JPS6113459B2 - - Google Patents
Info
- Publication number
- JPS6113459B2 JPS6113459B2 JP52016635A JP1663577A JPS6113459B2 JP S6113459 B2 JPS6113459 B2 JP S6113459B2 JP 52016635 A JP52016635 A JP 52016635A JP 1663577 A JP1663577 A JP 1663577A JP S6113459 B2 JPS6113459 B2 JP S6113459B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- hydrogen atom
- represented
- parts
- compound according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000004480 active ingredient Substances 0.000 claims description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 230000000895 acaricidal effect Effects 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- -1 cyclopropanecarboxylic acid ester Chemical class 0.000 claims description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000642 acaricide Substances 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000002917 insecticide Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000000749 insecticidal effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 239000000839 emulsion Substances 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 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 5
- 229920000151 polyglycol Polymers 0.000 description 5
- 239000010695 polyglycol Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 241000238631 Hexapoda Species 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 241001454293 Tetranychus urticae Species 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241001327638 Cimex lectularius Species 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WABPPBHOPMUJHV-UHFFFAOYSA-N Sesamex Chemical compound CCOCCOCCOC(C)OC1=CC=C2OCOC2=C1 WABPPBHOPMUJHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 2
- 241000253994 Acyrthosiphon pisum Species 0.000 description 2
- 206010004194 Bed bug infestation Diseases 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 241000256257 Heliothis Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 241000238814 Orthoptera Species 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 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
- 241000256248 Spodoptera Species 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 240000006677 Vicia faba Species 0.000 description 2
- 235000010749 Vicia faba Nutrition 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 235000013601 eggs Nutrition 0.000 description 2
- 239000004495 emulsifiable concentrate Substances 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 125000000913 palmityl 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])C([H])([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 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 210000002784 stomach Anatomy 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UXPPDBVMSPAPCL-UHFFFAOYSA-N 1-prop-1-ynoxyprop-1-yne Chemical compound CC#COC#CC UXPPDBVMSPAPCL-UHFFFAOYSA-N 0.000 description 1
- HRQBQVOUHQTQFJ-UHFFFAOYSA-N 2,2-dimethyl-3-(2-phenylethenyl)cyclopropane-1-carboxylic acid Chemical compound OC(=O)C1C(C)(C)C1C=CC1=CC=CC=C1 HRQBQVOUHQTQFJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GXUQMKBQDGPMKZ-UHFFFAOYSA-N 2-hydroxy-2-(3-phenoxyphenyl)acetonitrile Chemical compound N#CC(O)C1=CC=CC(OC=2C=CC=CC=2)=C1 GXUQMKBQDGPMKZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241001143309 Acanthoscelides obtectus Species 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 241000132121 Acaridae Species 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- 241001425390 Aphis fabae Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241001674044 Blattodea Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- 241001498622 Cixius wagneri Species 0.000 description 1
