024113 allethrin Drugs 0.000 description 5
- 150000001733 carboxylic acid esters Chemical class 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 230000002140 halogenating effect Effects 0.000 description 5
- 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 5
- 229960000490 permethrin Drugs 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 241000251468 Actinopterygii Species 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 241001414720 Cicadellidae Species 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 229950005499 carbon tetrachloride Drugs 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- NYPJDWWKZLNGGM-UHFFFAOYSA-N fenvalerate Chemical compound C=1C=C(Cl)C=CC=1C(C(C)C)C(=O)OC(C#N)C(C=1)=CC=CC=1OC1=CC=CC=C1 NYPJDWWKZLNGGM-UHFFFAOYSA-N 0.000 description 4
- 239000002917 insecticide Substances 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229940108410 resmethrin Drugs 0.000 description 4
- 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 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 241000238876 Acari Species 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 241000256259 Noctuidae Species 0.000 description 3
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- IWVHNUTWENFQDB-UHFFFAOYSA-N diethyl 2-(3,3-dichloroprop-2-enyl)-2-propan-2-ylpropanedioate Chemical compound CCOC(=O)C(CC=C(Cl)Cl)(C(C)C)C(=O)OCC IWVHNUTWENFQDB-UHFFFAOYSA-N 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- ASYNSFPROOUSEC-UHFFFAOYSA-N ethyl 3-methyl-2-(2-oxoethyl)butanoate Chemical compound CCOC(=O)C(C(C)C)CC=O ASYNSFPROOUSEC-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229960005235 piperonyl butoxide Drugs 0.000 description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 3
- 239000003380 propellant Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 2
- 241000238657 Blattella germanica Species 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
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000426497 Chilo suppressalis Species 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 241001466042 Fulgoromorpha Species 0.000 description 2
- FSYXMFXBRJFYBS-UHFFFAOYSA-N Furamethrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OCC1=CC=C(CC#C)O1 FSYXMFXBRJFYBS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 241000721451 Pectinophora gossypiella Species 0.000 description 2
- 241001608567 Phaedon cochleariae Species 0.000 description 2
- 241000227425 Pieris rapae crucivora Species 0.000 description 2
- 241000500437 Plutella xylostella Species 0.000 description 2
- 241000276427 Poecilia reticulata Species 0.000 description 2
- 241001522839 Saturnia japonica Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000007239 Wittig reaction Methods 0.000 description 2
- 230000003187 abdominal effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 2
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- BYQFBFWERHXONI-UHFFFAOYSA-N diethyl 2-propan-2-ylpropanedioate Chemical compound CCOC(=O)C(C(C)C)C(=O)OCC BYQFBFWERHXONI-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000000266 injurious effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 238000005949 ozonolysis reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- GWLJTAJEHRYMCA-UHFFFAOYSA-N phospholane Chemical compound C1CCPC1 GWLJTAJEHRYMCA-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000003389 potentiating effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 230000000699 topical effect Effects 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 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
- RLLPVAHGXHCWKJ-IEBWSBKVSA-N (3-phenoxyphenyl)methyl (1s,3s)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-IEBWSBKVSA-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
- WIQIRUONTRQXRN-UHFFFAOYSA-N 1,1,3-tribromoprop-1-ene Chemical compound BrCC=C(Br)Br WIQIRUONTRQXRN-UHFFFAOYSA-N 0.000 description 1
- JFEVIPGMXQNRRF-UHFFFAOYSA-N 1,1,3-trichloroprop-1-ene Chemical compound ClCC=C(Cl)Cl JFEVIPGMXQNRRF-UHFFFAOYSA-N 0.000 description 1
- RWICTFHJZGFXRW-UHFFFAOYSA-N 1,1-dibromo-3-chloroprop-1-ene Chemical compound ClCC=C(Br)Br RWICTFHJZGFXRW-UHFFFAOYSA-N 0.000 description 1
- MYBOTUJPOSBJSE-UHFFFAOYSA-N 1,2,3,7,8,9,10,10a-octahydropyrido[1,2-a][1,4]diazepine Chemical compound C1=CCNCC2CCCCN21 MYBOTUJPOSBJSE-UHFFFAOYSA-N 0.000 description 1
- OGFAWKRXZLGJSK-UHFFFAOYSA-N 1-(2,4-dihydroxyphenyl)-2-(4-nitrophenyl)ethanone Chemical compound OC1=CC(O)=CC=C1C(=O)CC1=CC=C([N+]([O-])=O)C=C1 OGFAWKRXZLGJSK-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- DQEUFPARIOFOAI-UHFFFAOYSA-N 2-propan-2-ylpropanedioic acid Chemical compound CC(C)C(C(O)=O)C(O)=O DQEUFPARIOFOAI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XXOSFUYRYSLQEN-UHFFFAOYSA-N 3,3,3-tribromoprop-1-ene Chemical compound BrC(Br)(Br)C=C XXOSFUYRYSLQEN-UHFFFAOYSA-N 0.000 description 1
- VKEIPALYOJMDAC-UHFFFAOYSA-N 3,3,3-trichloroprop-1-ene Chemical compound ClC(Cl)(Cl)C=C VKEIPALYOJMDAC-UHFFFAOYSA-N 0.000 description 1
- LLMLSUSAKZVFOA-UHFFFAOYSA-N 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(O)=O LLMLSUSAKZVFOA-UHFFFAOYSA-N 0.000 description 1
- JMURNZDCVGWDRG-UHFFFAOYSA-N 3-bromo-1,1-dichloroprop-1-ene Chemical compound ClC(Cl)=CCBr JMURNZDCVGWDRG-UHFFFAOYSA-N 0.000 description 1
- FAKIWEMTUHKHCG-UHFFFAOYSA-N 5,6,7,8-tetrahydro-1h-pyrazolo[1,2-a]pyridazine Chemical compound C1CCCN2CC=CN21 FAKIWEMTUHKHCG-UHFFFAOYSA-N 0.000 description 1
- VZXWRVKAQVLXGL-UHFFFAOYSA-N 5-(2,2-dichloroethenyl)-4,4-dimethyloxolan-2-one Chemical compound CC1(C)CC(=O)OC1C=C(Cl)Cl VZXWRVKAQVLXGL-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 206010002091 Anaesthesia Diseases 0.000 description 1
- 241000254175 Anthonomus grandis Species 0.000 description 1
- 101100006371 Arabidopsis thaliana CHX3 gene Proteins 0.000 description 1
- 241000238660 Blattidae Species 0.000 description 1
- 241000219198 Brassica Species 0.000 description 1
- 235000011331 Brassica Nutrition 0.000 description 1
- 241000907223 Bruchinae Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000257161 Calliphoridae Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241001124134 Chrysomelidae Species 0.000 description 1
- 241001414835 Cimicidae Species 0.000 description 1
- 241000255749 Coccinellidae Species 0.000 description 1
- 241000256113 Culicidae Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 description 1
- 241001466044 Delphacidae Species 0.000 description 1
- 241001481702 Dermanyssidae Species 0.000 description 1
- 241000131287 Dermestidae Species 0.000 description 1
- 241001414830 Diaspididae Species 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000002024 Gossypium herbaceum Species 0.000 description 1
- 235000004341 Gossypium herbaceum Nutrition 0.000 description 1
- 241000238816 Gryllidae Species 0.000 description 1
- 241001243087 Gryllotalpidae Species 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 241001147381 Helicoverpa armigera Species 0.000 description 1
- 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 1
- 241001470016 Laodelphax Species 0.000 description 1
- 241001124557 Lymantriidae Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- 241000555300 Mamestra Species 0.000 description 1
- 241000555303 Mamestra brassicae Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 241001556089 Nilaparvata lugens Species 0.000 description 1
- 241001579683 Patania ruralis Species 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241001415279 Pseudococcidae Species 0.000 description 1
- 241000258921 Pulicidae Species 0.000 description 1
- 241000255893 Pyralidae 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
- 241001124072 Reduviidae Species 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
- 241000254062 Scarabaeidae Species 0.000 description 1
- 241000176086 Sogatella furcifera Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 240000004460 Tanacetum coccineum Species 0.000 description 1
- 241000254107 Tenebrionidae Species 0.000 description 1
- 241000255588 Tephritidae Species 0.000 description 1
- 241001454295 Tetranychidae Species 0.000 description 1
- 241000896028 Tettigoniidae Species 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 241000130767 Tineidae Species 0.000 description 1
- 241000131339 Tipulidae Species 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ROVGZAWFACYCSP-MQBLHHJJSA-N [2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(C\C=C/C=C)C(=O)C1 ROVGZAWFACYCSP-MQBLHHJJSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000001949 anaesthesia Methods 0.000 description 1
- 230000037005 anaesthesia Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000006364 carbonyl oxy methylene group Chemical group [H]C([H])([*:2])OC([*:1])=O 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
- 230000007665 chronic toxicity Effects 0.000 description 1
- 231100000160 chronic toxicity Toxicity 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 244000038559 crop plants Species 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- ZLDOMUPTDYCDBS-UHFFFAOYSA-N ethyl 3,3-dimethylpent-4-enoate Chemical compound CCOC(=O)CC(C)(C)C=C ZLDOMUPTDYCDBS-UHFFFAOYSA-N 0.000 description 1
- PGDYJLZMIAGNNP-UHFFFAOYSA-N ethyl 6,6,6-trichloro-3,3-dimethylhexanoate Chemical compound CCOC(=O)CC(C)(C)CCC(Cl)(Cl)Cl PGDYJLZMIAGNNP-UHFFFAOYSA-N 0.000 description 1
- IKKRNFXTRYSMAF-UHFFFAOYSA-N ethyl 6,6-dichloro-3,3-dimethylhex-5-enoate Chemical compound CCOC(=O)CC(C)(C)CC=C(Cl)Cl IKKRNFXTRYSMAF-UHFFFAOYSA-N 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003958 fumigation Methods 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000002420 orchard Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- SBNFWQZLDJGRLK-UHFFFAOYSA-N phenothrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 SBNFWQZLDJGRLK-UHFFFAOYSA-N 0.000 description 1
- 229960003536 phenothrin Drugs 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 125000004591 piperonyl group Chemical group C(C1=CC=2OCOC2C=C1)* 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 229940015367 pyrethrum Drugs 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003903 river water pollution Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229960005199 tetramethrin Drugs 0.000 description 1
- 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 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 210000000115 thoracic cavity Anatomy 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/06—Unsaturated carboxylic acids or thio analogues thereof; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/32—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/52—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/64—Acyl halides
- C07C57/76—Acyl halides containing halogen outside the carbonyl halide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The pesticidal composition contains, as active ingredient, an alpha - or beta -substituted isovaleric ester of the formula <IMAGE> in which Z<1> denotes hydrogen, <IMAGE> or <IMAGE>, Z<2> denotes <IMAGE> or <IMAGE>, if Z<1> denotes hydrogen, or denotes hydrogen, if Z<1> denotes <IMAGE> or <IMAGE>, A denotes cyano or ethynyl if Z<1> denotes <IMAGE> or, if not, hydrogen, cyano or ethynyl, and X and Y are identical or different and denote chlorine or bromine.
