JPS6248675B2 - - Google Patents
Info
- Publication number
- JPS6248675B2 JPS6248675B2 JP17345679A JP17345679A JPS6248675B2 JP S6248675 B2 JPS6248675 B2 JP S6248675B2 JP 17345679 A JP17345679 A JP 17345679A JP 17345679 A JP17345679 A JP 17345679A JP S6248675 B2 JPS6248675 B2 JP S6248675B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- atom
- general formula
- formula
- halogen atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 phosphate ester Chemical class 0.000 claims description 21
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 230000000895 acaricidal effect Effects 0.000 claims description 9
- 239000000642 acaricide Substances 0.000 claims description 8
- 239000002917 insecticide Substances 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 6
- 125000003282 alkyl amino group Chemical group 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 3
- 150000002366 halogen compounds Chemical class 0.000 claims description 3
- 150000003015 phosphoric acid halides Chemical class 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 13
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 8
- 241000254173 Coleoptera Species 0.000 description 7
- 241000244206 Nematoda Species 0.000 description 7
- 241000607479 Yersinia pestis Species 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 241000209094 Oryza Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 241000238876 Acari Species 0.000 description 4
- 241001414720 Cicadellidae Species 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 241001674048 Phthiraptera Species 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 241000239290 Araneae Species 0.000 description 3
- 241001313742 Callosobruchus chinensis Species 0.000 description 3
- 241000336797 Eoeurysa flavocapitata Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 241001124076 Aphididae Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001388466 Bruchus rufimanus Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241001124134 Chrysomelidae Species 0.000 description 2
- 241000254171 Curculionidae Species 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 241001517923 Douglasiidae Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 241000256602 Isoptera Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 241001600434 Plectroglyphidodon lacrymatus Species 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 235000014443 Pyrus communis Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 241001454295 Tetranychidae Species 0.000 description 2
- 241001454293 Tetranychus urticae Species 0.000 description 2
- 241000254234 Xyeloidea Species 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- RTEXIPZMMDUXMR-UHFFFAOYSA-N benzene;ethyl acetate Chemical compound CCOC(C)=O.C1=CC=CC=C1 RTEXIPZMMDUXMR-UHFFFAOYSA-N 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- MDHYEMXUFSJLGV-UHFFFAOYSA-N beta-phenethyl acetate Natural products CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- OTNVGWMVOULBFZ-UHFFFAOYSA-N sodium;hydrochloride Chemical class [Na].Cl OTNVGWMVOULBFZ-UHFFFAOYSA-N 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- AALQBIFJJJPDHJ-UHFFFAOYSA-K trisodium;thiophosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=S AALQBIFJJJPDHJ-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 241001143309 Acanthoscelides obtectus Species 0.000 description 1
- 241001014341 Acrosternum hilare Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000003840 Amygdalus nana Nutrition 0.000 description 1
- 244000296825 Amygdalus nana Species 0.000 description 1
- 241001425390 Aphis fabae Species 0.000 description 1
- 241000952610 Aphis glycines Species 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000525025 Cicadula smithi Species 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 241000255749 Coccinellidae Species 0.000 description 1
- 241000193882 Corbicula Species 0.000 description 1
- 241000700133 Cryptomys Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241001060517 Dicranolaius bellulus Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 241001425477 Dysdercus Species 0.000 description 1
- 241001555556 Ephestia elutella Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 241000578422 Graphosoma lineatum Species 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 241000255967 Helicoverpa zea Species 0.000 description 1