- 241000255749 Coccinellidae Species 0.000 description 1
- 241001465977 Coccoidea Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000256113 Culicidae Species 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical class NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- 241000237365 Helicidae Species 0.000 description 1
- 241000256244 Heliothis virescens Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000258915 Leptinotarsa Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000257229 Musca <genus> Species 0.000 description 1
- 241000257159 Musca domestica Species 0.000 description 1
- 241000721621 Myzus persicae Species 0.000 description 1
- 241000256259 Noctuidae Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 244000141353 Prunus domestica Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241000256250 Spodoptera littoralis Species 0.000 description 1
- 235000002098 Vicia faba var. major Nutrition 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229920005551 calcium lignosulfonate Polymers 0.000 description 1
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000007931 coated granule Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 239000004491 dispersible concentrate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 231100000487 gastrotoxic Toxicity 0.000 description 1
- 230000002162 gastrotoxic effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000021332 kidney beans Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- OSOBRNLAUDAQKA-UHFFFAOYSA-N prop-1-ynyl dihydrogen phosphate Chemical compound CC#COP(O)(O)=O OSOBRNLAUDAQKA-UHFFFAOYSA-N 0.000 description 1
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical class 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 244000045561 useful plants Species 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は新規シクロプロパンカルボン酸エステ
ルおよびその製造方法ならびにそれぞれを含有す
る殺虫、殺ダニ剤に関する。
本発明のシクロプロパンカルボン酸エステル
は、
次式：
（式中、
R1は水素原子またはメチル基を表わし、
R2は水素原子、メチル、シアノまたはエチニ
ル基を表わし、
Ｘは水素原子、ハロゲン原子またはメチル基を
表わし、
ｎは１または２を表わす。）
で表わされる。
ハロゲン原子は弗素、塩素、臭素および／また
は沃素原子を意味するが、好ましくは塩素原子を
意味する。
R1が水素原子またはメチル基であり、R2が水
素原子、シアノまたはエチニル基であり、Ｘが水
素原子、弗素原子、塩素原子またはメチル基であ
り、ｎが１である式の化合物が作用の点で好ま
しい。
式の化合物は公知方法に準じて、例えば次の
ようにして製造することが出来る。
（式中、R1、R2、Ｘおよびｎは式で表わしたの
と同じ意味を有し、Ｚはハロゲン原子特に塩素ま
たは臭素原子、或いは水酸基を表わし、ＹはＺが
ハロゲン原子の場合は水酸基を、Ｚが水酸基の場
合はハロゲン原子特に塩素または臭素原子を表わ
す。）
（式中、R1、R2、Ｘおよびｎは式で表わしたの
と同じ意味を有する。）
上記第１法における酸結合剤としては、特にト
リアルキルアミンやピリジンの様な第三級アミン
およびアルカリ金属やアルカリ土類金属の水酸化
物、酸化物、炭酸塩、重炭酸塩ならびにアルカリ
金属、アルカリ土類金属更にはカリウム第三ブチ
ラートやナトリウムメチラートの様なアルカリ金
属アルコラートが好ましい。上記第２法における
脱水剤はたとえばジシクロヘキシルカルボジイミ
ドである。
上記第１および２法の反応は、−10ないし100
℃、通常は20ないし80℃の温度で、常圧または加
圧下で、好ましくは該反応に不活性な溶媒または
希釈剤中で行う。適当な溶媒または希釈剤は、た
とえばジエチルエーテル、ジプロピルエーテル、
ジオキサン、ジメトキシエタン、テトラヒドロフ
ランの様なエーテルおよびエーテル性化合物；
Ｎ・Ｎ−ジアルキルカルボン酸アミドの様なアミ
ド；脂肪族、芳香族およびハロゲン化炭化水素、
特にベンゼン、トルエン、キシレン、クロロホル
ム、クロロベンゼン；アセトニトリルの様なニト
リル；ジメチルスルホキシド；アセトンやメチル
エチルケトンの様なケトンである。上記第１法に
おいてＺが水酸基であり、Ｙがハロゲン原子であ
る場合には反応は水溶液中でも行い得る。
式、a、、aの出発原料は公知である
か、あるいはそうでない場合は公知方法に準じて
製造し得る。
式の化合物は、出発原料が単一の光学活性化
合物またはシス／トランス異性体でない場合は、
光学異性体およびシス／トランス異性体混合物と
して得られる。異種の安定な異性体の混合物は公
知方法により、それぞれの異性体に分離すること
が出来る。本発明細書で使用する「式の化合
物」なる語は、個々の異性体およびそれらの混合
物を包含する。式の化合物は種々の動物および
植物に有害な生物の防除に適している。これらは