Description
(54) OPTIONALLY a-SUBSTITUTED PHENOXYBENZYL
ESTERS OF (a OR p)-HALOALKENYL ISOVALERIC ACIDS AND
PESTICIDAL COMPOSITIONS CONTAINING THEM
(71) We, KURARAY CO. LTD., a company organised under the laws of
Japan, of 1621, Sakazu, Kurashiki-city, Japan, do hereby declare the invention, for which we pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to pesticidal compositions. The compositions of the present invention contain, as an active ingredient, an isovaleric acid ester substituted in the a- or p-position and having the general formula:
in which Z' is hydrogen and Z2 is CX2 = CII-CH2-I or CX2 = CH-CHY-, or is CX2 = CH- or CX2 = CH-CH2- and Z2 is hydrogen; when Z' is CX2 = CH-; and each X and Y, which may be the same or different, represents chlorine or bromine.
The isovaleric acid esters substituted in the a- or p-position as represented by general formula (I) comprise the four types of substituted isovaleric acid esters which may be designated by the following general formulae (I-A), (I-B), (I-C) and (l-D), respectively.
Since the discovery of BHC and dichlorodiphenyltrichloroethane, there has been an amazing development of insecticides containing, as an active ingredient, such compounds as organophosphorus compounds, carbamates and chlorinated organic compounds. Such insecticides have been used in farming and gardening and their use had resulted in marked increases in the yields of crops, thus enabling a stabilized supply of crops to be secured without being intiuenced by climatic conditions. However, this success has been more or less offset by the fact that such agricultural and horticultural insecticides have not only high toxicity to human beings and domesticated animals but also a high tendency to cause environmental pollution. Thus, the chronic toxicity and accumulation of such poisons have become major concerns of our times. Furthermore, in many geographical areas, agricultural pests such as green-rice leafhoppers and plant hoppers have been acquiring resistance to the common pesticides comprising organic phosphorus compounds or carbamates, and the development of substitutes for those chemicals is a pressing need today. Pyrethroid pesticides, such as allethrin, phthalthrin, resmethrin, furamethrin and pyrethrin, which have hitherto been used for the purpose of controlling household pests, not only are low in toxicity to man and domestic animals but also have excellent pesticidal activities and fast-acting properties against noxious insects, which acquire resistance to such compounds only with difficulty. However, because of their extremely low stability to light and low residual activity, these compounds cannot be used as agricultural or horticultural pesticides replacing organophosphorus or carbamate pesticides.
Under the circumstances, there have been some developments in agricultural and horticultural pesticides that take advantage of the characteristics of pyrethroids, which are not possessed by the conventional agricultural pesticides.
Among the pesticides recently developed are 3 - phenoxybenzyl (+) - cis, trans - 2,2 - dimethyl - 3 - (2,3 - dichlorovinyl)cyclopropanecarboxylate (Permethrin, U.S.P. No. 4,024,163), which has the structural formula:
and a - cyano - 3 - phenoxybenzyl a - (4 - chlorophenyl)isovalerate (Fenvalerate,
U.S.P. No. 3,996,244) which has the structural formula:
However, because of their high toxicity to fish, the applicability of these compounds is considerably restricted in geographical areas where, if used, they would contaminate natural waters such as river water.
Further, 3 - phenoxybenzyl a - (2,2 - dichlorovinyl)isovalerate, which has the structural formula:
and a - (allyl or 3,3 - dimethylallyl)isovaleric acid esters, which have the following structural formula:
(where A' is hydrogen, alkynyl or cyano) are reported to have pesticidal activity against agricultural, horticultural and household pests. (Published examined Japanese Patent Application No. 125723/1976 and U.S.P. No.4,042,710). However, none of these compounds possesses fully satisfactory pesticidal activity.
With a view to developing a pesticide that would have the characteric properties of pyrethroids and yet would display a higher residual activity than pyrethroids, a number of isovaleric acid esters having a substituent in the a- or position were synthesized and their pesticidal activity was investigated. The investigation revealed that certain a- or p-substituted isovaleric acid esters of the general formula (I) above possessed a markedly increased pesticidal activity as compared with the commonly used allethrin, as well as excellent resistance to light and hydrolysis and excellent residual activity, with many of such compounds being low in toxicity to fish. The present invention is based on the above discoveries.
It has been found that a- or p-substituted isovaleric acid esters of general formula (I) not only are pesticidally active against pests injurious to such plants as paddy rice plants, dry-field crop plants, cotton plants and orchard trees, which pests include green rice hoppers (Nephotettia cinticeps U,HLER), plant hoppers (e.g.
Sogatella furcifera HORVATH, Nilaparvata lugens STAL and Laodelphax stiatellus
FALLEN), rice-stem borers (Chilo suppressalis WALKER), cabbage armyworm (Mamestra brassica LINE), diamond-back moth (Plutella maculi-pennis CURTIS), owlet moths and underwings, common cabbage worm (Pieris rapae crucivora
BOISDUVAL), Japanese giant silk moth (Dictyoploca japonica BUTLER), bean web worm (Syllepte ruralis SCOPOLI), aphids, scale, mustard beetles (Phaedon cochleariae Fab.), boll weevils, pink bollworms (Pectinophora gossypiella Saund), tobacco budworms and mites, but also display excellent pesticidal activity against household pests such as houseflies, mosquitoes, and cockroaches (Blatella germanica). It should be understood that where the a- or p-substituted isovaleric acid ester of general formula (I) is a racemate, excellent effects will still be obtained if the racemate is resolved.
Among the compounds of general formula (I), those of general formulae (I-A) and (I-B) have particularly good pesticidal activity against the aforementioned variety of pests: they also have more potent killing effects upon agricultural and horticultural pests such as green rice leafhoppers than the known compound 3 - phenoxybenzyl a - (2,2 - dichlorovinyl)isovalerate. The a - (cyano or ethynyl) - 3 - phenoxybenzyl esters of a - (2,2 - dihalogenovinyl or 3,3 dihalogenoallyl)isovaleric acids have especially excellent killing effects upon agricultural and horticultural pests.
Regarding the compounds of general formula (I-C) and (I-D), the 2 phenoxybenzyl esters have good pesticidal activity against household pests such as houseflies, while the a - (cyano or ethynyl) - 3 - phenoxybenzyl esters have potent killing effects upon agricultural and horticultural pests such as green rice leafhoppers. Most of the a- or p-substituted isovaleric acid esters are extremely low in toxicity to fish and have promising applications as pesticides in localities where river water pollution and contamination are liable to take place. Thus, notwithstanding their varied pesticidal activities, the a- or p-substituted isovaleric acid esters of general formula (I) are low in toxicity to man and animals, with most of then being sparingly toxic to fish, are invariably highly resistant to light and hydrolysis, and have excellent residual activity.
Furthermore, the a- or p-substituted isovaleric acid esters of general formula (I) are not only insecticidal but also have promising repelling activity against mites, or/and produce synergistic effects with other biologically active compounds. Thus, the compounds (I) can be made available at low cost as control agents against agricultural and horticultural insects, forest insects, insects injurious to harvested crops, household insects, mites and other pests belonging to the following families:
Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Pyrrocoridae,
Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae, - Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae,
Noctuidae, Lymantriidae, Pyralidae, Culicidae, Tipulidae, Stomoxydae, Trypetidae,
Muscidae, Calliphoridae, Pulicidae, Tetranychidae and Dermanyssidae.
The following are examples of the a- or ,B-substituted isovaleric acid esters of general formula (I) according to this invention.
Compound No. Structural formula
a-Cyano-3-phenoxybenzyl a-(2,2-dichlorovinyl) isovalerate
a-Ethynyl-3-phenoxybenzyl a-(2,2-dichlorovinyl) isovalerate
a-Cyano-3-phenoxybenzyl a-(2,2-dibromovinyl) isovalerate
a-Ethynyl-3-phenoxybenzyl a-(2,2-dibromovinyl) isovalerate
3-Phenoxy benzyl a-(3,3-dichloroallyl)isovalerate
a-Cyano-3-phenoxybenzyl a-(3,3-dichlorallyl) isovalerate
Compound No. Structural formula
a-Ethynyl-3-phenoxybenzyl a-(3,3-dichlorallyl) isovalerate
3-Phenoxybenzyl a-(3 ,3-dibromoallyl) isovalerate
a-Cyano.3.phenoxybenzyl a-(3,3-dibromoallyl) isovalerate
a-Ethynyl-3-phenoxybenzyl a-(3 ,3-dibromoallyl) isovalerate
3-Phenoxybenzyl p-(3,3dichlorallyl) isovalerate
a-Cyano-3-phenoxybenzyl p-(3,3-dichlorallyl) isovalerate
Compound No. Structural formula
a-Ethylynyl-3-phenoxybenzyl P(3,3-dichlorallyl) isovalerate
3-Phenoxy benzyl p-(3,3-dibromoallyl) isovalerate
a-Cyano-3-phenoxybenzyl p-(3,3-dibromoallyl) isovalerate
a-Ethylynyl-3-phenoxybenzyl p-(3,3-dibromoallyl) isovalerate
3-Phenoxybenzyl p-(1,3,3-trichloroallyl) isovalerate
a-Cyano-3-phenoxybenzyl P-(l ,3,3-trichloroallyl) isovalerate
Compound No. Structural formula
a-Ethynyl-3-phenoxybenzyl P-(l ,3,3-trichloroallyl) isovalerate
3-Phenoxybenzyl p-(I-chloro-3,3-dibromoallyl) isovalerate
a-Cyano-3-phenoxybenzyl -(1-chloro-3,3- dibromoallyl)isovalerate
a-Ethynyl-3-phenoxybenzyl p-(1-chloro-3,3- dibromoallyl)isovalerate
3-Phenoxybenzyl -(I-bromo-3,3-dichloroallyl) isovalerate
a-Cyano-3-phenoxybenzyl -(1-bromo-3,3- dichloroallyl) isovalerate
Compound No. Structural formula
a-Ethynyl-3-phenoxybenzyl p-(1-bromo-3,3- dichloroallyl) isovalerate
3-Phenoxybenzyl 3-(1,3,3-tribromoallyl) isovalerate
a-Cyano-3-phenoxybenzyl p-(1,3,3-tribromoallyl) isovalerate
a-Ethynyl-3-phenoxybenzyl P-(l ,3,3-tribromoallyl) isovalerate
Among the a- or p-substituted isovaleric acid esters of general formula (I), the a-substituted isovaleric acid esters of general formula (I-A), the a-substituted isovaleric acid esters of general formula (I-B) and the p-substituted isovaleric acid esters of general formula (I-C) are novel compounds, and according to the results of researches made by the present inventors, can each be easily produced by the following processes (i) to (iii).