- 241000258937 Hemiptera Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 241001149911 Isopoda Species 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241001470017 Laodelphax striatella Species 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000131091 Lucanus cervus Species 0.000 description 1
- 241000993151 Melanagromyza obtusa Species 0.000 description 1
- DBTDEFJAFBUGPP-UHFFFAOYSA-N Methanethial Chemical compound S=C DBTDEFJAFBUGPP-UHFFFAOYSA-N 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
- 240000000249 Morus alba Species 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 241000257159 Musca domestica Species 0.000 description 1
- 241000409991 Mythimna separata Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 241001556089 Nilaparvata lugens Species 0.000 description 1
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- 241000238814 Orthoptera Species 0.000 description 1
- 241000255947 Papilionidae Species 0.000 description 1
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- 241000219833 Phaseolus Species 0.000 description 1
- 241000593806 Phyllis Species 0.000 description 1
- 241000497192 Phyllocoptruta oleivora Species 0.000 description 1
- 235000011432 Prunus Nutrition 0.000 description 1
- 241001466030 Psylloidea Species 0.000 description 1
- CVQUWLDCFXOXEN-UHFFFAOYSA-N Pyran-4-one Chemical compound O=C1C=COC=C1 CVQUWLDCFXOXEN-UHFFFAOYSA-N 0.000 description 1
- 244000088415 Raphanus sativus Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- 241000866500 Reticulitermes speratus Species 0.000 description 1
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- 241000545593 Scolytinae Species 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 241000270295 Serpentes Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000254152 Sitophilus oryzae Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
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- 241001414833 Triatoma Species 0.000 description 1
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-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
- 150000001408 amides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 235000001436 butterbur Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- XFBJRFNXPUCPKU-UHFFFAOYSA-N chloro-dimethoxy-sulfanylidene-$l^{5}-phosphane Chemical compound COP(Cl)(=S)OC XFBJRFNXPUCPKU-UHFFFAOYSA-N 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004440 column chromatography Methods 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
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 244000013123 dwarf bean Species 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- YSIJNVMMMIMOSF-UHFFFAOYSA-N ethoxy-hydroxy-propylsulfanyl-sulfanylidene-lambda5-phosphane hydrochloride Chemical compound Cl.CCCSP(O)(=S)OCC YSIJNVMMMIMOSF-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000003958 fumigation Methods 0.000 description 1
- 235000021331 green beans Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 150000004694 iodide salts Chemical class 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
- 239000000865 liniment Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000003094 microcapsule 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
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 235000010204 pine bark Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 235000014774 prunus Nutrition 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 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
- 230000000391 smoking effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は新規なリン酸エステル誘導体、その製
造法および該誘導体を有効成分として含有するこ
とを特徴とする殺虫・殺ダニ剤に関するものであ
る。
本発明の化合物は新規化合物であり、下記の一
般式
（式中R1は低級アルコキシ基またはフエニル
基、R2は低級アルコキシ基、低級アルキルアミ
ノ基、低級アルキルメルカプト基またはフエニル
アルキルメルカプト基、Ｙは酸素原子またはイオ
ウ原子、R3は水素原子、低級アルキル基、フエ
ニル基、シクロヘキシル基、ニトロ基またはハロ
ゲン原子、Ｘはハロゲン原子を示す）で表わされ
るリン酸エステル誘導体である。
本発明の化合物は、下記一般式
（式中R3，Ｘは上記の通りである）で表わさ
れる３―ハイドロキシ―γ―ピロン類と下記一般
式
（式中R1，R2，Ｙは上記の通りであり、Halは
ハロゲン原子を示す）で表わされるリン酸ハライ
ド類とを反応させることにより製造される。
また本発明化合物は下記一般式
（式中R1，R3，Ｘ，Ｙは上記の通りであり、
Ｍはアルカリ金属原子を示す）で表わされるリン
酸塩と一般式
R4―Hal （Ｖ）
（式中R4は低級アルキル基又はフエニルアル
キル基、Halはハロゲン原子を示す）で表わされ
るハロゲン化合物とを反応させることによつて得
られる。
本発明の化合物は農作物に寄生する各種の農業
害虫の防除作用を有し、特に農園芸用殺虫・殺ダ
ニ剤として有用である。
殺虫剤、殺ダニ剤は農作物に寄生する各種の農
業害虫を防除することにより農業生産の水準を著
しく高めている。しかし一方では人畜に対する毒
性や、自然環境汚染をはじめとする様々な問題が
重視されるようになり、これら有効な殺虫剤、殺
ダニ剤の使用が危ぶまれる事態にまで進展した。
この様な見地から環境汚染などの心配がなく、
種々の害虫に対して有効な殺虫剤、殺ダニ剤の開
発が待望されている。
本発明者らは上述の目的に添うすぐれた殺虫
剤、殺ダニ剤を開発する為に種々研究を重ねた結
果、一般式（）で表わされる本発明化合物が上
述の目的に合致するすぐれた特性を有する事を見
い出し本発明を完成したものである。
本発明のリン酸エステル誘導体は文献未載の新
規化合物であつて本発明者らによつて初めて見い
出されたものである。しかし、殺虫剤、殺ダニ剤