特に昆虫およびダニ目の代表的なものの防除に適
している。たとえばキリギリス科、コウロギ科、
ケラ科、ゴキブリ科、サシガメ科、ホシカメムシ
科、トコジラミ科、ウンカ科、アブラムシ科、マ
ルカイガラムシ科、コナカイガラムシ科、コガネ
ムシ科、カツオブシムシ科、テントウムシ科、ゴ
ミムシダマシ科、ハムシ科、マメゾウムシ科、ヒ
ロズコガ科、ヤガ科、ドクガ科、メイガ科、カ
科、ガガジボ科、サシバエ科、ミバエ科、イエバ
エ科、クロバエ科およびノミ科の昆虫ならびにハ
ダニ科およびサシダニ科に対して使用し得る。
式の化合物は、特に観賞用植物や有用植物の
栽培において植物を損傷する昆虫、とりわけ食害
をもたらす昆虫、特に木綿栽培における害虫〔た
とえばスポドプテラ・リトラリス（Spodoptera
littoralisおよびヘリオチス・ビレツセンス
（Heliothis virescens）〕や野菜栽培における害虫
〔たとえばレプチノタルサ・デムセリネアータ
（Leptinotarsa demceli−neata）およびモモアカ
アブラムシ（Myzus persicae）〕の防除に適して
いる。式の有効成分は、イエバエ（Musca
domestica）のようなハエ、および蚊の幼虫に対
しても極めて良好な作用を示す。
この殺虫および殺ダニ作用は、他の殺虫剤およ
び／または殺ダニ剤の添加によつて実質的に拡大
され、また与えられた還境に適応させることが出
来る。適当な添加剤としては、たとえば次のもの
があげられる：
有機燐化合物、
ニトロフエノール類およびその誘導体、
ホルムアミジン類、
尿素類、
他のピレトリン系化合物、
カルバメート類、
塩素化炭化水素。
式の化合物を、ピレスロイドの共力剤または
強化剤と組合せるのも特に有利である。そのよう
な化合物としては、とりわけピペロニルブトキシ
ド、プロピニルエーテルおよびプロピニルホスフ
エート、２−（３・４−メチレンジオキシフエノ
キシ）−３・６・９−トリオキサウンデカン〔セ
サメツクス（Sesamex）またはセソキサン
（Sesoxane）〕、Ｓ・Ｓ・Ｓ−トリブチルホスフオ
ロトリチオエートおよび１・２−メチレン−ジオ
キシ−４−〔（２−オクチルスルホニル）−プロピ
ル〕−ベンゼンがあげられる。
式の化合物は単味で、または適当な担体およ
び／または添加剤とともに使用し得る。適当な添
加剤は固体でも液体でもよく、製剤上慣用される
もの、例えば天然および再生物質、溶剤、分散
剤、湿潤剤、固着剤、シツクナー、結合剤、肥料
等である。
本発明の有害生物防除用組成物は、式の有効
成分を適当な担体と共に、場合によつては有効成
分に対し不活性な分散剤または溶剤を添加して緊
密に混合および／または摩砕する等、公知方法に
より製造される。本発明の有効成分は次の様な形
で使用し得る：
固体製剤：粉剤、散布剤、顆粒（被覆顆粒、含
浸顆粒、均質顆粒）
液体製剤：
(a) 有効成分の水分散性濃厚物：水和剤、ペース
ト、エマルジヨン、
(b) 溶液。
上記組成物中の有効成分含量は0.1ないし95％
である。
式の有効成分は例えば以下の様に配合し得
る：
(1) 粉剤
下記の各成分を用いて(a)５％粉剤、(b)２％粉
剤を製造する：
(a) 有効成分 ５部
タルク 95部
(b) 有効成分 ２部
高分散性硅酸 １部
タルク 97部
有効成分を担体と混合し、摩砕する。
(2) 顆粒
下記の各成分を用いて５％顆粒を製造する：
有効成分 ５ 部
エピクロルヒドリン 0.25部
セチルポリグリコールエーテル 0.25部
ポリエチレングリコール 3.50部
カオリン（粒径0.3−0.8mm） 91 部
有効成分をエピクロルヒドリンと混合し、ア
セトン６部に溶解し、次にポリエチレングリコ
ールとセチルポリグリコールエーテルを添加す
る。この溶液をカオリンにスプレーし、次にア
セトンを留去する。
(3) 水和剤
下記の各成分を用いて(a)40％、(b)および(c)25
％、(d)10％水和剤を製造する：
(a) 有効成分 40部
リグニンスルホン酸ナトリウム ５部
ジブチルナフタリンスルホン酸ナトリウム
１部
硅 酸 54部
(b) 有効成分 25 部
リグニシスルホン酸カルシウム 4.5部
シヤンペンチヨーク／ヒドロキシエチルセル
ロース混合物（１：１） 1.9部
ジブチルナフタリンスルホン酸ナトリウム
1.5部
硅 酸 19.5部
シヤンペンチヨーク 19.5部
カオリン 28.1部
(c) 有効成分 25 部
イソオクチルフエノキシ−ポリオキシエチレ
ン−エタノール 2.5部
シヤンペンチヨーク／ヒドロキシエチルセル
ロース混合物（１：１） 1.7部
硅酸アルミニウムナトリウム 8.3部
硅藻土 16.5部
カオリン 46 部
(d) 有効成分 10 部
飽和硫酸化脂肪アルコールのナトリウム塩の
混合物 ３ 部
ナフタリンスルホン酸／ホルムアルデヒド縮
合物 ５ 部
カオリン 82 部
有効成分を適当な混合機中で添加剤と緊密に
混合し、この混合物を適当な粉砕機、ローラー
で粉砕する。水で所望濃度の懸濁液に希釈し得
る水和剤が得られる。
(4) 乳化性濃厚物
下記の各成分を用いて(a)10％、(b)25％、(c)50
％乳化性濃厚物を製造する：
(a) 有効成分 10 部
エポキシ化植物油 3.4部
脂肪アルコールポリグリコールエーテルとア
ルキルアリールスルホン酸カルシウムから成
る複合乳化剤 3.4部
ジメチルホルムアミド 40 部
キシレン 43.2部
(b) 有効成分 25 部
エポキシ化植物油 2.5部
アルキルアリールスルホネート／脂肪アルコ
ールポリグリコールエーテル混合物 10 部
ジメチルホルムアミド ５ 部
キシレン 57.5部
(c) 有効成分 50 部
トリブチルフエノール−ポリグリコールエー
テル 4.2部
ドデシルベンゼンスルホン酸カルシウム
5.8部
シクロヘキサノン 20 部
キシレン 20 部
これらの濃厚物は水で希釈して所望濃度の乳
液に調製することが出来る。
(5) 噴霧剤
下記の各成分を用いて(a)５％、(b)95％噴霧剤
を製造する：
(a) 有効成分 ５部
エピクロルヒドリン １部
リグロイン（沸点160−190℃） 94部
(b) 有効成分 95部
エピクロルヒドリン ５部
次に本発明を実施例により説明する。
実施例 １
２・２−ジメチル−３−（2′−フエニルビニ
ル）−シクロプロパンカルボン酸−3″−フエノ
キシ−α−シアノベンジルエステルの製造
２・２−ジメチル−３−（2′−フエニルプロピ
ル）−シクロプロパンカルボン酸22ｇをヘキサン
300に加えた液に、塩化チオニル17ｇを滴下す
る。反応混合物を４時間還流する。ヘキサンを留
去して得られる酸クロライドを、メチルエチルケ
トン300mlと３−フエノキシ−α−シアノベンジ
ルアルコール23ｇ並びにピリジン10mlの混合物中
に、５−10℃で撹拌しつゝ滴下する。１時間撹拌
後室温で12時間放置し、次に反応混合物を100ml
の水希釈ベンゼン、３％塩酸、水、３％炭酸ナト
リウム溶液、水で順次洗滌し、続いて硫酸ナトリ
ウムで乾燥する。溶媒を留去して得られる油状粗
生成物を、エーテル／ヘキサン（１：６）を溶離
剤としてクロマトグラフイーにかけて精製する。
次式：
の化合物が、屈折率ｎ２０ Ｄ＝1.5695の無色油状物と
して得られる。この生成物は異性体混合物である
（純砕のシス体の屈折率はｎ２０ Ｄ＝1.5710）。
同様にして以下の化合物が得られる：