CX3Y Treatment x + X aY with base COOR COOR JCOOR (1L) (ill) Xy Reduction XX Hydrolysis )C COOR X COOR x HOCHq (IV) X Hciogenoting X HOCHQ ('V) xM COOH Halogenoti x cov Tertiary amne (I"-A) (I"'-A ) Ester inter change X < XCOOC A t (l-A) LCOOR Xx#VY(vli COOR or COOR COOR X (Vii) (Vl I" ccooR (V) Treatment with X Hydrolysis base > (VI11) \ < COOH; X COOR x (lxi ii, - I X X ondor XyCŎHH H x (X) (1-B) HoCAH I Ester interchange COO COUCH H (I-B)
(i-1) Ozonolysis ( 93 P/CXL COOR i;ni cxrrl y X yCOOR COOR (I' -B) (iii) OH H CH3C(ORi3 E a,, mQCOOR 3 CHX3 H Catclyst Ixm (rev) #COOR HX XM#COOR X 3C Treatment with base (XV) ( 1' -C) H)iHy I Ester interchange X A O (iii -1) yCOOR Ozonolysis,, oHc gCOOR 3 4 P/Cx (Xvii X > < XzC OOR I x tr-c
(where R is lower alkyl; X and Y are the same or different and each means chlorine or bromine; A is hydrogen, cyano or ethynyl).
The a-substituted isovaleric acid esters of general formula (I-A) are produced by the above process (i). First, a compound of general formula (II) and a tetrahalomethane, e.g. tetrachloromethane (carbon tetrachloride), tetrabromomethane (carbon tetrabromide) or monobromotrichloromethane, are heated to SO--1500C in the presence of a radical initiator such as benzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), acetyl peroxide or t-butyl perbenzoate to obtain a compound of general formula (III), which is then treated with a base such as 1,5 diazabicyclo[3,4,Oinonene - 5(DBN), 1,5 - diazabicyclo[5,4,Oiundecene - 5 (DBU), sodium ethoxide, potassium t-butoxide or sodium hydroxide, and the resultant product is reduced to a compound of general formula (I'-A). The above treatment with a base is desirably carried out in a solvent such as chloroform, tetrachloromethane, benzene, toluene, methanol, ethanol, tetrahydrofuran or n-hexane at a temperature of 0 C to 1000C. The reduction reaction is preferably carried out in an atmosphere of hydrogen gas and in the presence of a reduction catalyst, e.g.
palladium-on-carbon, palladium-on-barium-sulphate or palladium black, using a
solvent such as methanol, ethanol or n-hexane at a temperature which may range
from room temperature to 1000C. Then, the compound of general formula (l'-A) is hydrolysed in a conventional manner to the free carboxylic acid (I"-A) which,
in turn, is treated with a halogenating agent such as thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride or phosphorus oxybromide to obtain the corresponding carboxylic acid halide (I"--A). This carboxylic acid halide (l"'-A) is further reacted with an alcohol of general formula (IV) in the presence of a tertiary amine such as pyridine or triethylamine. By the above procedure is obtained the a-substituted isovaleric acid ester of general formula (I-A). An a-substituted isovaleric acid ester of general formula (I-A) may also be produced from a compound of general formula (I'-A) or a free carboxylic acid of general formula (I"-A) by several other alternative processes known per se, viz. (a) transesterification by reacting a compound of general formula (I'-A) directly with an alcohol of general formula (IV), (b) an esterification reaction involving a dehydrative condensation by reacting a free carboxylic acid of general formula (I"-A) with an alcohol (IV), (c) an esterification reaction in which a salt of free carboxylic acid (I"-A) with an alkali metal, silver or organic tertiary base is reacted with a sulfoxylate or halide of an alcohol (IV) or a quaternary ammonium salt thereof and (d) an esterification reaction by reacting the acid anhydride of a free carboxylic acid (I"-A) with an alcohol (IV).
The a-substituted isovaleric acid esters of general formula (I-B) can be produced by the above process (ii). First, a lower alkyl ester of isopropylmalonic acid of general formula (V) is reacted with a halogen compound of general formula (VI) or (VII), such as 1,1 - dichloro - 3 - bromo - 1 - propene, 1,1 - dibromo - 3 chloro - I - propene, 1,1,3 - trichloro - 1 - propene, 1,1,3 - tribromo - propene, 3,3,3 - trichloro - 1 - propene or 3,3,3 - tribromo - 1 - propene in the presence of a basic reagent at a temperature in the range 0 to 1000C to prepare a compound of general formula (VIII). As examples of said basic reagent may be mentioned sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium tbutoxide, sodium hydride, sodium amide, butyllithium, sodium hydroxide, potassium hydroxide, sodium carbonate, 1,5 - diaazabicyclo[5,4,0]undecene 5[DBU] and 1,5 - diazabicyclo[3,4,0]nonene - 5(DBN). Then, the compound of general formula (VIII) is saponified, e.g. with potassium hydroxide or sodium hydroxide, and then neutralized with acid. By this hydrolytic treatment, which is conventional per se, the monoester of general formula (IX) and/or dicarboxylic acid of general formula (X) can be obtained. Thus, depending on the conditions of hydrolysis, including the relative amount of potassium hydroxide or sodium hydroxide based on the compound of general formula (VIII), and the time and temperature of reaction, a compound of general formula (IX), a compound of general formula (X), or a mixture of (IX) and (X) is obtained. The mono-ester of general formula (IX) and/or the dicarboxylic acid of general formula (X) are/is subjected to decarboxylation reaction by heating at a temperature in the range of 120 to 2500C, whereby a compound of general formula (I'-B) and/or a free carboxylic acid of general formula (I"-B) is obtained. Where the compound of general formula (I'-B) and the free carboxylic acid of general formula (I"-B) are obtained as a mixture; these compounds may be separated from each other, e.g.
by distillation, or, alternatively, the mixture may be hydrolysed so as to convert the compound of general formula (I '-B) to the free carboxylic acid (I"-B). The compound of general formula (I'-B) can also be easily produced by the process (ii-l).
Thus, ozone gas is bubbled into a solution of the y,b-unsaturated carboxylic acid ester of general formula (XI) in a solvent such as methanol or n-hexane at -200C to -10"C, whereby an aldehyde of general formula (XII) is obtained. This compound of general formula (XII) is subjected to the so-called Wittig's reaction, that is to say, reacted with the phospholane as formed from triphenylphosphine and carbon tetrahalide (U.S.P. No. 4,024,163), whereby a compound of general formula (I'-B) can be easily obtained. the carbon tetrahalide mentioned above is preferably carbon tetrachloride or carbon tetrabromide. The Wittig reaction is expediently accomplished in the solvent used in the preparation of phospholane, although it may be conducted in any other solvent that does not interfere with the Wittig reaction, such as methylene chloride or benzene. The asubstituted isovaleric acid ester of general formula (I-B) can be obtained by subjecting either the compound of general formula (I '-B) or the free carboxylic acid of general formula (I"-B) to an ester interchange reaction similar to the above-mentioned process (i).
The p-substituted isovaleric acid ester of general formula (I-C) can be
produced by the above process (iii). Thus, in the first place, an orthocarboxylic acid
ester (XIII) acts upon 3 - methyl - 2 - buten - I - owl in the presence of an acidic
catalyst such as propionic acid, butyric acid, valeric acid, p-toluenesulfonic acid,
phenol or hydroquinone at a temperature in the range 120 to 1600C. to produce the v,-unsaturated carboxylic acid ester (XIV) (Published unexamined Japanese
Patent Applications Nos. 65710/1976 and 86410/1976). This y,X-unsaturated carboxylic acid ester (XIV) is then reacted with chloroform in the presence of a
catalyst, for example in the presence of a radical initiator such as azobisisobutyro
nitrile (AIBN), benzoyl peroxide (BPO), acetyl peroxide, di-t-butyl peroxide, t
butyl peracetate, t-butyl perbenzoate, t-butyl perphthalate or t-butyl
hydroperoxide at a temperature in the range 60 to 1500C, whereby the addition
compound (XV) is obtained. This addition compound (XV) is then treated with a
base such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t
butoxide, sodium isoamylate, 1,5 - diazabicyclo[5,4,0]undecene - 5 (DBU), 1,5 diazabicyclo[3,4,0] noriene - 5 (DBN), sodium hydroxide, potassium hydroxide,
sodium amide, sodium hydride or butyllithium at a temperature in the range -70" to +1500C, whereby a compound of general formula (I'-C) is obtained. The compound of general formula (I'-C) can also be produced by the method (iii-l).
This process can be effected by the same procedure as that of process (ii-l) except that the compound of general formula (XVI) is used in lieu of the compound of general formula (XI). By an ester interchange reaction of the compound of general formula (I'-C) in a manner analogous to that of the above process (i), the p substituted isovaleric acid ester of general formula (I-C) can be obtained.
The psubstituted isovaleric acid ester of general formula (I-D) is known only as an intermediate compound in the synthesis of 2,2 - dimethyl - 3 - (2,2 dichlorovinyl)cyclopropanecarboxylic acid, which is the acid residue of the
aforementioned permethrin. (Published unexamined Japanese Patent ADplications Nows. 98248/1976, 125251/1976 and 125252/1976). The p-substituted isovaleric acid
esters'of general formula (I-D) can be easily produced, for example by the following process (iv).
(iv) x xCOY xf Halogenating agent 0 x y o (Xvlt) (T"'-D) HCACIH (1 A $CCOCAIH H X Y O Tertiary amine X y OU (I - D) (where X and Y are the same or different and each is chlorine or bromine and A is hydrogen, cyano or ethynyl).
Thus, in the first place a y-lactone of general formula (XVII) is reacted with a halogenating agent to prepare a carboxylic acid halide of general formula (I"'-D).