として驚くべき特性を有している為に農業分野の
発展に大きく寄与するものである。
本発明の化合物は前記一般式（）の３―ハイ
ドロキシ―γ―ピロン類と一般式（）のリン酸
ハライド類を反応させて得られるが、出発原料で
ある一般式（）及び（）の置換基R1，R2，
R3のうち低級アルキル基、低級アルコキシ基、
低級アルキルアミノ基、低級アルキルメルカプト
基、フエニルアルキルメルカプト基において含ま
れる各アルキル基としては炭素数１〜８のものが
好ましく、具体的にはメチル、エチル、プロピ
ル、ヘキシル、オクチル等を例示することができ
る。
一般式（）の３―ハイドロキシ―γ―ピロン
類の具体例としては例えば
５―クロロ―３―ハイドロキシ―γ―ピロン
５―ブロモ―３―ハイドロキシ―γ―ピロン
５―ブロモ―３―ハイドロキシ―２―ブロモ―
γ―ピロン
５―クロロ―３―ハイドロキシ―２―ブロモ―
γ―ピロン
５―クロロ―３―ハイドロキシ―２―クロロ―
γ―ピロン
５―ブロモ―３―ハイドロキシ―２―ニトロ―
γ―ピロン
５―クロロ―３―ハイドロキシ―２―ニトロ―
γ―ピロン
５―クロロ―３―ハイドロキシ―２―メチル―
γ―ピロン
５―ブロモ―３―ハイドロキシ―２―エチル―
γ―ピロン
５―クロロ―３―ハイドロキシ―２―イソブチ
ル―γ―ピロン
５―クロロ―３―ハイドロキシ―２―ｎ―アミ
ル―γ―ピロン
５―ブロモ―３―ハイドロキシ―２―フエニル
―γ―ピロン
５―クロロ―３―ハイドロキシ―２―シクロヘ
キシル―γ―ピロン
５―ブロム―３―ハイドロキシ―２―アリール
―γ―ピロン
等を挙げることができる。
また一般式（）のリン酸ハライド類の具体例
としては例えば
Ｏ，Ｏ―ジメチルチオリン酸クロライド
Ｏ，Ｏ―ジメチルリン酸クロライド
Ｏ，Ｏ―ジエチルチオリン酸クロライド
Ｏ，Ｏ―ジエチルリン酸クロライド
Ｏ，Ｏ―ジエチルチオリン酸クロライド
Ｏ―エチル―Ｏ―メチルチオリン酸クロライド
Ｏ―エチル―Ｏ―メチルリン酸クロライド
Ｏ―エチル―Ｓ―ｎ―プロピルチオリン酸クロ
ライド
Ｏ―エチル―Ｓ―ｎ―プロピルジチオリン酸ク
ロライド
Ｏ―エチル―Ｓ―ｎ―プロピルジチオリン酸ク
ロライド
Ｏ―エチル―Ｓ―iso―プロピルチオリン酸ク
ロライド
Ｏ―エチル―Ｓ―iso―プロピルジチオリン酸
クロライド
Ｏ―エチル―Ｓ―ｎ―ブチルジチオリン酸クロ
ライド
Ｏ―エチル―Ｓ―ｎ―アミルチオリン酸クロラ
イド
Ｏ―エチル―Ｓ―ｎ―アミルジチオリン酸クロ
ライド
Ｏ―エチル―Ｓ―ベンジルチオリン酸クロライ
ド
Ｏ―エチル―Ｓ―ベンジルジチオリン酸クロラ
イド
Ｏ―エチルフエニルリン酸クロライド
Ｏ―エチルフニエルチオリン酸クロライド
Ｏ―エチルフエニルチオリン酸クロライド
Ｏ―エチルメチルチオリン酸クロライド
Ｏ―エチルメチルリン酸クロライド
Ｏ―メチルメチルリン酸クロライド
Ｏ―メチルメチルチオリン酸クロライド
Ｏ―エチルエチルチオリン酸クロライド
Ｏ―エチル―Ｎ―メチルチオリン酸クロライド
Ｏ―エチル―Ｎ―エチルチオリン酸クロライド
Ｏ―エチル―Ｎ―ｎ―プロピルチオリン酸クロ
ライド
Ｏ―メチル―Ｎ―エチルチオリン酸クロライド
Ｏ―メチル―Ｎ―ｎ―プロピルチオリン酸クロ
ライド
Ｏ―エチル―Ｎ―ｎ―ブチルチオリン酸クロラ
イド
Ｏ―エチル―Ｎ―isoブチルチオリン酸クロラ
イド
Ｏ―メチル―Ｎ―ｎ―ブチルチオリン酸クロラ
イド
Ｏ―メチル―Ｎ―isoブチルチオリン酸クロラ
イド
等が挙げられる。
本発明の化合物は一般式（）のリン酸塩と一
般式（）のハロゲン化合物とを反応させること
によつても得られるが、上記一般式の置換基であ
る低級アルキル基とは炭素数１〜８のアルキル基
が良く、Ｍはナトリウム、リチウム等のアルカリ
金属原子を示す。
一般式（）のリン酸塩の具体例としては例え
ば
Ｏ―エチル―Ｏ―（５―クロロ―γ―ピロン―
３―イル）チオリン酸ナトリウム
Ｏ―エチル―Ｏ―（５―クロロ―γ―ピロン―
３―イル）チオリン酸ナトリウム
Ｏ―エチル―Ｏ―（５―クロロ―２―ブロモ―
γ―ピロン―３―イル）チオリン酸ナトリウム
Ｏ―エチル―Ｏ―（５―ブロモ―２―ニトロ―
γ―ピロン―３―イル）チオリン酸ナトリウム
Ｏ―エチル―Ｏ―（５―クロロ―２―メチル―
γ―ピロン―３―イル）チオリン酸ナトリウム
Ｏ―エチル―Ｏ―（５―ブロモ―２―エチル―
γ―ピロン―３―イル）チオリン酸ナトリウム
Ｏ―エチル―Ｏ―（５―クロロ―２―フエニル
―γ―ピロン―３―イル）チオリン酸ナトリウム
Ｏ―エチル―Ｏ―（５―ブロモ―２―シクロヘ
キシル―γ―ピロン―３―イル）チオリン酸ナト
リウム
Ｏ―エチル―Ｏ―（５―ブロモ―２―アリール
―γ―ピロン―３―イル）チオリン酸ナトリウム
及びこれらの相当するカリウム塩等を挙げること
ができる。
一般式（）のハロゲン化合物の具体例として
は例えば臭化エチル、臭化ｎ―プロピル、臭化
iso―ピロピル、臭化ｎ―ブチル、臭化ｎ―アミ
ル、臭化ベンジル及びこれらの相当する塩化物、
沃化物等を挙げることができる。
上記２種の反応は適当な溶媒中で行うのが好ま
しく、特に前者の一般式（）及び（）の化合
物の反応においては酸受体の存在下に反応を行う
のが好ましい。
反応に用いられる溶媒としては、例えばジオキ
サン、テトラヒドロフラン等のエーテル類、塩化
メチレン、クロロホルム等のハロゲン化炭化水素
類、アセトン、メチルエチルケトン等のケトン
類、ベンゼン、トルエン等の芳香族炭化水素類、
アセトニトリル、プロピオニトリル等のニトリル
類、ジメチルホルムアミド、ジメチルアセトアミ
ド等のアミド類、ジメチルスルホキサイド等のス
ルホキサイド類などを挙げることができる。
酸受体としては一般的な酸結合剤を使用でき
る。水酸化ナトリウム、水酸化カリウム等の水酸
化アルカリ金属化合物、炭酸ナトリウム、炭酸カ
リウム、重炭酸ナトリウム、重炭酸カリウム等の
炭酸アルカリ金属化合物、ナトリウムメチラー
ト、ナトリウムエチラート等のアルコラート類、
トリエチルアミン、ジメチルアミン、ジエチルア
ニリン、ピリジンなどの脂肪族、芳香族、複素環
式アミン類などを挙げることが出来る。これらの
酸受体化合物の使用量は出発原料（）に対して
約0.5〜3.0倍モル、好ましくは約1.0〜1.5倍モル
用いるのが良い。
本反応の出発原料は通常等モルずつ、或いは一
方を若干過剰量用いるのが好ましい。
本発明の反応は広い温度範囲に於いて実施する
ことが可能で一般に−30℃〜溶媒の沸点温度の間
で実施され、好ましくは約０〜100℃の間で実施
される。
本発明の反応時間は反応を行う出発原料によつ
ても異なるが１〜10時間、好ましくは約３〜５時
間の範囲が好ましい。この様にして得られる本発
明の化合物は通常の分離手段、例えば溶媒抽出
法、溶媒希釈法、蒸留法、再結晶法、カラムクロ
マトグラフイー等により、容易に単離精製でき、
目的とする一般式（）で表わされるリン酸エス
テル誘導体を高純度で得ることが出来る。
前述した様に本発明化合物は優れた殺虫及び殺
ダニ活性を有していることが特徴である。即ち、
本発明化合物は農作物に発生する害虫、ダニ、又
衛生害虫に対して特に活性を示す。
本発明化合物は植物に対して耐性であり、害虫
及びダニに対してのみ活性を有しており、あらゆ
る分野で発生する昆虫、ダニの駆除に使用出来、
その敏感性は全ての成長段階又は特定の成長段階
に対しても効果を示す。
上述した害虫に次の様なものが挙げられる。等
脚目のもの、たとえばオカダンゴムシ、シミ目の
もの、たとえばレプシマサツカリナ、粘管目のも
の、たとえばヤギトビムシモドキ、オニチウルス
アルマツス、等翅目のもの、たとえばイエシロア
リ、ヤマトシロアリ、シラミ目のもの、たとえば
ヒトジラミ、ケモノジラミ、ケモノホリジラミ、
ハジラミ目のもの、たとえばケモノハジラミ、総
翅目のもの、たとえばイネアザミウマ、ネギアザ
ミウム、隠翅目のもの、たとえばヒトノミ、ネズ
ミノミ、直翅目のもの、たとえばハネナガイナ
ゴ、トノサマバツタ、エンマコウロギ、ケラ、ワ
モンゴキブリ、ブラツタオリエンタリス、半翅目
のもの、たとえばマメアブラムシ、ダイズアブラ
ムシ、ダイコンアブラムシ、イネクロカメムシ、
イネカメムシ、ミドリメクラガメ、クワコナカイ
ガラムシ、オオワタカイガラモドキ、コンマカイ
ガラムシ、ツノロウムシ、ヒメトビウンカ、ツマ
グロヨコバイ、フタテンヒメヨコバイ、ナシキジ
ラミ、キジラミ、ナシグンバイムシ、アオバハゴ
ロモ、リンゴワタムシ、ジスデルクス・インテル
メジウス、ビエスマ・クワドラタ、ロドニウス・
プロリクス、トリアトマ、クリプトミミズ・リビ
ス、ドラリス・フラバエ、ムギヒゲナカアブラム
シ、コブアブラムシ、ヒメヨコバイ、ユースセリ
ス・ビロバツス、鱗翅目のもの、たとえばアオム
シ、アゲハ、アケビコノハ、イラガ、ウスエグリ
バ、ウメクンガ、エビガラスズメ、クリミガ、ウ
メケムシ、マメヒメサヤムシ、アメリカシロヒト
リ、ウラナミシジミ、ナカジロシタバ、ナシノセ
スジシヤクトリ、タバコガ、バクガ、イネタテハ
マキ、フキノメイガ、ニカメイガ、イネヨトウ、
トリトリクス・ビリダナ、ハチミツガ、鞘翅目の
もの、たとえばイネドロオイムシ、クワカミキ
リ、マツノキクイムシ、ゾウムシ、コクゾウム
シ、アズキゾウムシ、イネゾウムシ、ニジヨウヤ
ホシテントウ、ドウガネブイブイ、マメハンミヨ
ウ、クワハムシ、ハリガネムシ、ソラマメゾウム
シ、膜翅目のもの、たとえばカブラハバチ、ダイ
ズハバチ、双翅目のもの、たとえばキリウジガガ
ンボ、イネカラバエ、イネハモグリバエ、ハモグ
リバエ、ダイズサヤタマバエ、ミバエ類、イエバ
エ、ハダニ類のもの、たとえばミカンハダニ、ニ
セナミハダニ、オウトウハダニ、クローバーハダ
ニ、ネダニ、ミカンサビダニ、線虫類のもの、た
とえばネコブセンチユウ、サヤクセンチユウ、イ
チゴメセンチユウ、サツマイモネコゴセンチユ
ウ、ミナミネグサレセンチユウ等である。
これら生物活性を有する本発明の化合物は乳
剤、水和剤、水溶剤、懸濁剤、濃厚懸濁剤、粒
剤、微粒剤、顆粒剤、粉剤、水和性粉剤、塗布
剤、フオームスプレー用製剤、エアゾール製剤、
マイクロカプセル製剤、天然あるいは合成物質へ
の含浸製剤、薫蒸用製剤、薫煙用製剤、濃厚少量
散布用製剤等の形態で用いることができる。
これら製剤を造るに当つては乳化、分散、懸