The present invention relates to novel cyclopropane carboxylic acid esters, methods for producing the same, and insecticides and acaricides containing each. The cyclopropane carboxylic acid ester of the present invention has the following formula: (In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom, methyl, cyano, or ethynyl group, X represents a hydrogen atom, a halogen atom, or a methyl group, and n represents 1 or 2. ). Halogen atom means fluorine, chlorine, bromine and/or iodine atom, preferably chlorine atom. A compound of the formula in which R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom, a cyano or ethynyl group, X is a hydrogen atom, a fluorine atom, a chlorine atom or a methyl group, and n is 1 acts. It is preferable in this respect. The compound of the formula can be produced according to a known method, for example, as follows. (In the formula, R 1 , R 2 , When Z is a hydroxyl group, it represents a halogen atom, especially a chlorine or bromine atom.) (In the formula, R 1 , R 2 , Preferred are alkali metal and alkaline earth metal hydroxides, oxides, carbonates, bicarbonates and alkali metal, alkaline earth metal and alkali metal alcoholates such as potassium tert-butyrate and sodium methylate. The dehydrating agent in the second method is, for example, dicyclohexylcarbodiimide. The reactions of the first and second methods above are -10 to 100
The reaction is carried out at a temperature of 0.degree. C., usually from 20 to 80.degree. C., under normal or elevated pressure, preferably in a solvent or diluent inert to the reaction. Suitable solvents or diluents are, for example, diethyl ether, dipropyl ether,
ethers and ethereal compounds such as dioxane, dimethoxyethane, tetrahydrofuran;
amides such as N.N-dialkylcarboxylic acid amides; aliphatic, aromatic and halogenated hydrocarbons;
In particular, benzene, toluene, xylene, chloroform, chlorobenzene; nitriles such as acetonitrile; dimethyl sulfoxide; and ketones such as acetone and methyl ethyl ketone. In the first method, when Z is a hydroxyl group and Y is a halogen atom, the reaction can also be carried out in an aqueous solution. The starting materials of formula, a , , a are known or may otherwise be prepared according to known methods. Compounds of formula, if the starting material is not a single optically active compound or a cis/trans isomer,
Obtained as optical isomers and cis/trans isomer mixtures. A mixture of different stable isomers can be separated into individual isomers by known methods. As used herein, the term "compound of formula" includes the individual isomers and mixtures thereof. The compounds of formula are suitable for controlling organisms harmful to various animals and plants. They are particularly suitable for controlling insects and representatives of the order Acarina. For example, katydids, katydids,
Molecular family, Cockroach family, Assassinidae, Bedbug family, Bed bug family, Planthopper family, Aphid family, Mealyptidae, Mealyptidae, Scarabidae, Mealyptidae, Ladybug family, Mealybug family, Chrysophyllidae, Bean weevil family, Bedbug family, It can be used against insects of the families Noctuidae, Helicidae, Poritedae, Mothidae, Agaridae, Speridae, Fruitflyae, Muscatidae, Thrushidae, and Fleaidae, as well as the Arididae and Acaridae families. Compounds of the formula are suitable for use against insects that damage plants, especially in the cultivation of ornamental and useful plants, in particular insects that cause feeding damage, and in particular pests in cotton cultivation [such as Spodoptera litoralis].