When the halogenating agent is thionyl chloride, phosphorus pentachloride or phosphorus oxychloride, there is obtained a compound of general formula (I"'-D) in which Y is a chlorine, while a compound of general formula (I"'-D) in which Y is bromine is obtained when thionyl bromide or phosphorus pentabromide, for instance, is used as halogenating agent (Published unexamined Japanese Patent
Application No. 12160-1977). The carboxylic acid halide of general formula (I"'-D) can also be produced by the method that we have previously discovered, that is to say by reacting a y-lactone of general formula (XVII) with a thionyl halide in the presence of a Lewis acid catalyst, e.g. zinc chloride or tin tetrachloride, and a hydrogen halide. Then, in an inert solvent, the carboxylic acid halide of general formula (I"'-D) is reacted with an alcohol of general formula (IV) in the presence of a tertiary amine such as pyridine or triethylamine, whereby a -substituted isovaleric acid ester of general formula (I-D) is easily obtained. (Published unexamined Japanese Patent Application No. 125150/1977).
The a- or -substituted isovaleric acid ester of general formula (I) (hereinafter referred to as the active compound) can be used in the form of conventional formulations such as solutions, emulsifiable concentrates, wettable powders, suspensions, dusts, granules, microfine granules, powders, coatings, aerosols, mosquito incense coils, (these are helical coils of paper impregnated with insecticide and incense, which are stood on a saucer and burn away very slowly), fumigants, slow-acting fumigants, electric mosquito incense mats and capsules.
These formulations may be prepared by conventional procedures, for example by admixing the active compound with a volume-builder, such as a liquid, solid or liquefied gas diluent or carrier (optionally with a surfactant, i.e. an emulsifier and/or a dispersing agent and/or a foaming agent). Where water is used as the volume building, an organic solvent may be used as a co-solvent.
Suitable liquid diluents usually include aromatic hydrocarbons such as xylene, toluene, benzene and alkylnaphthalenes; chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene and methylene chloride; aliphatic or alicyclic hydrocarbons such as cyclohexane and paraffin (e.g. mineral oil distillate); alcohols such as butanol and glycol; glycol ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; highly polar solvents such as dimthylformamide, dimethylsulfoxide and acetonitrile; and water.
By "liquified gas diluent" is meant a material that is gaseous at normal temperature and pressure but can be liquified under pressure, such as aerosol propellants e.g. dichlorodifluoromethane and trichlorofluoromethane.
Preferred examples of solid diluent or carrier are finely divided naturally occurring minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth; and finely divided synthetic minerals such as alumina and silicates.
As preferred examples of emulsifiers and foaming agents may be mentioned nonionic and anionic emulsifying agents such as polyoxyethylene-aliphatic carboxylic acid esters; polyoxyethylene-aliphatic alcohol ethers such as alkyl aryl polyglycol ether; alkylsulfonates, alkylsulfates, arylsulfonates and albumin hydrolysate. Preferred examples of the dispersing agents include spent lignosulfite liquor and methylcellulose.
Adhesive agents such as carboxymethylcellulose; powdery, granular or latextype naturally occurring or synthetic high-molecular-weight compounds such as gum Arabic, polyvinyl alcohol and polyvinyl acetat (resmethrin), 5 - propargylturturyl chrysanthemate(turamethrin) 5 - propargyl 2 - methyl - 3 - furylmethyl chrysanthemate(proparthrin), 3 - phenoxybenzyl chrysanthemate(phenothrin), a - ethynyl - 3 - phenoxybenzyl chrysanthemate, 3 phenoxy - benzyl 2,2 - dimethyl - 3 - (2,2 - dichlorovinyl)cyclopropanecarboxylate(permethrin), a - ethynyl - 3 - phenoxybenzyl 2,2 - dimethyl - 3 - (2,2 dichlorovinyl)cyclopropanecarboxylate and a - cyano - 3 - phenoxybenzyl 2,2 dimethyl - 3 - (2,2 - dichlorovinyl)cyclopropanecarboxylate; and substituted acetic acid esters such as a - cyano - 3 - phenoxybenzyl a - (4 - chlorophenyl)isovalerate and a - ethynyl - 3 - phenoxybenzyl a - (4 - chlorophenyl)isovalerate.
In each formulation, the active compound is generally incorporated at the level of 0.01 to 95 weight percent, preferably 0.1 to 90 weight percent.
The active compound of this invention can be used in any of the aforementioned varied types of formulations or as further formulated into various application forms. The content of the active compound in such an application form may be varied over a broad range. The concentration of active compound in such an application form may range from 0.0000001 to 100 weight percent, preferably from 0.001 to 10 weight percent.
The pesticides containing any of the active compounds according to this invention can be put to use by routine procedures suited to modes of application.
The following examples of synthesis, testing examples, formulation examples and examples of effects are further illustrative of this invention. In the formulation examples and effect examples, all parts are by weight. The compound numbers correspond to the a- or -substituted isovaleric acid esters (I) to (28) of the general formula (I) mentioned hereinbefore.
Example of Synthesis-l
To a mixture of 4.4 g of ethyl a-isopropylacrylate and 40 g of monobromotrichloromethane was added 0.14 g of t-butyl perbenzoate and the entire mixture was heated at 1200C for 12 hours. The reaction mixture was distilled to remove the low-boiling fraction and then further subjected to distillation under reduced pressure to recover 8.5 g. of ethyl a-bromo-a-(2,2,2-trichloroethyl)isovalerate, b.p.
132--136"C/0.8 mmHg (yield 81%).
In 20 g of chloroform was dissolved 6.ü g of the ethyl a-bromo-a-(2,2,2-tri- chloroethyl)isovalerate and, after the addition of 3.5 g of 1,5-diazabicylco[5,4,0]- undecene-5 (DBU), the solution was stirred at room temperature for 2 hours. The reaction mixture was then diluted with diethyl ether, washed with water and dilute aqueous hydrogen chloride and dried over anhydrous magensium sulfate. The lowboiling fraction was removed by distillation, whereupon 4.6 g of oily product was obtained. Based on its NMR spectrum and .gc-mass spectrum, this product was identified to be ethyl a-isopropyl-p-trichloromethylacrylate containing a certain amount of ethyl a-bromo-a-(2,2,-dichlorovinyl) isovalerate. In 50 ml of ethanol was dissolved 4.6 g of the oily product obtained above and, following the addition of 0.4 g of 5% palladium-on-carbon, the solution was stirred in an atmosphere of hydrogen gas at 550C for 6 hours. Thereafter, the reaction mixture was filtered to remove the catalyst and the ethanol was distilled off. By the above procedure was obtained 3.9 g of ethyl a-(2,2-dichlorovinyl)isovalerate as oil. then, 3.9 g of this ethyl a-(2,2-dichlorovinyl)isovalerate was dissolved in 20 ml of ethanol and a solution of 2.0 g of sodium hydroxide in 10 ml of water was added to the above ethanol solution. The mixture was stirred at room temperature for 10 hours, at the end of which time the ethanol was distilled off. The residue was neutralized with aqueous hydrogen chloride and extracted with diethyl ether. The ethereal solution yielded 2.9 g of a-(2,2-dichlorovinyl)isovaleric acid having the following NMR spectrum [yield: 84% based on ethyl a-bromo-a-(2,2,2-trichloroethyl)isovaleratei.
NMR spectrum (60 MHz) a TCMIs: 0.97(d, J = 7Hz), l.03(d, J = 7Hz), 6H; 1.83--2.36(m)ln; 3.23(d, J = t0Hz), 3.35(d, J = 10Hz)lH; 6.04(d, J = 10Hz)lH.
In 15 ml of dry benzene was dissolved 1.8 g of a-(2,2-dichlorovinyl)isovaleric acid, followed by the addition of 3.5 g of thionyl chloride. The mixture was refluxed for 5 hours and, then, distilled to remove the low-boiling fraction. By the above procedure was obtained a-(2,2-dichlorovinyl)isovaleroyl chloride. This chloride was dissolved in 20 ml of benzene, and 2.0 g of a-ethynyl-3-phenoxybenzyl alcohol was added. This was followed by the addition of 2.9 g of pyridine and the mixture was stirred at room temperature for 8 hours. The resultant reaction mixture was diluted with diethyl ether, washed with water and dilute aqueous hydrogen chloride and dried over anhydrous magnesium sulfate. The low-boiling fraction was then distilled off and the residue was chromatographed on a column of silica gel (benzene/n-hexane = 1:1 v/v). By the above procedure was obtained 2.6 g of cu- ethynyl-3-phenoxybenzyl a-(2,2-dichlorovinyl)isovalerate[compound (2)] [yield: 71% based on a-(2,2-dichlorovinyl)isovaleric acid].
NMR spectrum (60 MHz) a CDCl3
TMS 0.78--1.06(m)6H, 1.80--2.47(m)lH, 2.61(d, J=2Hz)lH, 3.29 (dd, J=7Hz &
10Hz)lH, 6.00(d, J = l0Hz)lH, 6.44(d, J = 2Hz) 1H, 6.85-7.55(m)9H Elemental analysis (calcd. in parentheses): C% 65.65(65.52) H% 5.09 (5.00)
Example of Synthesis-2.
In 20 ml of dry benzene was dissolved 2.0 g of a-(2,2-dichlorovinyl)isovaleric acid, followed by the addition of 6.0 g of thionyl chloride. The mixture was refluxed overnight. It was then distilled to remove the low-boiling fraction, whereby a-(2,2dichlorovinyl)isovaleroyl chloride was obtained. This a-(2,2-dichlorovinyl)- isovaleroyl chloride was dissolved in 25 ml of dry benzene, followed by the addition of 2.3 g of zr-cyano-3-phenoxybenzyl alcohol and, then, 2.4 g of pyridine.
The mixture was stirred at room temperature overnight. The resultant reaction mixture was diluted with diethyl ether, washed with water and dilute aqueous hydrogen chloride, dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. Column chromatography was carried out on the residue to obtain 3.2 g of a-cyano-3-phenoxybenzyl e-(2,2-dichlorovinyl)isovalerate [Compound (I)] which was shown to have the properties given below [yield: 78% based on a-(2,2-dichlprovinyl)isovaleric acid].
NMR spectrum (60 MHz) 8 CDCl3
TMS 0.78--1.04(m)6H, 1.74--2.40(m)lH, 3.31(dd, J=7Hz & lûHz)lH 5.95(d, J = lOHz)lH, 6.33(s)lH, 6.87-7.53(m)9H Elemental analysis (calcd. in parentheses): C% 62.28(62.39)
H% 4.70(4.74)
Example of Synthesis-3
10.5 g of sodium hydride (ca. 50%) was washed with n-hexane and suspended in 430 g of benzene with stirring. To this suspension was added 36.8 g of diethyl isopropylmalonate and the mixture was refluxed for about 40 minutes. The reaction mixture was then allowed to stand and cool for about 20 minutes, after which 37.9 g of I,I.dichloro-3-bromo-l-propene was added in several instalments. The mixture was then stirred under reflux for 1.5 hours. After cooling, the reaction mixture was washed with water and dilute hydrochloric acid, dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. The resultant oil was further distilled under reduced pressure to obtain 52.3 g of diethyl isopropyl-(3,3dichloroallyl)malonate which was shown to have the tollowlng NMK spectrum [yield: 92% based on diethyl isopropylmalonate].