濁、発泡させる為に各種界面活性剤を用いること
ができ、たとえば非イオン界面活性剤としてポリ
オキシエチレンアルキルエーテル、ポリオキシエ
チレンアルキルエステル、ポリオキシエチレンソ
ルビタンアルキルエステル、ソルビタンアルキル
エステル、陰イオン界面活性剤としてアルキルベ
ンゼンスルホネート、アルキルスルホサクシネー
ト、アルキルサルフエート、ポリオキシエチレン
アルキルサルフエート、アリルスルホネート、リ
ングニン亜硫酸塩等を使用することができる。
また溶解剤、希釈剤、担体としては、各種有機
溶媒、各種エアゾール噴射剤、各種天然鉱物およ
び値物ならびに各種合成化合物等を用いることが
できる。たとえば有機溶媒として種々あるが特に
好ましいのはベンゼン、トルエン、キシレン、エ
チルベンゼン、クロルベンゼン、アルキルナフタ
リン、、ジクロルメタン、クロルエチレン、シク
ロヘキサン、シクロヘキサノン、アセトン、メチ
ルエチルケトン、メチルイソブチルケトン、アル
コール類、ジメチルホルムアミド、ジメチルスル
ホオキシド、アセトニトリル、鉱油留分および水
等である。
エアゾール噴射剤としてはたとえばプロパン、
ブタン、ハロゲン化炭化水素、窒素、二酸化炭素
等を例示できる。
鉱物質としては、たとえばカオリン、タルク、
ベントナイト、ケイソウ土、粘土、モンモリロナ
イト、チヨーク、方解石、軽石、海泡石、ドロマ
イト等を挙げることができる。
値物類としては、たとえばクルミ殻、タバコ
茎、おがくず等、合成高分子化合物としては、た
とえばアルミナ、ケイ酸塩、糖重合体等、また括
着剤としては、たとえばカルボキシメチルセルロ
ース、アラビアゴム、ポリビニルアルコール、ポ
リビニルアセテート等を挙げることができる。こ
れら製剤には有機あるいは無機染料を用いて着色
することも可能である。
本発明においては上記各種製剤を製造するに当
つて本発明の化合物を約0.1〜95重量％、好まし
くは約0.5〜90重量％を含有するように製剤する
ことができる。
調製された製剤はそのままあるいは担体もしく
は水で希釈して用いられるが目的に合わせて約
0.00001〜100重量％の範囲で自由に希釈すること
ができ、好ましくは約0.0001〜10重量％の活性物
質を含むように希釈し使用するのが良い。以下に
本発明化合物の製造例を示す。
実施例 １
５―クロル―２―メチル―３―ハイドロキシ―
γ―ピロン3.2ｇ（0.02モル）をアセトニトリル
50mlに溶解させ、この中へ無水炭酸カリウム3.0
ｇを添加してかき混ぜながら30分間還流する。つ
ぎに反応混合物を室温まで冷却して０，０―ジエ
チルチオリン酸クロライド3.77ｇ（0.02モル）を
少量ずつ滴下する。滴下後、50〜55℃で３時間か
き混ぜた後、室温まで冷却して固形物を口別し、
口液にベンゼン150mlを注加する。ベンゼン溶液
を５％塩酸水溶液、飽和重ソウ水、そして飽和食
塩水で洗浄後、無水硫酸マグネシウムで乾燥す
る。溶媒を留去した残留物をシリカゲルカラム
（ベンゼン―酢エチ＝10：１）に通すと淡黄色油
状のＯ，Ｏ―ジエチル―（５―クロロ―２―メチ
ル―γ―ピロン―３―イル）―チオホスフエート
5.76ｇ（92％）が得られる。
IR（neat）；1640，1580（Ｃ＝Ｃ）、1670（Ｃ
＝Ｏ）、805，610cm-1（Ｐ＝Ｓ）
NMR（CDCl3；1.40（ｔ，6H，CH3―Ｃ）、
2.34（ｄ，3H，CH3―Ｃ）、4.30（ｍ，AH，
CH2―Ｏ）、8.26（ｄ，1H，CH＝Ｃ）
実施例 ２
５―ブロム―３―ハイドロキシ―γ―ピロン
3.8ｇ（0.02モル）アセトン50mlに溶解させ、こ
の中へ無水炭酸カリウム3.0ｇを添加してかき混
ぜながら30分間還流する。つぎに反応混合物を室
温まで冷却してＯ―メチル―Ｓ―ｎ―プロピルチ
オリン酸クロライド3.77ｇ（0.02モル）を少量ず
つ滴下する。滴下後50〜55℃で４時間かき混ぜた
後、室温まで冷却して固形物をロ別し、ロ液にベ
ンゼン150mlを注加する。ベンゼン溶液を５％塩
酸水溶液、飽和重ソウ水、そして飽和食塩水で洗
浄後、無水硫酸マグネシウムで乾燥する。溶媒を
留去した残留物をシリカゲルカラム（ベンゼン―
酢酸エチル＝10：１）に通すと淡黄色油状のＯ―
メチル―Ｓ―ｎ―プロピル―（５―クロロ―γ―
ピロン―３―イル）ジチオホスフエート6.22ｇ
（91％）が得られる。
IR（neat）；1640，1580（Ｃ＝Ｃ）、1670（Ｃ
＝Ｏ）、814，648cm-1（Ｐ＝Ｓ）
NMR（CDCl3）＝δ1.1（ｍ，3H，CH3−Ｃ）、
2.72（ｍ，4H，CH2CH2S）、3.74（ｓ，3H，
CH，CH3O）、8.04（ｄ，1H，CH＝Ｃ）、
8.22（ｓ，1H，CH＝Ｃ）
実施例 ３
Ｏ―エチル―Ｏ―〔３―（５―クロル―γ―ピ
ラニル）〕チオリン酸ナトリウム6.17ｇ（0.02モ
ル）とベンジルブロマイド3.4ｇ（0.02モル）の
アセトン溶液100mlを５時間還流後、室温まで冷
却して固形物をロ別し、ロ液を濃縮する。残留物
をベンゼン200mlに溶解させ、ベンゼン溶液を飽
和食塩水で洗浄後、無水硫酸マグネシウムで乾燥
する。溶媒を留去した残留物をシリカゲルカラム
（ベンゼン―酢エチ＝10：１）に通すと黄色油状
のＯ―エチル―Ｓ―ベンジル―（５―クロロ―γ
―ピロン―３―イル）ジチオホスフエート6.34ｇ
（87％）が得られる。
IR（neat）；1640，1580（Ｃ＝Ｃ）、1670（Ｃ
＝Ｏ）、810，648cm-1（Ｐ＝Ｓ）
NMR（CDCl3）；δ1.42（ｔ，3H，CH3―
Ｃ）、4.27（ｍ，2H，CH2―Ｏ）、4.92（ｄ，
2H，CH2S）、7.1〜7.4（broad，5H，
The present invention relates to a novel phosphate ester derivative, a method for producing the same, and an insecticide/acaricide containing the derivative as an active ingredient. The compound of the present invention is a new compound, and has the following general formula: (In the formula, R 1 is a lower alkoxy group or phenyl group, R 2 is a lower alkoxy group, lower alkylamino group, lower alkylmercapto group, or phenylalkylmercapto group, Y is an oxygen atom or a sulfur atom, R 3 is a hydrogen atom, It is a phosphate ester derivative represented by a lower alkyl group, a phenyl group, a cyclohexyl group, a nitro group, or a halogen atom (X represents a halogen atom). The compound of the present invention has the following general formula: 3-hydroxy-γ-pyrones represented by (in the formula, R 3 and X are as above) and the following general formula (In the formula, R 1 , R 2 and Y are as described above, and Hal represents a halogen atom). In addition, the compound of the present invention has the following general formula: (In the formula, R 1 , R 3 , X, Y are as above,
M represents an alkali metal atom) and a halogen represented by the general formula R 4 -Hal (V) (wherein R 4 is a lower alkyl group or phenyl alkyl group, and Hal represents a halogen atom) Obtained by reacting with a compound. The compounds of the present invention have a controlling effect on various agricultural pests that parasitize agricultural crops, and are particularly useful as insecticides and acaricides for agriculture and horticulture. Insecticides and acaricides have significantly improved the level of agricultural production by controlling various agricultural pests that parasitize agricultural crops. However, on the other hand, various problems such as toxicity to humans and livestock and pollution of the natural environment have become more important, and the situation has progressed to the point where the use of these effective insecticides and acaricides is in doubt.