littoralis and Heliothis virescens] and pests in vegetable cultivation such as Leptinotarsa demceli-neata and Myzus persicae. The active ingredient in the formula is house fly (Musca
It is also very effective against flies such as P. domestica) and mosquito larvae. This insecticidal and acaricidal action can be substantially extended and adapted to the given environment by the addition of other insecticides and/or acaricides. Suitable additives include, for example: organophosphorus compounds, nitrophenols and their derivatives, formamidines, ureas, other pyrethrin compounds, carbamates, chlorinated hydrocarbons. It is also particularly advantageous to combine the compounds of the formula with pyrethroid synergists or enhancers. Such compounds include, inter alia, piperonyl butoxide, propynyl ether and propynyl phosphate, 2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane (Sesamex or Sesoxane). )], S.S.S-tributylphosphorotrithioate and 1,2-methylene-dioxy-4-[(2-octylsulfonyl)-propyl]-benzene. Compounds of formula may be used alone or with suitable carriers and/or excipients. Suitable additives may be solid or liquid and are those customary in pharmaceutical formulations, such as natural and recycled substances, solvents, dispersants, wetting agents, fixing agents, thickeners, binders, fertilizers, etc. The pest control composition of the present invention is prepared by intimately mixing and/or grinding the active ingredient of the formula with a suitable carrier, optionally with the addition of a dispersant or solvent inert to the active ingredient. etc., by a known method. The active ingredient according to the invention can be used in the following forms: Solid formulations: powders, dusting powders, granules (coated granules, impregnated granules, homogeneous granules) Liquid formulations: (a) Water-dispersible concentrates of the active ingredient: Wettable powders, pastes, emulsions, (b) solutions. The active ingredient content in the above composition is 0.1 to 95%
It is. The active ingredients of the formula can be formulated, for example, as follows: (1) Powder The following ingredients are used to produce (a) 5% powder and (b) 2% powder: (a) Active ingredient 5 parts talc. 95 parts (b) Active ingredient 2 parts highly dispersed silicic acid 1 part talc 97 parts The active ingredient is mixed with the carrier and ground. (2) Granules Manufacture 5% granules using the following ingredients: Active ingredients 5 parts epichlorohydrin 0.25 parts cetyl polyglycol ether 0.25 parts polyethylene glycol 3.50 parts Kaolin (particle size 0.3-0.8 mm) 91 parts Epichlorohydrin and dissolve in 6 parts of acetone, then add polyethylene glycol and cetyl polyglycol ether. This solution is sprayed onto the kaolin and then the acetone is distilled off. (3) Wettable powder: (a) 40%, (b) and (c) 25% by using each of the following ingredients.