NMR spectrum (60 MHz) 8 CHCM4s:
HMS 0.94(d, J = 7Hz)6H, 1.22(t, J = 7Hz)6H, 2.04-2.44(m)lH, 2.64 (d, J = 7Hz)2H, 4. 16(q, J = 7Hz)4H, 5.90(t, J = 7Hz)l H In 20 g of ethanol was dissolved 8.8 g of the above diethyl isopropyl-(3,3 dichloroallyl)malonate and a solution of 6.4 g of potassium hydroxide in 10 g of water was added to the above ethanol solution. The mixture was refluxed overnight. Then, the reaction mixture was distilled to remove the ethanol and a sufficient amount of dilute hydrochloric acid was added to make the residue acidic.
The residue was extracted with diethyl ether and the ethereal layer was dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. By this procedure was obtained a mixture of isopropyl-(3,3-dichloroallyl)malonic acid and monoethyl isopropyl-(3,3-dichloroallyl)malonate. This mixture was subjected to decarboxylation reaction at 180 to 2300C under a reduced pressure. of 35 to 60 mmHg, whereupon 6.0 g of a mixture of a-(3,3-dichloroallyl)isovaleric acid and ethyl a-(3,3-dichloroallyl)isovalerate was obtained. In 20 g of ethanol was dissolved 6.0 g of the above decarboxylated mixture and a solution of 1.2 g of sodium hydroxide in 10 g of water was added to the above solution. The mixture was refluxed for 4 hours, after which the ethanol was distilled off. The residue was made acidic with dilute hydrochloric acid and extracted with diethyl ether. The ethereal layer was dried over anhydrous magnesium sulfate and distilled to remove the lowboiling fraction. By the above procedure was obtained 4.2 g of a-(3,3-dichloroallyl)isovaleric acid, the NMR spectrum of which appears below [yield: 70% based on diethyl isopropyl-(3,3-dichloroallyl)malonate].
NMR spectrum (60 MHz) a CHCM4s: HMS
1.01(d, J=7Hz)6H, 1.67--2.67(m) 4H, 5.94(t, J=7Hz)lH
To 2.1 g of a-(3,3-dichloroallyl)isovaleric acid was added 3.0 g of thionyl chloride as well as 10 g of benzene and the mixture was refluxed for 5 hours.
Then, the reaction mixture was distilled to remove the low-boiling fraction.
By this procedure was obtained cw-(3,3-dichloroallyl)isovaleroyl chloride. This chloride was dissolved in 30 g of dry benzene, followed by the addition of 2.0 g of 3-phenoxybenzyl alcohol. Then, 2.0 g of pyridine was added dropwise and the mixture was stirred at room temperature overnight. The reaction mixture was then diluted with diethyl ether, washed with dilute hydrochloric acid and water, dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction.
The residual viscous oil was purified by column chromatography to recover 3.1 g of 3-phenoxybenzyl a-(3,3-dichloroallyl)isovalerate[Compound (5)] having the following properties [yield: 79% based on a-(3,3-dichloroallyl)isovalerylic acid].
NMR spectrum (60 MHz) a CDCI, 0.94(d, J = 7Hz)6H, 1.65--2.66(m)4H, 5.14(s)2H, 5.87(t, J = 7Hz)lH, 6.83-7.60(m)9H Elemental analysis (calcd. in parentheses): C% 64.20(64.13)
H% 5.58(5.64)
Examples of Synthesis-4 & 5.
The procedure of Example of Synthesis-3 was repeated except that 2.3 g of a- cyano-3-phenoxybenzyl alcohol or 2.3 g of a-ethynyl-3-phenoxybenzyl alcohol was used in lieu of 2.0 g of 3-phenoxybenzyl alcohol. By these procedures were obtained the corresponding a-(3,3-dichloroallyl)isovaleryl acid esters [Compound (6) and Compound (7)], respectively. The yields, NMR spectra and elemental analyses of these esters are shown below.
Compound (6): yield 3.5 g (84%)
NMR spectrum (60 MHz) a TCMSCii: 0.78-I .05(m)6H, I .63-2.52(m)4H, 5.60--5.94(m)lH, 6.38(s)lH, 6.85-7.55(m)9H Elemental analysis (calcd. in parentheses): C% 63.09 (63.17)
H% 4.95(5.06)
Compound (7): yield 3.0 g (72%) NMR spectrum (60 MHz) a CDCl3
TMS 0.81-I .05(m)6H, 1 .62-2.55(m)4H, 2.63(d, J = 2Hz) 1 H, 5.67--5.98(m)1H, 6.47(d, J = 2Hz)lH, 6.87-7.55(m)9H Elemental analysis (calcd. in parentheses): C% 66.31(66.20) H% 5.38(5.31)
Example of Synthesis-6
In 100 g of methanol was dissolved 10.0 g of ethyl a-allylisovalerate [general formula (XI) where R = -CH2CH3] and, under cooling at -20--100C and stirring, ozone gas was bubbled into the solution for 8 hours. Then, at room temperature, the reaction mixture was added to 100 g of dimethyl sulfide and the mixture was stirred at that temperature overnight. The reaction mixture was then distilled under reduced pressure to remove the low-boiling fraction and the residue was diluted with 50 g of diethyl ether. Following the addition of 4 g of calcium chloride, HCI gas was bubbled into the mixture at room temperature for 10 minutes. Then, 5 g of anhydrous potassium carbonate was added and the mixture was thoroughly stirred.
The diethyl ether solution was taken, washed with water, dried over anhydrous magnesium sulfate and distilled under reduced pressure to remove the low-boiling fraction. By the above procedure was obtained 9.0 g of ethyl 2 - isopropyl - 3 formyl - propionate[general formula (XII) wherein R=-CH2CH3][yield: 89% based on ethyl a-allylisovalerate; the NMR spectrum of the aldehyde (60 MHz)
a HMS : 9 9.74] In 240 g of methylene chloride was dissolved 12.5 g of carbon tetrabromide, followed by the addition of 19.8 g of triphenylphosphine. The mixture was thoroughly stirred. To this mixed solution was added 5.0 g of the ethyl 2 isopropyl - 3 - formyl - propionate prepared above and the mixture was stirred at room temperature overnight. Thereafter, the low-boiling fraction was distilled off under reduced pressure and the residue was stirred well with diethyl ether and water. The diethyl ether layer was taken and distilled under reduced pressure to remove the low-boiling fraction. To the residue was added petroleum ether and, after thorough stirring, the petroleum ether solution was taken and further distilled under reduced pressure to remove the low-boiling fraction. The resultant oily residue was purified by distillation under reduced pressure. By the above procedure was obtained 4.6 g of ethyl sr-(3,3-dibromoallyl)isovalerate[yield: 48% based on ethyl 2 - isopropyl - 3 - formyl - propionate] NMR spectrum (60 MHz) a CDCI,
HMS 0.88(d, J = 6.5Hz)6H, 1.20(t, J = 7Hz)3H, 1.65--2.38(m)4H, 4.09(q,
J = 7Hz)2H, 6.35(t, J = 7Hz)lH
In a mixture of 7 g of water and 20 g of ethanol was dissolved 1.1 g of sodium hydroxide and 4.6 g of the ethyl a-(3,3-dibromoallyl)isovalerate obtained above was added to the above solution. The mixture was stirred at room temperature overnight and, then, refluxed for 3 hours. The reaction mixture was then distilled to remove the ethanol and the residue was made acidic by the addition of dilute hydrochloric acid and extracted with diethyl ether. The ethereal layer was dried over anhydrous magnesium sulfate and the low-boiling fraction was distilled off. By the above procedure was obtained 3.7 g of a-(3,3-dibromoallyl)isovaleric acid, the
NMR spectrum of which is shown below [yield: 88% based on ethyl a-(3,3dibromoallyl)isovalerate] .
NMR spectrum (60 MHz) a CDCI, HMS
0.92(d, J = 6.5Hz)6H, 1.67--2.42(m)4H, 6.39(t, J = 7Hz) 1H, 10.63(s)lH In 20 g of benzene was dissolved 2.0 g of cg-(3,3-dibromoallyl)isovaleric acid,
followed by the addition of 4.7 g of thionyl chloride and 2 drops of N,N-dimethylformamide. The mixture was refluxed overnight and, then, distilled to remove the low-boiling fraction. As the residue was obtained a-(3,3-dibromoallyl)isovaleroyl chloride. This a-(3,3-dichloroallyl)isovaleroyl chloride was dissolved in 30 g of dry benzene and 1.5 g of a-ethynyl-3-phenoxybenzyl alcohol was added. This was further followed by the dropwise addition of 1.6 g of pyridine and the mixture was stirred at room temperature overnight. Thereafter, the reaction mixture was further stirred at 40--500C for 2 hours, after which it was diluted with diethyl ether, washed with dilute hydrochloric acid and water, dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. The resultant viscous oil was purified by column chromatography to recover 2.0 g of a-ethylnyl-3-phenoxybenzyl a-(3,3-dibromoallyl)isovalerate [Compound (10)] which was shown to have the properties indicated below. [yield: 59% based on a-(3,3-dibromoallyl)isovaleric acid] NMR spectrum (60 MHz) a CDCl3
HMS
0.74--1.03(m)6H, 1.60--2.43(m)4H, 2.53--2.63(m)1H, 6.12--6.50(m)2H,
6.84-7.50(m) Elemental analysis (calcd. in parentheses): C% 54.66(54.57)
H% 4.40(4.38)
Examples of Synthesis-7 & 8.
The procedure described in Example of Synthesis-6 was followed except that
1.4 g of 3-phenoxybenzyl alcohol or 1.5 g of a-cyano-3-phenoxybenzyl alcohol was
used in lieu of 1.5 g of a-ethynyl 3-phenoxybenzyl alcohol. By these procedures were obtained the corresponding a-(3,3-dibromoallyl)isovaleric acid esters compound (8) and Compound (9)], respectively. The yields, NMR spectra and
elemental analyses of these esters are given below.