From this perspective, there is no need to worry about environmental pollution,
The development of insecticides and acaricides that are effective against various pests is eagerly awaited. The present inventors have conducted various studies to develop excellent insecticides and acaricides that meet the above objectives, and as a result, the compound of the present invention represented by the general formula () has excellent properties that meet the above objectives. The present invention was completed by discovering that the present invention has the following properties. The phosphoric acid ester derivative of the present invention is a novel compound that has not been described in any literature and was discovered for the first time by the present inventors. However, because it has surprising properties as an insecticide and acaricide, it greatly contributes to the development of the agricultural field. The compound of the present invention is obtained by reacting the 3-hydroxy-γ-pyrones of the general formula () with the phosphoric acid halides of the general formula (), but the starting materials, the general formula () and (), are substituted. Groups R 1 , R 2 ,
Among R 3 , lower alkyl group, lower alkoxy group,
Each alkyl group contained in the lower alkylamino group, lower alkylmercapto group, and phenylalkylmercapto group preferably has 1 to 8 carbon atoms, and specific examples include methyl, ethyl, propyl, hexyl, octyl, etc. be able to. Specific examples of 3-hydroxy-γ-pyrones of general formula () include 5-chloro-3-hydroxy-γ-pyrone 5-bromo-3-hydroxy-γ-pyrone 5-bromo-3-hydroxy-2 -Bromo-
γ-pyrone 5-chloro-3-hydroxy-2-bromo-
γ-pyrone 5-chloro-3-hydroxy-2-chloro-
γ-pyrone 5-bromo-3-hydroxy-2-nitro-
γ-pyrone 5-chloro-3-hydroxy-2-nitro-
γ-pyrone 5-chloro-3-hydroxy-2-methyl-
γ-pyrone 5-bromo-3-hydroxy-2-ethyl-
γ-pyrone 5-chloro-3-hydroxy-2-isobutyl-γ-pyrone 5-chloro-3-hydroxy-2-n-amyl-γ-pyrone 5-bromo-3-hydroxy-2-phenyl-γ-pyrone Examples include 5-chloro-3-hydroxy-2-cyclohexyl-γ-pyrone, 5-bromo-3-hydroxy-2-aryl-γ-pyrone, and the like. Further, specific examples of the phosphoric acid halides of the general formula () include O,O-dimethylthiophosphoric acid chloride O, O-dimethylphosphoric acid chloride O, O-diethylthiophosphoric acid chloride O, O-diethylphosphoric acid chloride O, O-diethylthiophosphoric acid chloride O-ethyl-O-methylthiophosphoric acid chloride O-ethyl-O-methylphosphoric acid chloride O-ethyl-Sn-propylthiophosphoric acid chloride O-ethyl-Sn-propyldithiophosphoric acid chloride O -Ethyl-S-n-propyldithiophosphoric acid chloride O-ethyl-S-iso-propyldithiophosphoric acid chloride O-ethyl-S-iso-propyldithiophosphoric acid chloride O-ethyl-S-n-butyldithiophosphoric acid chloride O-ethyl -S-n-amylthiophosphoric acid chloride O-ethyl-S-n-amyldithiophosphoric acid chloride O-ethyl-S-benzylthiophosphoric acid chloride O-ethyl-S-benzyldithiophosphoric acid chloride O-ethyl phenylphosphoric acid chloride O- Ethylphenylthiophosphoric acid chloride O - Ethylphenylthiophosphoric acid chloride O - Ethylmethylthiophosphoric acid chloride O - Ethylmethylphosphoric acid chloride O - Methylmethylphosphoric acid chloride O - Methylmethylthiophosphoric acid chloride O - Ethyl ethylthiophosphoric acid chloride O -Ethyl-N-methylthiophosphoric acid chloride O-ethyl-N-ethylthiophosphoric acid chloride O-ethyl-Nn-propylthiophosphoric acid chloride O-methyl-N-ethylthiophosphoric acid chloride O-methyl-Nn-propyl Thiophosphoric acid chloride O-ethyl-N-n-butylthiophosphoric acid chloride O-ethyl-N-isobutylthiophosphoric acid chloride O-methyl-N-n-butylthiophosphoric acid chloride O-methyl-N-isobutylthiophosphoric acid chloride, etc. can be mentioned. The compound of the present invention can also be obtained by reacting a phosphate of the general formula () with a halogen compound of the general formula (), but the lower alkyl group as a substituent in the above general formula has 1 carbon number. ~8 alkyl groups are preferred, and M represents an alkali metal atom such as sodium or lithium. Specific examples of phosphates of general formula () include O-ethyl-O-(5-chloro-γ-pyrone-
3-yl) Sodium thiophosphate O-ethyl-O-(5-chloro-γ-pyrone-
Sodium 3-yl)thiophosphate O-ethyl-O-(5-chloro-2-bromo-
Sodium γ-pyron-3-yl)thiophosphate O-ethyl-O-(5-bromo-2-nitro-
Sodium γ-pyron-3-yl)thiophosphate O-ethyl-O-(5-chloro-2-methyl-
Sodium γ-pyron-3-yl)thiophosphate O-ethyl-O-(5-bromo-2-ethyl-
Sodium γ-pyron-3-yl)thiophosphate Sodium O-ethyl-O-(5-chloro-2-phenyl-γ-pyron-3-yl)thiophosphate O-ethyl-O-(5-bromo-2- Sodium cyclohexyl-γ-pyron-3-yl)thiophosphate, sodium O-ethyl-O-(5-bromo-2-aryl-γ-pyron-3-yl)thiophosphate and their corresponding potassium salts, etc. Can be done. Specific examples of halogen compounds of general formula () include ethyl bromide, n-propyl bromide,
iso-pyropyl, n-butyl bromide, n-amyl bromide, benzyl bromide and their corresponding chlorides,
Examples include iodides. The above two reactions are preferably carried out in a suitable solvent, and particularly in the former reaction of compounds of general formulas () and (), it is preferable to carry out the reaction in the presence of an acid acceptor. Examples of the solvent used in the reaction include ethers such as dioxane and tetrahydrofuran, halogenated hydrocarbons such as methylene chloride and chloroform, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene and toluene,
Examples include nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide and dimethylacetamide, and sulfoxides such as dimethylsulfoxide. A common acid binder can be used as the acid acceptor. Alkali metal hydroxide compounds such as sodium hydroxide and potassium hydroxide; alkali metal carbonate compounds such as sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; alcoholates such as sodium methylate and sodium ethylate;