%, (d) Produce a 10% hydrating powder: (a) Active ingredients 40 parts sodium lignin sulfonate 5 parts sodium dibutylnaphthalene sulfonate
1 part Silicic acid 54 parts (b) Active ingredients 25 parts Calcium lignosulfonate 4.5 parts Cyanpentyoke/Hydroxyethyl cellulose mixture (1:1) 1.9 parts Sodium dibutylnaphthalene sulfonate
1.5 parts Silicic acid 19.5 parts Shinpentyoke 19.5 parts Kaolin 28.1 parts (c) Active ingredients 25 parts Isooctylphenoxy-polyoxyethylene-ethanol 2.5 parts Shinpentyoke/Hydroxyethyl cellulose mixture (1:1) 1.7 parts Silicic acid Sodium aluminum 8.3 parts Diatomaceous earth 16.5 parts Kaolin 46 parts (d) Active ingredient 10 parts Mixture of sodium salts of saturated sulfated fatty alcohols 3 parts Naphthalene sulfonic acid/formaldehyde condensate 5 parts Kaolin 82 parts Combine the active ingredients in a suitable blender. The mixture is mixed intimately with the additives in a suitable grinder or roller. A wettable powder is obtained which can be diluted with water to a suspension of the desired concentration. (4) Emulsifiable concentrates: (a) 10%, (b) 25%, (c) 50% using each of the following ingredients:
% emulsifiable concentrate is prepared: (a) Active ingredients 10 parts Epoxidized vegetable oil 3.4 parts Complex emulsifier consisting of fatty alcohol polyglycol ether and calcium alkylaryl sulfonate 3.4 parts Dimethylformamide 40 parts Xylene 43.2 parts (b) Active ingredients 25 parts Epoxidized vegetable oil 2.5 parts Alkylaryl sulfonate/fatty alcohol polyglycol ether mixture 10 parts Dimethylformamide 5 parts Xylene 57.5 parts (c) Active ingredients 50 parts Tributylphenol-polyglycol ether 4.2 parts Calcium dodecylbenzenesulfonate
5.8 parts cyclohexanone 20 parts xylene 20 parts These concentrates can be diluted with water to form an emulsion of the desired concentration. (5) Propellant Prepare (a) 5%, (b) 95% propellant using each of the following ingredients: (a) Active ingredients 5 parts epichlorohydrin 1 part ligroin (boiling point 160-190°C) 94 parts ( b) Active ingredient: 95 parts epichlorohydrin 5 parts Next, the present invention will be explained with reference to Examples. Example 1 Production of 2,2-dimethyl-3-(2'-phenylvinyl)-cyclopropanecarboxylic acid-3''-phenoxy-α-cyanobenzyl ester 2,2-dimethyl-3-(2'-phenylpropyl ) - 22g of cyclopropanecarboxylic acid in hexane
Add 17 g of thionyl chloride dropwise to the solution added to 300. The reaction mixture is refluxed for 4 hours. The acid chloride obtained by distilling off the hexane is added dropwise to a mixture of 300 ml of methyl ethyl ketone, 23 g of 3-phenoxy-α-cyanobenzyl alcohol and 10 ml of pyridine while stirring at 5-10°C. After stirring for 1 hour, leave at room temperature for 12 hours, then add 100 ml of the reaction mixture.
of water-diluted benzene, 3% hydrochloric acid, water, 3% sodium carbonate solution, water, followed by drying over sodium sulfate. The oily crude product obtained by distilling off the solvent is purified by chromatography using ether/hexane (1:6) as eluent. The following formula: is obtained as a colorless oil with a refractive index n 20 D =1.5695. This product is a mixture of isomers (refractive index of the pure cis form is n 20 D =1.5710). Similarly, the following compounds are obtained:
【表】【table】
【表】【table】
【表】
実施例 ２
(A) 胃毒殺虫作用
タバコおよびジヤガイモの木に、有効成分の
0.05％水性乳液（10％乳化性濃厚物から調製）
を噴霧した。
被膜が乾燥した後、L3−段階のヘリオチ
ス・ビレツセンスおよびスポドプテラ・リトラ
リスの青虫を、これらの木に付着させた。試験
は24℃、相対湿度60％で行つた。
この試験において、実施例１の化合物は、ヘ
リオチス・ビレツセンスおよびスポドプテラ・
リトラリスの青虫に対し、良好な胃毒殺虫作用
を示した。
(B) 接触殺虫作用
有効成分乳液を適用する前日に、ポツト栽培
のソラマメ（Vicia faba）の木に一本あたり
200匹のマメアブラムシ（Aphis fabae）を寄
生させた。1000ppm濃度のスプレー乳液（25
％水和剤から調製）を圧搾空気噴霧機を用いて
ソラマメの葉に適用した。24時間後に評価を行
つた。この試験において実施例１の化合物はマ
メアブラムシに対し良好な接触殺虫作用を示し
た。
実施例 ３
殺ダニ作用
有効成分を適用する12時間前に、インゲンマメ
（Phaseolus vulgaris）に、ナミハダニ
（Tetranychus urticae）を集団培養した葉片を用
いて寄生させた。寄生させた可動期のナミハダニ
に試験化合物の乳剤を、クロマトグラフイー用ス
プレーを用いて、スプレー液が溢出しない様に注
意して噴霧した。２〜７日後に、生存および死亡
幼虫、成虫、卵の数を双眼顕微鏡で調べ、結果を
パーセントで表わした。処理植物は試験期間中25
℃の温室に入れておいた。
実施例１の化合物は、ナミハダニの幼虫、成
虫、卵に対し、良好な作用を示した。
以上の実施例２の胃毒殺虫作用、接触殺虫作
用、実施例３の殺ダニ作用にもとづく実施例１の
化合物の100％殺虫、殺ダニ効果を示す最少濃度
をまとめると次表のように表わすことができる。[Table] Example 2 (A) Insecticidal action of stomach poison
0.05% aqueous emulsion (prepared from 10% emulsifying concentrate)
was sprayed. After the coating had dried, L 3 -stage Heliothis viretscens and Spodoptera littoralis caterpillars were attached to these trees. The test was conducted at 24°C and 60% relative humidity. In this test, the compound of Example 1 was tested for Heliothis viretscens and Spodoptera
It showed good gastrotoxic insecticidal action against litoralis caterpillars. (B) Contact insecticidal action: The day before application of the active ingredient emulsion, it was applied to each Vicia faba tree grown in pots.