Compound (8): yield 2.6 g (81%)
NMR spectrum (60 MHz) a TCMCsl3: 0.91(d, J=6.5Hz)6H, 1.65--2.50(m)4H, 5.09(s)2H, 6.35(t, J=7Hz)lH, 6.87-7.50(m)9H Elemental analysis (calcd. in parentheses): C% 52.18(52.31)
H%4.55(4.60)
Compound (9): yield 2.2 g (65%)
Elemental analysis (calcd. in parentheses): C% 51.97(52.10)
H% 4.12(4.17)
Example of Synthesis-9
A pressure-resistant tubular reactor was charged with a mixture of 20.0 g of ethyl 3,3-dimethyl-4-pentenate, 200 g of chloroform and 1.0 g of t-butyl perbenzoate and, after the tube was sealed, the contents were heated at 12 C for 20 hours. Then, the reaction mixture was distilled to remove the low-boiling fraction and further subjected to distillation under reduced pressure. By the above procedure was obtained 27.2 g of ethyl p-(3,3,3-trichloropropyl)isovalerate(ethyl 6,6,6-trichloro-3,3-dimethylhexanoate) (yleld: 77%).
b.p. 90-920C/0.6 mmHg NMR spectrum (60 MHz) a CDCl3:
TMS 1.07(s), 1.26(t, J = 7Hz)9H; 1.67--2.03(m)2H; 2.24(s)2H; 2.60--2.95(m)2H; 4.17(q, J = 7Hz)2H
In 50 g of ethanol was dissolved 2.5 g of sodium metal and 20.0 g of the above ethyl p-(3,3,3-trichloropropyl)isovalerate was added to the solution. The mixture was refluxed for 8 hours. The reaction mixture was neutralized with a solution of hydrogen chloride in dry ethanol and concentrated to about one-twentieth of its original volume. To this concentrate was added 100 g of ice-water and the mixture was extracted with diethyl ether. The ethereal layer was dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. By the above procedure was obtained 13.7 g of ethyl p-(3,3-dichloroallyl)isovalerate (ethyl 6,6dichloro-3,3-dimethyl-5-hexenoate), the NMR spectrum of which is given below.
(yield: 79 /O) NMR spectrum (60 MHz) a CHCM4s:
HMS 0.99(s)6H, 1.20(t, J = 7.5Hz)3H, 2.09-2.35(m)4H, 4.07(q, J = 7.5Hz)2H, 5.94
(t, J = 7.5Hz)lH
To a solution of 2.2 g of sodium hydroxide in 15 g of water was added 10.0 g of
the above ethyl p-(3,3-dichloroallyl)isovalerate as well as 20 g of ethanol, and the
mixture was refluxed for 4 hours. The reaction mixture was distilled to remove the
ethanol, made acidic with aqueous hydrogen chloride and extracted with diethyl
ether. The ethereal layer was dried over anhydrous magnesium sulfate and distilled
to remove the low-boiling fraction. By the above procedure was obtained 8.2 g of P- (3,3-dichloroallyl)isovaleric acid (6,6-dichloro-3,3-dimethyl-5-hexanoic acid), the
NMR spectrum of which is given below. (yield: 93%) CCl
NMR spectrum (60 MHz) a HMS : 1.04(s)6H, 2.14-2.34(m)4H, 5.94(t, J = 7.5Hz)lH
To 2.1 g of p-(3,3-dichloroallyl)isovaleric acid was added 3.0 g of thionyl chloride and 10 g of benzene, and the mixture was refluxed for 5 hours. The reaction mixture was then distilled to remove the low-boiling fraction and recover ,B-(3,3-dichloroallyl)isovaleroyl chloride as the residue. This -(3,3-dichloroallyl)- isovaleroyl chloride was dissolved in 30 g of dry benzene and 2.0 g of 3-phenoxybenzyl alcohol was added to the solution. This was further followed by the dropwise addition of 1.6 g of pyridine and the mixture was stirred at room temperature overnight. Thereafter, the reaction mixture was diluted with diethyl ether, washed with dilute aqueous hydrogen chloride and water, dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. The resulting oily residue was purified by column chromatography to obtain 2.8 g of 3-phenoxybenzyl P-(3,3- dichloroallyl)isovalerate [Compound (I I)] having the following properties. [yield: 71% based on p(3,3-dichloroallyl)isovalen.c acid] NMR spectrum (60 MHz) a HCM4s:
HMS 0.93(s)6H, 2.03-2.23(m)4H, 4.98(s)2H, 5.88(t, J = 7.5Hz) 1H, 6.76-7.50(m)9H Elemental analysis (calcd. in parentheses): C /O 64.08(64.13)
H% 5.60(5.64)
Examples of Synthesis-lO & II.
The procedure described in Example of Synthesis-9 was repeated except that 2.2 g of a-cyano-3-phenoxybenzyl alcohol or 2.2 g of a-ethynyl-3-phenoxybenzyl alcohol was used in lieu of 2.0 g of 3-phenoxybenzyl alcohol. By these procedures were obtained the corresponding esters of p-(3,3-dichloroallyl)isovaleric acid [Compound (12) and Compound (13)], respectively. The yields, NMR spectra and
elemental analysis of these esters are given below.
Compound (12):
Yield 3.4 g (81%) NMR spectrum (60 MHz) a TMS 3
TMS 1.01(s)6H; 2.19(d, J = 8Hz), 2.30(s)4H; 5.89(t, J = 8Hz)lH; 6.38(s)1H: 6.907.50(m)9H Elemental analysis (calcd. in parentheses): C% 62.98(63.17)
H% 5.06(5.06)
Compound (13)
Yield 3.3 g(79%) NMR spectrum (60 MHz) a CDCl3
TMS 0.96(s)6H, 2.07-2.28(m)4H, 2.53(d, J=2Hz)lH, 5.87(t, J=8Hz)lH, 6.44(d, J=2Hz)lH, 6.83-7.50(m)9H Elemental analysis (calcd. in parentheses): C% 66.05(66.20)
H% 5.19(5.31)
Example of Synthesis-12.
In 150 g of benzene was dissolved 62.7 g of 3,3-dimethyl-4-(2,2-dichlorovinyl)4-butanolide and, at room temperature, hydrogen chloride gas was bubbled into the solution for one hour. Then, 3.0 g of zinc chloride was added and the mixture was refluxed. While the introduction of hydrogen chloride gas was continued, 107.0 g of thionyl chloride was added dropwise over a period of one hour. The mixture was further heated at that temperature for one hour. The mixture was further heated at that temperature for 4 hours, after which time the excess of thionyl chloride and benzene were distilled off under reduced pressure. The residue was subjected to distillation under reduced pressure to recover 49.1 g of 3,3-dimethyl4,6,6-trichloro-5-hexanoyl chloride which was shown to have the following properties. (yield: 62%)
b.p. 798laC/0.65 mmHg NMR spectrum (60 MHz) # CCl4 :
HMS 1.14(s)3H, 1.17(s)3H, 2.87(d, J= 17Hz)lH, 3.22(d, J= 17Hz)lH, 4.83(d, J= l0.5Hz)lH, 6.04(d, J= 10.5Hz)lH In 30 g of dry benzene was dissolved 2.6 g of 4,6,6-trichloro-3,3-dimethyl-5- hexanoyl chloride and 2.0 g of 3-phenoxybenzyl alcohol was added to the solution.
This was followed by the dropwise addition of 2.4 g of pyridine and the mixture was stirred at room temperature overnight. The reaction mixture was then diluted with diethyl ether, washed with dilute aqueous hydrogen chloride and water, dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. The residual viscous oil was purified by column chromatography. By the above procedure was obtained 3.9 g of 3-phenoxybenzyl -(1,3,3-trichloroallyl)- isovalerate [3-phenoxybenzyl 4,6,6-trichloro-3,3-dimethyl-5-hexanoate, Compound (17)], the NMR spectrum and elemental analysis of which are given below. (yield: 91%) NMR spectrum (60 MHz) a CCl4
HMS I.03(s)6H, 2.18(d, J= 15Hz)lH, 2.52(d, J= 15Hz)lH, 4.87 (d, J= 10.5Hz)lH, 5.02(s)2H, 6.02(d, J= 10.5Hz)lH, 6.807.50(m)9H Elemental analysis (calcd. in parentheses): C% 58.85(58.97)
H% 5.02 (4.97)
Examples of Synthesis-13 & 14.
The procedure described in Example of Synthesis-12 was repeated except that 2.3 g of a-cyano-3-phenoxybenzyl alcohol or 2.3 g of a-ethynyl-3-phenoxybenzyl alcohol was used in lieu of 2.0 g of 3-phenoxybenzyl alcohol. By the above procedures were obtained the corresponding esters of p-(1,3,3-trichloroallyl)- isovaleric acid [Compound (18) and Compound (19)], respectively. The yields,
NMR spectra and elemental analyses of these esters are as follows.
Compound (18):
Yield 3.8 g (84%) CDCl
NMR spectrum (60 MHz) a TMS 1.08(s)6H; 2.33(bd, J = 15Hz), 2.66(bd, J = 15Hz)2H; 4.80(d, J = 10.5Hz)lH; 6.02(d, J=10.5Hz)1H; 6.36(s)1H; 6.92-7.58(m)9iH Elemental analysis (calcd. in parentheses): C% 58.45(58.36)
H% 4.41(4.45)
Compound (19): Yield 3.6 g (80%) NMR spectrum (60 MHz) a CDCl3:
TMS
0.94(s)6H; 2.11(d, J=l5Hz), 2.14(d, J= 15Hz), 2.38 (d, J=l5Hz), 2.41(d, J = 15Hz), 2.45(d, J = 2Hz)3H; 4.69(d, J = 11Hz), 4.72(d, J = I 1Hz)1H; 5.86(d,
J= IlHz)lH; 6.30(d, J=2Hz)lH; 6.77.25(m)9H Elemental analysis (calcd. in parentheses): C% 61.25(61.14)
H
TABLE 1
Mortality ("/o) Test compound No. 10 pg"fly Ig?ly (1, 100 100 (2) 100 100 (5) 100 100 (6) 100 100 (7) 100 90 (8) 100 100 (9) 100 100 (10) 100 100 (11) 100 100 (12) 100 (13) 100 (17) 100 100 (18) 100 (19) 100 Allethrin 100 50 X,:ooCH, O 0 5!$COOCH2 - 0 Test Example 2.
A killing test against green rice leafhoppers by the topical application method
Each test compound was accurately weighed and a 0.1% solution in acetone was prepared. Female adults of green rice leafhopper (Nephotettix cincticeps
UHLER) were anaesfhetized w'ith carbon dioxide gas and 0.5 y1 of the above solution was micropipetted onto the thoracic abdominal part of each leafhopper.
Then, the test leafhoppers were kept at 25 (: with access to rice plant seedlings.
Each group comprised 15 green rice leafhoppers. After 24 hours, the leafhoppers were inspected for deaths and the mortality (%) was calculated for each compound.