Examples include aliphatic, aromatic, and heterocyclic amines such as triethylamine, dimethylamine, diethylaniline, and pyridine. The amount of these acid acceptor compounds to be used is about 0.5 to 3.0 times the mole, preferably about 1.0 to 1.5 times the amount of the starting material (2). It is preferable to use the starting materials for this reaction in equimolar amounts, or in a slightly excess amount of one of them. The reaction of the present invention can be carried out over a wide temperature range and is generally carried out between -30°C and the boiling point of the solvent, preferably between about 0 and 100°C. The reaction time in the present invention varies depending on the starting materials used for the reaction, but is preferably in the range of 1 to 10 hours, preferably about 3 to 5 hours. The compound of the present invention obtained in this manner can be easily isolated and purified by conventional separation methods such as solvent extraction, solvent dilution, distillation, recrystallization, column chromatography, etc.
The desired phosphate ester derivative represented by the general formula () can be obtained with high purity. As mentioned above, the compound of the present invention is characterized by having excellent insecticidal and acaricidal activity. That is,
The compounds of the present invention are particularly active against pests, mites, and sanitary pests that occur on agricultural crops. The compound of the present invention is resistant to plants, has activity only against pests and mites, and can be used to exterminate insects and mites occurring in all fields.
The sensitivity can be effective for all growth stages or even for specific growth stages. The pests mentioned above include the following: Isopoda, such as vulgare, Pitiformes, such as Lepsimus satucarina, Vectinidae, such as Phyllis vulgare, Onythiurus almatus, Isoptera, such as the domestic termite, the Japanese termite, Members of the order Lice, such as human lice, furry lice, furry lice,
members of the orders of the orders of the orders of the orders such as the order Physiformes, such as the woolly lice, the orders of the orders of the orders order of the orders of order, such as the occidental fleas, and the orders of the order order of the order of orthoptera, such as the serpentine locust, the serpent, and the American cockroach; Bracta orientalis, Hemiptera such as bean aphid, soybean aphid, radish aphid, rice black stink bug,
Rice stink bug, green stink bug, silver scale bug, giant bollworm, comma scale bug, horned beetle, black leafhopper, black leafhopper, dwarf leafhopper, pear leafhopper, psyllid leafhopper, pear leafhopper, green leaf beetle, apple boll beetle, Dysdercus intermezius, Biesma quadrata , Rodnius
Prolichus, Triatoma, Cryptomys livis, Dralis flabae, Black-bellied aphid, Black leafhopper, Yellow leafhopper, Eusceris bilobatus, Lepidoptera such as green leaf beetle, swallowtail butterfly, Akebikonoha, Iraga, Usuegriba, Umekunga, Long-tailed sparrow, Chrysalis moth, Prunus moth , Bean beetle, American white flycatcher, Uranami corbicula, Nakajirotaba, Nashinosejisyakutori, Tobacco moth, Bacillus moth, Rice caterpillar moth, Butterbur moth, Japanese moth, Rice armyworm,
Tritrix viridana, honey beetle, Coleoptera, such as rice beetle, mulberry beetle, pine bark beetle, weevil, brown weevil, adzuki bean weevil, rice weevil, rainbow lady beetle, brown beetle, bean weevil, stag beetle, hedge beetle, broad bean weevil, Hymenoptera , such as the yellowtail sawfly, the soybean sawfly, those of the order Diptera, such as the yellowtail spider mite, the rice carabium, the rice leafminer, the leafminer leafminer, the soybean pod fly, fruit flies, the house fly, and the spider mites, such as the citrus spider mite, the false red spider mite, the red spider mite, the clover spider mite, These include bed mites, citrus rust mites, and nematode species, such as nematode nematode, nematode nematode, nematode nematode, strawberry nematode, sweet potato nematode, and southern nematode. These biologically active compounds of the present invention can be used in emulsions, wettable powders, aqueous solutions, suspensions, concentrated suspensions, granules, fine granules, granules, powders, wettable powders, liniments, and foam sprays. formulations, aerosol formulations,
It can be used in the form of microcapsule preparations, preparations for impregnating natural or synthetic substances, preparations for fumigation, preparations for smoking, preparations for spraying in concentrated small quantities, and the like. In producing these preparations, various surfactants can be used for emulsification, dispersion, suspension, and foaming. For example, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, and Ethylene sorbitan alkyl ester, sorbitan alkyl ester, alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, allyl sulfonate, lingnin sulfite, etc. can be used as anionic surfactants. As the solubilizing agent, diluent, and carrier, various organic solvents, various aerosol propellants, various natural minerals and valuables, and various synthetic compounds can be used. For example, there are various organic solvents, but particularly preferred are benzene, toluene, xylene, ethylbenzene, chlorobenzene, alkylnaphthalene, dichloromethane, chloroethylene, cyclohexane, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohols, dimethylformamide, dimethyl These include sulfoxide, acetonitrile, mineral oil fraction and water. Examples of aerosol propellants include propane,
Examples include butane, halogenated hydrocarbons, nitrogen, carbon dioxide, and the like. Examples of minerals include kaolin, talc,
Bentonite, diatomaceous earth, clay, montmorillonite, tyoke, calcite, pumice, sepiolite, dolomite, etc. may be mentioned. Values include walnut shells, tobacco stems, sawdust, etc. Synthetic polymer compounds include alumina, silicates, sugar polymers, etc. Binding agents include carboxymethylcellulose, gum arabic, polyvinyl, etc. Alcohol, polyvinyl acetate, etc. can be mentioned. These preparations can also be colored using organic or inorganic dyes. In the present invention, when producing the above-mentioned various formulations, the compounds of the present invention can be formulated to contain about 0.1 to 95% by weight, preferably about 0.5 to 90% by weight. The prepared preparation can be used as it is or diluted with a carrier or water, depending on the purpose.