Infested with 200 pea aphids (Aphis fabae). Spray emulsion with a concentration of 1000ppm (25
% hydration powder) was applied to broad bean leaves using a compressed air sprayer. Evaluation was performed 24 hours later. In this test, the compound of Example 1 showed good contact insecticidal activity against pea aphids. Example 3 Acaricidal action Twelve hours before application of the active ingredient, kidney beans (Phaseolus vulgaris) were infested with leaf pieces on which two-spotted spider mites (Tetranychus urticae) had been collectively cultured. An emulsion of the test compound was sprayed onto parasitized two-spotted spider mites in the mobile stage using a chromatography sprayer, taking care not to overflow the spray solution. After 2-7 days, the number of live and dead larvae, adults, and eggs was examined under a binocular microscope and the results were expressed as a percentage. 25 treated plants during the test period
It was kept in a greenhouse at ℃. The compound of Example 1 showed good effects on larvae, adults, and eggs of two-spotted spider mites. Based on the stomach poisoning insecticidal action and contact insecticidal action of Example 2 and the acaricidal action of Example 3, the minimum concentration showing 100% insecticidal and acaricidal effects of the compound of Example 1 is summarized as shown in the following table. be able to.
【表】【table】
【表】【table】
【表】【table】
Claims (1)
ル基を表わし、 Ｘは水素原子、ハロゲン原子またはメチル基を
表わし、 ｎは１または２を表わす。） で表わされるシクロプロパンカルボン酸エステ
ル。 ２ R1が水素原子またはメチル基であり、R2が
水素原子、シアノまたはエチニル基であり、Ｘが
水素原子、弗素原子、塩素原子またはメチル基で
あり、ｎが１である特許請求の範囲第１項記載の
化合物。 ３ 次式： で表わされる特許請求の範囲第２項記載の化合
物。 ４ 次式： で表わされる特許請求の範囲第２項記載の化合
物。 ５ 次式： で表わされる特許請求の範囲第２項記載の化合
物。 ６ 次式： で表わされる特許請求の範囲第２項記載の化合
物。 ７ 次式： で表わされる特許請求の範囲第２項記載の化合
物。 ８ 次式： で表わされる特許請求の範囲第２項記載の化合
物。 ９ 次式： で表わされる特許請求の範囲第２項記載の化合
物。 １０ 次式： で表わされる特許請求の範囲第２項記載の化合
物。 １１ 次式： で表わされる特許請求の範囲第２項記載の化合
物。 １２ 次式： で表わされる特許請求の範囲第２項記載の化合
物。 １３ 次式： （式中、 R1は水素原子またはメチル基を表わし、 Ｘは水素原子、ハロゲン原子またはメチル基を
表わし、 ｎは１または２を表わし、 Ｚはハロゲン原子または水酸基を表わす。） で表わされる化合物を、酸結合剤の存在下に、次
式： （式中、 R2は水素原子、メチル、シアノまたはエチニ
ル基を表わし、 Ｙは、Ｚがハロゲン原子の場合は水酸基を、Ｚ
が水酸基の場合はハロゲン原子を表わす。） で表わされる化合物と反応させることを特徴とす
る、次式： （式中、R1、R2、Ｘおよびｎは前記と同じ意味を
表わす。） で表わされるシクロプロパンカルボン酸エステル
の製造方法。 １４ 次式ａ： （式中、 R1は水素原子またはメチル基を表わし、 Ｘは水素原子、ハロゲン原子またはメチル基を
表わし、 ｎは１または２を表わす。） で表わされる化合物を、脱水剤の存在下に次式
ａ： （式中、R2は水素原子、メチル、シアノまたはエ
チニル基を表わす。） で表わされる化合物と反応させることを特徴とす
る、次式： （式中、R1、R2、Ｘおよびｎは前記と同じ意味を
表わす。） で表わされるシクロプロパンカルボン酸エステル
の製造方法。 １５ 有効成分として、 次式： （式中、 R1は水素原子またはメチル基を表わし、 R2は水素原子、シアノまたはエチニル基を表
わし、 Ｘは水素原子、ハロゲン原子またはメチル基を
表わし、 ｎは１または２を表わす。） で表わされるシクロプロパンカルボン酸エステル
を含有する殺虫、殺ダニ剤。[Claims] Primary formula: (In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom, methyl, cyano, or ethynyl group, X represents a hydrogen atom, a halogen atom, or a methyl group, and n represents 1 or 2. .) Cyclopropane carboxylic acid ester. 2 Claims in which R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom, a cyano or ethynyl group, X is a hydrogen atom, a fluorine atom, a chlorine atom or a methyl group, and n is 1 A compound according to item 1. Cubic formula: The compound according to claim 2, which is represented by: Quaternary formula: The compound according to claim 2, which is represented by: 5th order formula: The compound according to claim 2, which is represented by: Sixth formula: The compound according to claim 2, which is represented by: 7 Formula: The compound according to claim 2, which is represented by: 8th formula: The