The results are set forth in Table 2.
TABLE 2
Test compound No. | Mortality (No) (1) Not less than 90% (2) (6) (7) (9) (leo) (12) (13) Ass's 40% c S co0cH242 40% ot Test Example 3.
A killing test against cockroaches by the topical application method
Each test compound was accurately weighed and made in a 1% solution in acetone. ?hen, I y1 of the above solution was micropipetted onto the abdominal part of each female cockroach (Blattella germanica Linne) under ether anaesthesia.
The roaches were released in a high-walled dish together with feed and, after the dish was covered with a metal wire net, it was maintained at 250C. Fifteen roaches per group were used. After 24 hours, the test roaches were inspected for deaths and the mortality (%) for each group was calculated. The results are set forth in Table 3.
TABLE 3
Test compound No. Mortality (%) (1) 100 (2) 80 (6) 100 (7) 80 Test Example 4.
Light stability test
In 2.0 ml ol acetone was dissolved 80 mg of each test compound. A 5 y1 portion of the solution was taken and spread on a glas plate (Micro Standard Cover
Glass, 18m/mO No. 1, 200 pcs, Matsunami Glass Ind., Ltd) and the acetone was evaporated. Then, a similar glas plate was superimposed on the above plate in such a manner that the test solution was sandwiched. The specimen was exposed to direct sunlight at an atmospheric temperature of 12"C. for a predetermined exposure time. As an unexposed control, a similar specimen was covered with an aluminum foil. The test solution was washed away with 1.0 ml of methanol containing 0.04% of dioctyl phthalate as an internal reference and high-speed liquid chromatography was carried out on the washings to determine the residual amount of the test compound. The percent residue (%) is shown in Table 4. The residue (%) was calculated with the value for the aluminum-foil-covered control specimen as the standard.
Table 4.
Residue (%)
4 hours 8 hours
Test compound No. Exposure Exposure
93 90
2 97 100
5 99 98
6 92 92
7 96 96
10 97 97
11 100 96
12 92 90
13 100 100
17 100 100
18 98 97
19 97 92
Allethrin 35 17
Test Example 5.
Hydrolysis resistance test
In about 8 ml of acetone was dissolved 100 mg of each test compound and, then, 1.0 g of water was added to this solution to prepare a mixed solution. This mixed solution was refined for 2 days, after which the acetone was distilled off.
After concentration to about one half of the original volume and with the addition of dioctyl phthalate as an internal reference, the residual amount of the compound was determined by high-speed liquid chromatography. The residue (%) was then calculated. The results are set forth in Table 5.
Table 5.
Test compound No. Residue (%)
(2) more than 90
(6)
(7)
(11)
(12)
(18)
Test Example 6.
Fish Toxicity test
To 51 of water was added 250 mg of Sorpol SM-200 (registered trademark.
Toho Chemical Co., Ltd.) or Tween-20 (registered trademark) as an emulsifier (surfactant) as well as 2.5 ml of an acetone solution containing one of the test compounds in a predetermied concentration. The mixture was stirred well to prepare a test water. Ten female guppies from 3 to 4 months of age were released into the test water and kept at 250 C. The concentration of the test compound at which 90% or more of the guppies were killed during the ensuring 48 hours was determined. (This concentration is referred to as LCgo). The results are set forth in
Table 6.
TABLE 6
Test compound No. LC90 (2) Not less than 10 ppm (5) (7) (8) (10) (11) (12) (13) (17) (18) (19) Allethrin Not more than 0.5 ppm Permethrin Fenvalerate Formulation Example 1.
0.2 part of each of Compounds (1), (2), (5) to (13) and (17) were prepared and 0.8 part of piperonyl butoxude was added to each of them. To this mixture was added a sufficient amount of kerosene to make 100 parts, followed by stirring. By this procedure was obtained an oil preparation of each Compound.
Formulation Example 2.
To 0.1 part of each of Compounds (1) to (17) was added 0.1 part of resmethrin, followed by the addition of a sufficient amount of kerosene to make 100 parts. The mixture was stirred to obtain an oil preparation of each compound.
Formulation Example 3.
To 0.1 part of each of Compounds (1) to (28) was added 0.08 part of permethrin, followed by the addition of a sufficient amount of kerosene to make 100 parts. The mixture was stirred to obtain an oil preparation of each compound.
Formulation Example 4.
To 0.2 part of each of Compounds (1), (2), (5) to (13) and (17) to (19) was added 0.2 part of 2-isopropoxyphenyl N-methylcarbamate and 5 parts of xylene. The composition was dissolved in a sufficient amount of kerosene to make 100 parts. In the above manner, an oil preparation of each compound was obtained.
Formulation Example 5.
To 30 parts of each of Compounds (1), (2), (5) to (13) and (17) to (19) was added 50 parts of xylene and 20 parts of Sorpol SM-200 (a surfactant, trade mark of Toho
Chemical Co., Ltd.). The mixture was stirred well and dissolved to obtain a 30% emulsifiable concentrate.
Formulation Example 6.
To 20 parts of each of Compounds (1), (2), (5) to (9) and (Il) to (13) wad added 20 parts of 0,0 - dimethyl - 0 - 4 - cycanophenyl phosphorothioate [Thianox, trademark of Sumitomo Chemical Co., Ltd.], 20 parts of Sorpol SM-200 (a surfactant, trade mark of Toho Chemical Co., Ltd.) and 40 parts of xylene. The mixture was stirred well to dissolve, whereby an emulsifiable concentrate of each compound was obtained.
Formulation Example 7.
To 20 parts of each of Compounds (1), (2), (5) to (13), (17) to (19) and (2)) ways added 5 parts of Sorpol SM-200 (a surfactant, trade mark of Toho Chemical Co.,
Ltd.), followed by thorough mixing. With the addition of 75 parts of 300-mesh talc, the mixture was thoroughly stirred in a triturator. By the above procedure was obtained a wettable powder of each compound.
Formulation Example 8.
To 15 parts of each of Compounds (1), (2) and (5) to (13) was added 15 parts of l-naphthyl N-methylcarbamate and 5 parts of Sorpol SM-200 (a surfactant, trade mark of Toho Chemical Co., Ltd.), followed by thorough mixing. With the addition of 65 parts of 300-mesh talc, the mixture was thoroughly stirred in a triturator to obtain a settable powder of each compound.
Formulation Example 9.
To one part of each of Compounds (1), (2), (5) to (13) and (17) to (20) was added 5 parts of piperonyl butoxide and the mixture was dissolved in 20 parts of acetone. With the addition of 94 parts of 300-mesh diatomaceous earth, the mixture was stirred well and mixed in a triturator and the acetone was evaporated off. By the above procedure was obtained a powder containing each compound.
Formulation Example 10.
To 0.4 part of each of Compounds (I) to (19) was added 0.1 part of resmethrin, 1.5 parts of octachlorodipropyl ether and 28 parts of refined kerosene. The solution thus obtained was dispensed into aerosol containers and, after the valve was attached, each container was filled with 70 parts of propellant (liquefied petroleum gas). By this procedure was obtained an aerosol preparation of each compound.
Formulation Example 1 1 To 0.3 part of each of Compounds (1), (2) and (5) to (13) was added 0.3 part of
DDVP and the mixture was dissolved in a mixture of xylene and refined kerosene to make a total of 15 parts. Each solution was dispensed into aerosol containers and, after the valve was attached, each container was filled with 85 parts of a propellant (liquified petroleum gas) through the filling valve. By the above procedure was obtained an aerosol preparation of each compound.
Formulation Example 12.
To 0.5 part of each of Compounds (1) to (13) was added 0.5 part of BHT and 99.0 parts of moxquito incense coil materials including pyrethrum marc, sawdust and starch. The mixture was evenly blended and processed into a moxquito coil in the manner conventional per se.
Formulation Example 13.
To 0.05 g of each of Compounds (1), (2), (5), (8), (10) and (11) was added 0.02 g of furamethrin, 0.15 g of piperonyl butoxide and 0.1 g of BHT and the mixture was dissolved in an appropriate amount of chloroform. This solution was adsorbed uniformly on the surface of an asbestos mat having a size of 2.5 cm x 1.5 cm and a thickness of 0.3 mm, and another asbestos mat of the same size and thickness was superimposed on the treated surface. By this procedure was obtained a fibrous fumigation pesticidal composition (mat) for heating on a hot plate.
Effect Example 1.
The emulsifiable concentrate prepared from Compounds (1), (2), (6), (7), (9), (10), (12) and (13) in Formulation Example 5 were each diluted 300-fold with water.
Then, each of the dilutions was sprayed over rice seedlings 25 days after sawing at the rate of 10 ml/pot. The pot was covered with a wire-net and 15 green rice leafhoppers were released under the net. After 24 hours, the leafhoppers were examined for deaths. The mortality (%) was not less than 90% for each of
Compounds (1), (2), (6), (7), (9), (10), (12) and (13).
Effect Example 2.
By the settling mist method, a killing test against houseflies (Musca domestica) was carried out using the oil preparations obtained according to Formulation
Example I from Compounds (1), (2), (5), to (11) and (17). After 24 hours, the flies were examined for deaths. The mortality (%) was not less than 90 for each of
Compounds (1), (2), (5), to (11) and (17).
Effect Example 3.
By the settling mist method, a killing test against houseflies was carried out using the oil preparations made in Formulation Example 2 from Compounds (I), (2), (5), to (11) and (17). After 24 hours, the flies were examined for deaths. The mortality (%) was not less than 90% for each of Compounds (1), (2), (5), to (11) and (17).
Effect Example 4.
By the settling mist method, a killing test against houseflies was carried out using the oil preparations obtained in Formulation Example 3 from Formulation
Example 3 from Compounds (1), (2), (5) to (11) and (17). After 24 hours, the flies were axamined for deaths. The % mortality (%) was not less than 90% for each of
Compounds (1), (2), (5), to (11) and (17).
WHAT WE CLAIM IS:- 1. A pesticidal composition containing as an active ingredient an a- or substituted isovaleric acid ester of the general formula:
in which Z' is hydrogen and Z2 iS CX2 = CH-CH2 or CX2 = CH-CHY-, or Zt iS CX2 = CH- or CX2 = CH-CH2- and Z2 iS hydrogen; A is hydrogen, cyano or ethynyl, except that A is not hydrogen when Z' is CX2 = CH-; and each X and Y, which may be the same or different, represents chlorine or bromine.
2. A pesticidal composition as claimed in Claim 1 in which the active ingredient is an a-substituted isovaleric acid ester of the general formula:
where A is cyano or ethynyl and X is chlorine or bromine.