It can be freely diluted in the range of 0.00001 to 100% by weight, preferably to contain about 0.0001 to 10% by weight of the active substance. Examples of manufacturing the compounds of the present invention are shown below. Example 1 5-chloro-2-methyl-3-hydroxy-
3.2 g (0.02 mol) of γ-pyrone in acetonitrile
Dissolve in 50ml and add anhydrous potassium carbonate 3.0
g and reflux for 30 minutes while stirring. Next, the reaction mixture was cooled to room temperature, and 3.77 g (0.02 mol) of 0,0-diethylthiophosphoric acid chloride was added dropwise little by little. After dropping, stir at 50-55℃ for 3 hours, cool to room temperature and separate the solids.
Add 150 ml of benzene to the oral fluid. The benzene solution is washed with a 5% aqueous hydrochloric acid solution, a saturated sodium hydrogen chloride solution, and a saturated saline solution, and then dried over anhydrous magnesium sulfate. When the solvent was distilled off and the residue was passed through a silica gel column (benzene-ethyl acetate = 10:1), pale yellow oily O,O-diethyl-(5-chloro-2-methyl-γ-pyron-3-yl) was obtained. -Thiophosphate
5.76 g (92%) is obtained. IR (neat); 1640, 1580 (C=C), 1670 (C
=O), 805, 610cm -1 (P=S) NMR (CDCl 3 ; 1.40 (t, 6H, CH 3 -C),
2.34 (d, 3H, CH 3 - C), 4.30 (m, AH,
CH 2 -O), 8.26 (d, 1H, CH=C) Example 2 5-bromo-3-hydroxy-γ-pyrone
Dissolve 3.8g (0.02mol) in 50ml of acetone, add 3.0g of anhydrous potassium carbonate, and reflux for 30 minutes while stirring. Next, the reaction mixture was cooled to room temperature, and 3.77 g (0.02 mol) of O-methyl-Sn-propylthiophosphoric acid chloride was added dropwise little by little. After the dropwise addition, the mixture was stirred at 50 to 55°C for 4 hours, cooled to room temperature, solid matter was filtered out, and 150 ml of benzene was added to the filtered liquid. The benzene solution is washed with a 5% aqueous hydrochloric acid solution, a saturated sodium hydrogen chloride solution, and a saturated saline solution, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was transferred to a silica gel column (benzene-
When passed through ethyl acetate = 10:1), a pale yellow oily O-
Methyl-S-n-propyl-(5-chloro-γ-
Pyrron-3-yl) dithiophosphate 6.22g
(91%) is obtained. IR (neat); 1640, 1580 (C=C), 1670 (C
= O), 814,648 cm -1 (P = S) NMR (CDCl 3 ) = δ1.1 (m, 3H, CH 3 -C),
2.72 (m, 4H, CH 2 CH 2 S), 3.74 (s, 3H,
CH, CH 3 O), 8.04 (d, 1H, CH=C),
8.22 (s, 1H, CH=C) Example 3 O-ethyl-O-[3-(5-chloro-γ-pyranyl)]sodium thiophosphate 6.17 g (0.02 mol) and benzyl bromide 3.4 g (0.02 mol) After refluxing 100 ml of the acetone solution for 5 hours, it was cooled to room temperature, the solid matter was filtered off, and the filtrate was concentrated. Dissolve the residue in 200 ml of benzene, wash the benzene solution with saturated saline, and dry over anhydrous magnesium sulfate. When the solvent was distilled off and the residue was passed through a silica gel column (benzene-ethyl acetate = 10:1), a yellow oily O-ethyl-S-benzyl-(5-chloro-γ) was obtained.
-pyron-3-yl) dithiophosphate 6.34g
(87%). IR (neat); 1640, 1580 (C=C), 1670 (C
=O), 810,648cm -1 (P=S) NMR (CDCl 3 ); δ1.42 (t, 3H, CH 3 -
C), 4.27 (m, 2H, CH 2 - O), 4.92 (d,
2H, CH2S ), 7.1~7.4(broad, 5H,
【式】）、8.06（ｓ，1H，CH＝Ｃ）、
8.22（ｄ，1H，CH＝Ｃ）
実施例 ４〜33
前記実施例に準じて本発明化合物を製造した若
干例を挙げる。尚実施例25，26及び29は実施例３
の方法により製造し、その他の実施例は実施例１
の方法により製造した。尚表中Me，Et，Prは
夫々メチル、エチル、プロピル基を表わす。[Formula]), 8.06 (s, 1H, CH═C), 8.22 (d, 1H, CH═C) Examples 4 to 33 Some examples of the compounds of the present invention produced according to the above examples are listed below. In addition, Examples 25, 26 and 29 are Example 3
Other examples are Example 1.
Manufactured by the method. In the table, Me, Et, and Pr represent methyl, ethyl, and propyl groups, respectively.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
本発明で得られた化合物の生物試験結果の若干
の例を供する。
試験例 １
ヒメトビウンカ（Laodel Phax Striatellus）
に対する試験
供試化合物２重量部をメタノール98重量部に溶
解する。これを0.04％展着剤入り水溶液を用いて
所定濃度に希釈する。ポツト値え水稲（Oryza
Satiua）に上記の如く調整された液剤を静かにた
れ落ちるまで噴霧し風乾後ヒメトビウンカ成虫を
供す。一定時間後に死虫率を求める。尚供試化合
物を用いない以外は同様にして行つた対照試験結
果をも併記する。[Table] Some examples of biological test results of compounds obtained according to the present invention are provided. Test example 1 Laodel Phax Striatellus
Test for: Dissolve 2 parts by weight of the test compound in 98 parts by weight of methanol. This is diluted to a predetermined concentration using an aqueous solution containing 0.04% spreading agent. Pot-worthy paddy rice (Oryza)
The solution prepared as above was sprayed on the sprayed plants until it dripped gently, and after air-drying, the adult brown planthoppers were provided. Calculate the mortality rate after a certain period of time. The results of a control test conducted in the same manner except that the test compound was not used are also listed.
【表】
試験例 ２
ニセナミハダニ（Tetranyohus Telarius）に
対する試験
供試化合物２重量部をアセトン98重量部に溶解
する。これを0.04％展着剤入り水溶液を用いて所
定濃度に希釈する。ポツト値えインゲン
（Phaseolus valqaris）にニセナミハダニ成虫を
接種し、上記の如く調整された液剤を噴霧する。
一定時間（１週間）後の死虫率を求める。[Table] Test Example 2 Test against Tetranyohus Telarius Dissolve 2 parts by weight of the test compound in 98 parts by weight of acetone. This is diluted to a predetermined concentration using an aqueous solution containing 0.04% spreading agent. Pot value green beans (Phaseolus valqaris) are inoculated with adult spider mites and sprayed with the solution prepared as above.
Obtain the mortality rate after a certain period of time (1 week).
【表】
試験例 ３
アズキゾウムシ（Allosobruchus chinensis）
のドライフイルム法試験
供試化合物２重量部をアセトン98重量部に溶解
させ、各所定濃度に調整する。各供試液の0.5ml
をミニシヤーレ（直径６cm）内に入れ、シヤーレ
の底面全体に広げ、室温で放置した。アセトンが
完全に蒸発した後にアズキゾウムシの成虫（羽化
後０〜24時間）を各々10頭、シヤーレ内に入れ、
室温で放置し、24時間後に生死を判別した。各区
２連、計20頭を１化合物、１濃度に供した。[Table] Test example 3 Adzuki bean weevil (Allosobruchus chinensis)
Dry film method test 2 parts by weight of the test compound are dissolved in 98 parts by weight of acetone and adjusted to each prescribed concentration. 0.5ml of each test solution
was placed in a mini chaat dish (6 cm in diameter), spread over the entire bottom of the chaat dish, and left at room temperature. After the acetone had completely evaporated, 10 adult adzuki bean weevils (0 to 24 hours after emergence) were placed in a shearer.
The animals were left at room temperature, and 24 hours later, they were determined to be alive or dead. A total of 20 animals were subjected to one compound and one concentration in two replicates for each group.
Claims (1)
基、R2は低級アルコキシ基、低級アルキルアミ
ノ基、低級アルキルメルカプト基又はフエニルア
ルキルメルカプト基、Ｙは酸素原子又は硫黄原
子、R3は水素原子、低級アルキル基、フエニル
基、シクロヘキシル基、ニトロ基又はハロゲン原
子、Ｘはハロゲン原子を示す）で表わされるリン
酸エステル誘導体。 ２ 一般式 （式中R3は水素原子、低級アルキル基、フエ
ニル基、シクロヘキシル基、ニトロ基又はハロゲ
ン原子、Ｘはハロゲン原子を示す）で表わされる
３―ハイドロキシ―γ―ピロン類と一般式 （式中R1は低級アルコキシ基又はフエニル
基、R2は低級アルコキシ基、低級アルキルアミ
ノ基、低級アルキルメルカプト基又はフエニルア
ルキルメルカプト基、Ｙは酸素原子又は硫黄原
子、Halはハロゲン原子を示す）で表わされるリ
ン酸ハライド類とを反応させることを特徴とする
一般式 （式中R1，R2，R3，Ｘ及びＹは上記に同じ）
で表わされるリン酸エステル誘導体の製造法。 ３ 一般式 （式中R1は低級アルコキシ基又はフエニル
基、Ｍはアルカリ金属原子、Ｙは酸素原子又は硫
黄原子、R3は水素原子、低級アルキル基、フエ
ニル基、シクロヘキシル基、ニトロ基又はハロゲ
ン原子、Ｘはハロゲン原子を示す）で表わされる
リン酸塩と一般式 R4―Hal （式中R4は低級アルキル基又はフエニルアル
キル基、Halはハロゲン原子を示す）で表わされ
るハロゲン化合物とを反応させることを特徴とす
る一般式 （式中R1，R3，Ｘ及びＹは上記に同じ、R5は
低級アルキルメルカプト基又はフエニルアルキル
メルカプト基を示す）で表わされるリン酸エステ
ル誘導体の製造法。 ４ 一般式 （式中R1は低級アルコキシ基又はフエニル
基、R2は低級アルコキシ基、低級アルキルアミ
ノ基、低級アルキルメルカプト基又はフエニルア
ルキルメルカプト基、R3は水素原子、低級アル
キル基、フエニル基、シクロヘキシル基、ニトロ
基又はハロゲン原子、Ｘはハロゲン原子、Ｙは酸
素原子又は硫黄原子を示す）で表わされるリン酸
エステル誘導体を有効成分として含有する農園芸
用殺虫・殺ダニ剤。[Claims] 1. General formula (In the formula, R 1 is a lower alkoxy group or a phenyl group, R 2 is a lower alkoxy group, a lower alkylamino group, a lower alkylmercapto group, or a phenylalkylmercapto group, Y is an oxygen atom or a sulfur atom, R 3 is a hydrogen atom, A phosphoric acid ester derivative represented by a lower alkyl group, a phenyl group, a cyclohexyl group, a nitro group, or a halogen atom (X represents a halogen atom). 2 General formula (In the formula, R 3 is a hydrogen atom, a lower alkyl group, a phenyl group, a cyclohexyl group, a nitro group, or a halogen atom, and X is a halogen atom) and the general formula (In the formula, R 1 is a lower alkoxy group or phenyl group, R 2 is a lower alkoxy group, lower alkylamino group, lower alkylmercapto group, or phenylalkylmercapto group, Y is an oxygen atom or a sulfur atom, and Hal is a halogen atom. ) A general formula characterized by reacting with a phosphoric acid halide represented by (In the formula, R 1 , R 2 , R 3 , X and Y are the same as above)
A method for producing a phosphate ester derivative represented by 3 General formula (In the formula, R 1 is a lower alkoxy group or phenyl group, M is an alkali metal atom, Y is an oxygen atom or a sulfur atom, R 3 is a hydrogen atom, a lower alkyl group, a phenyl group, a cyclohexyl group, a nitro group, or a halogen atom, is a halogen atom) and a halogen compound represented by the general formula R 4 -Hal (wherein R 4 is a lower alkyl group or phenylalkyl group, and Hal is a halogen atom) are reacted. A general formula characterized by A method for producing a phosphoric acid ester derivative represented by the formula (wherein R 1 , R 3 , X and Y are the same as above, and R 5 represents a lower alkylmercapto group or a phenylalkylmercapto group). 4 General formula (In the formula, R 1 is a lower alkoxy group or phenyl group, R 2 is a lower alkoxy group, lower alkylamino group, lower alkylmercapto group, or phenylalkylmercapto group, R 3 is a hydrogen atom, lower alkyl group, phenyl group, cyclohexyl group) An agricultural and horticultural insecticide and acaricide containing as an active ingredient a phosphoric acid ester derivative represented by a group, a nitro group, or a halogen atom, where X is a halogen atom, and Y is an oxygen atom or a sulfur atom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17345679A JPS5692293A (en) | 1979-12-26 | 1979-12-26 | Phosphoric ester derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17345679A JPS5692293A (en) | 1979-12-26 | 1979-12-26 | Phosphoric ester derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5692293A JPS5692293A (en) | 1981-07-25 |
| JPS6248675B2 true JPS6248675B2 (en) | 1987-10-15 |
Family
ID=15960802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17345679A Granted JPS5692293A (en) | 1979-12-26 | 1979-12-26 | Phosphoric ester derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5692293A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0192079U (en) * | 1987-12-10 | 1989-06-16 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6137789A (en) * | 1984-07-31 | 1986-02-22 | Otsuka Chem Co Ltd | Gamma-pyrrone phosphoric ester derivative, insecticide and acaricide for agriculture and horticulture comprising it as active ingredient |
-
1979
- 1979-12-26 JP JP17345679A patent/JPS5692293A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0192079U (en) * | 1987-12-10 | 1989-06-16 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5692293A (en) | 1981-07-25 |
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