3. A pesticidal composition as claimed in Claim 2 in which the active ingredient is a-cyano-3-phenoxybenzyl a-(2,2-dichlorvinyl)isovalerate.
4. A pesticidal composition as claimed in Claim 2 in which the active ingredient is a-ethynyl-3-phenoxybenzyl a-(2,2-dichlorovinyl)isovalerate.
5. A pesticidal composition as claimed in Claim 1 in which the active ingredient is an a-substituted isovaleric acid ester of the general formula:
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (18)
1. A pesticidal composition containing as an active ingredient an a- or substituted isovaleric acid ester of the general formula:
in which Z' is hydrogen and Z2 iS CX2 = CH-CH2 or CX2 = CH-CHY-, or Zt iS CX2 = CH- or CX2 = CH-CH2- and Z2 iS hydrogen; A is hydrogen, cyano or ethynyl, except that A is not hydrogen when Z' is CX2 = CH-; and each X and Y, which may be the same or different, represents chlorine or bromine.
2. A pesticidal composition as claimed in Claim 1 in which the active ingredient is an a-substituted isovaleric acid ester of the general formula:
where A is cyano or ethynyl and X is chlorine or bromine.
3. A pesticidal composition as claimed in Claim 2 in which the active ingredient is a-cyano-3-phenoxybenzyl a-(2,2-dichlorvinyl)isovalerate.
4. A pesticidal composition as claimed in Claim 2 in which the active ingredient is a-ethynyl-3-phenoxybenzyl a-(2,2-dichlorovinyl)isovalerate.
5. A pesticidal composition as claimed in Claim 1 in which the active ingredient is an a-substituted isovaleric acid ester of the general formula:
where A and X are as defined in Claim 2.
6. A pesticidal composition as claimed in Claim 5 in which the active ingredient is a-ethynyl-3-phenoxybenzyl a-(3,3-dibromoallyl)isovalerate.
7. A pesticidal composition as claimed in Claim 5 in which the active ingredient is a-cyano-3-phenoxybenzyl a-(3,3-dichloroallyl)isovalerate
8. A pesticidal composition as claimed in Claim 1 in which the active ingredient is a p-substituted isovaleric acid ester of the general formula:
where A and X are as defined in Claim 2.
9. A pesticidal composition as claimed in Claim I in which the active ingredient is a a-substituted isovaleric acid ester of the general formula:
where A and X are as defined in Claim 2.
10. An a-substituted isovaleric acid ester of the general formula:
where A is cyano or ethynyl and X is chlorine or bromine.
11. a-Cyano-3-phenoxybenzyl a-(2,2-dichlorovinyl)isovalerate.
12. a-Ethynyl-3-phenoxybenzyl a-(2,2-dichlorovinyl)isovalerate.
13. An a-substituted isovaleric acid ester of the general formula:
where A and X are as defined in Claim 2.
14. a-Ethynyl-3-phenoxybenzyl a-(3,3-dibromoallyl)isovalerate.
15. a-Cyano-3-phenoxybenzyl a-(3,3-dichloroallyl)isovaleraSte.
16. A p-substituted isovaleric acid ester of the general formula:
where A and X are as defined in Claim 2.
17. A composition as claimed in any one of Claims 1 to 9 in the form of solutions, emulsifiable concentrates, wettable powders, suspensions, dusts, granules, microfine granules, powders coatings. aerosols, mosquito incense coils, fumigants, slow-acting fumigants, electric mosquito incense mats or capsules.
18. A composition as claimed in Claim 1 substantially as hereinbefore described in any one of the Formulation Examples.
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP52027510A JPS6051456B2 (en) | 1977-03-11 | 1977-03-11 | Method for producing γ-halogeno-β,γ-unsaturated carboxylic acid ester |
JP52032863A JPS6051452B2 (en) | 1977-03-23 | 1977-03-23 | Substituted isovaleric acids and their esters |
JP3923777A JPS53124218A (en) | 1977-04-05 | 1977-04-05 | Alpha-(3,3-dihalogeno-3-propen-1-yl)isovaleric acid and its ester |
JP4181377A JPS53145917A (en) | 1977-04-11 | 1977-04-11 | Insecticidal, miticidal composition |
JP13502077A JPS5467030A (en) | 1977-11-09 | 1977-11-09 | Insecticide |
JP15619977A JPS5489024A (en) | 1977-12-23 | 1977-12-23 | Insecticide |
JP16041477A JPS5495528A (en) | 1977-12-30 | 1977-12-30 | New carboxylic acid ester and insecticide containing it as effective component |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1579514A true GB1579514A (en) | 1980-11-19 |
Family
ID=27564137
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9425/78A Expired GB1579514A (en) | 1977-03-11 | 1978-03-09 | Optionally substituted phenoxybenzyl esters of-haloalkenyl isovalenic acids and pesticidal compositions containing them |
Country Status (6)
Country | Link |
---|---|
CH (1) | CH640697A5 (en) |
DE (1) | DE2810031A1 (en) |
FR (2) | FR2382901B1 (en) |
GB (1) | GB1579514A (en) |
IT (1) | IT1115597B (en) |
NL (1) | NL7802626A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4291057A (en) | 1979-07-02 | 1981-09-22 | Union Carbide Corporation | Biocidal esters of halo-4-alkenoic acids |
DE3640596A1 (en) * | 1986-11-27 | 1988-06-01 | Basf Ag | METHOD FOR PRODUCING 3-PENTENIC ACID ESTERS FROM 2-PENTENIC ACID ESTERS |
DE19922934A1 (en) * | 1999-05-19 | 2000-11-23 | Bayer Ag | New 5,5-dihalo- or 4,5,5-trihalo-4-pentenoic acid derivatives, useful as bactericides, fungicides, insecticides, acaricides and nematocides, especially plant fungicides |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EG12446A (en) * | 1975-05-23 | 1979-06-30 | Shell Int Research | 2-substituted isovalerates compounds |
US4161536A (en) * | 1976-11-12 | 1979-07-17 | Ciba-Geigy Corporation | Pesticidal aliphatic carboxylates |
GB1571161A (en) * | 1976-12-01 | 1980-07-09 | Dainippon Jochugiku Kk | Isovaleric acid ester derivatives process for producing thereof and insecticides containing said derivatives |
FR2376118A1 (en) * | 1977-01-03 | 1978-07-28 | Hoffmann La Roche | Pesticidal phenoxy benzyl pentene carboxylate(s) - are prepd. by esterifying a phenoxy benzyl alcohol with a pentene carboxylic acid |
-
1978
- 1978-03-08 DE DE19782810031 patent/DE2810031A1/en not_active Ceased
- 1978-03-09 GB GB9425/78A patent/GB1579514A/en not_active Expired
- 1978-03-10 FR FR7807065A patent/FR2382901B1/fr not_active Expired
- 1978-03-10 NL NL7802626A patent/NL7802626A/en not_active Application Discontinuation
- 1978-03-10 CH CH266078A patent/CH640697A5/en not_active IP Right Cessation
- 1978-03-10 IT IT21130/78A patent/IT1115597B/en active
-
1979
- 1979-06-29 FR FR7917055A patent/FR2422629B1/fr not_active Expired
Also Published As
Publication number | Publication date |
---|---|
FR2382901A1 (en) | 1978-10-06 |
FR2422629A1 (en) | 1979-11-09 |
DE2810031A1 (en) | 1978-09-21 |
IT1115597B (en) | 1986-02-03 |
IT7821130A0 (en) | 1978-03-10 |
FR2382901B1 (en) | 1982-04-30 |
FR2422629B1 (en) | 1983-09-30 |
CH640697A5 (en) | 1984-01-31 |
NL7802626A (en) | 1978-09-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3973036A (en) | Cyclopropanecarboxylic acid esters | |
US4376785A (en) | Cyclopropanecarboxylates and a low fish toxic insecticide and/or acaricide containing them | |
US4496586A (en) | Cyclopropanecarboxylates, their production and insecticide containing them as an active ingredient | |
US4299839A (en) | Novel pesticides and pesticidal compositions cyclopropanecarboxylates and pesticidal method | |
AU595796B2 (en) | Novel carboxylic acid esters, methods for production thereof and insecticides containing them as the active ingredient | |
US4152455A (en) | Insecticidal α-trifluoromethyl-3-phenoxybenzyl carboxylates | |
US3932459A (en) | Novel cyclopropanecarboxylic acid esters | |
DE3028290A1 (en) | 2,2-DIMETHYL-3- (2 ', 2'-DIHALOGENVINYL) CYCLOPROPANCARBONIC ACID-2-METHYL-3- (2'-PROPINYL) -CYCLOPENT-2-EN-4-ON-L-YLESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN FIGHTING PAD INSECTS | |
GB1579514A (en) | Optionally substituted phenoxybenzyl esters of-haloalkenyl isovalenic acids and pesticidal compositions containing them | |
EP0031041B1 (en) | Pyrethroids and their preparation, their pesticidal composition; intermediates and their preparation | |
US4053625A (en) | Insecticides | |
US4409238A (en) | Insecticides and insecticidal compositions | |
US4599358A (en) | Pyrethroids | |
US4219562A (en) | 3-(Hydrocarbylthiomethyl)-2,2-dimethylcyclopropanecarboxylate pesticides | |
US4532258A (en) | Certain cyclopropane carboxylic acid esters and their pesticidal use | |
US4390547A (en) | 2,2-Dimethyl-3-(substituted ethyl)cyclopropane carboxylate pesticidal compositions and methods | |
US4162366A (en) | α-TRIFLUOROMETHYL-3-PHENOXYBENZYL ALCOHOL | |
JPS6313412B2 (en) | ||
JPH0641015A (en) | New pyrethrinoid ester derived from 6-(trifluoromethyl)benzyl alcohol, its production, and its use as harmful organism extermination agent | |
EP0037851A2 (en) | Carboxylates, a process for their production, an insecticidal and/or acaricidal composition and the use of the compounds as insecticides and/or acaricides | |
US4395567A (en) | 1R,Cis-3-(2-halo-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid derivatives | |
CH647224A5 (en) | SUBSTITUTED BENZYL ESTER OF A 2,2-DIMETHYL-3- (2,2-DIHALOGENVINYL) CYCLOPROPANCARBONIC ACID. | |
US4223155A (en) | 3-(Hydrocarbylthiomethyl)-2,2-dimethyl-cyclopropanecarboxylate pesticides and their preparation | |
US4219658A (en) | 6,6-Dimethyl-3-thiabicyclo[3.1.0]hexan-2-one | |
JPS6253497B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PS | Patent sealed [section 19, patents act 1949] | ||
PCNP | Patent ceased through non-payment of renewal fee |