compound according to claim 2, which is represented by: 9 Formula: The compound according to claim 2, which is represented by: 10th formula: The compound according to claim 2, which is represented by: 11 Formula: The compound according to claim 2, which is represented by: 12th equation: The compound according to claim 2, which is represented by: 13th formula: (In the formula, R 1 represents a hydrogen atom or a methyl group, X represents a hydrogen atom, a halogen atom, or a methyl group, n represents 1 or 2, and Z represents a halogen atom or a hydroxyl group.) , in the presence of an acid binder, the following formula: (In the formula, R 2 represents a hydrogen atom, methyl, cyano or ethynyl group, Y represents a hydroxyl group when Z is a halogen atom,
When is a hydroxyl group, it represents a halogen atom. ) characterized by reacting with a compound represented by the following formula: (In the formula, R 1 , R 2 , X and n have the same meanings as above.) A method for producing a cyclopropanecarboxylic acid ester represented by the following. 14 Formula a: (In the formula, R 1 represents a hydrogen atom or a methyl group, X represents a hydrogen atom, a halogen atom or a methyl group, and n represents 1 or 2.) Formula a: (In the formula, R 2 represents a hydrogen atom, methyl, cyano or ethynyl group.) (In the formula, R 1 , R 2 , X and n have the same meanings as above.) A method for producing a cyclopropanecarboxylic acid ester represented by the following. 15 As an active ingredient, the following formula: (In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom, cyano or ethynyl group, X represents a hydrogen atom, a halogen atom or a methyl group, and n represents 1 or 2.) An insecticide and acaricide containing a cyclopropanecarboxylic acid ester represented by:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH191076A CH602005A5 (en) | 1976-02-17 | 1976-02-17 | (3)-Phenoxy-benzyl styryl-cyclopropane carboxylates |
| CH5977 | 1977-01-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52100455A JPS52100455A (en) | 1977-08-23 |
| JPS6113459B2 true JPS6113459B2 (en) | 1986-04-14 |
Family
ID=25683390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1663577A Granted JPS52100455A (en) | 1976-02-17 | 1977-02-17 | Cyclopropane carboxylate ester process for preparing same and harmful living controlling agent containing same |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS52100455A (en) |
| DE (1) | DE2706184A1 (en) |
| FR (1) | FR2341554A1 (en) |
| GB (1) | GB1570928A (en) |
| IL (1) | IL51466A (en) |
| IT (1) | IT1076892B (en) |
| NL (1) | NL7701321A (en) |
| OA (1) | OA05647A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1260486A (en) * | 1976-08-27 | 1989-09-26 | John F. Engel | Insecticidal styryl- and substituted- styrylcyclopropanecarboxylates |
| DE2730515A1 (en) * | 1977-07-06 | 1979-01-18 | Bayer Ag | SUBSTITUTED PHENOXYBENZYLOXYCARBONYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES |
| DE2842542A1 (en) * | 1978-09-29 | 1980-04-17 | Bayer Ag | SUBSTITUTED BROMOSTYRYL CYCLOPROPANCARBONIC ACID PHENOXYBENZYL ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES |
| JPS55129507U (en) * | 1979-03-05 | 1980-09-12 | ||
| DE2916357A1 (en) * | 1979-04-23 | 1980-11-06 | Bayer Ag | METHOD FOR PRODUCING 3- (2-ARYL-VINYL) -2,2-DIMETHYL-CYCLOPROPAN-1-CARBONIC ACID ESTERS AND NEW INTERMEDIATE PRODUCTS THEREFOR |
| DE2916417A1 (en) * | 1979-04-23 | 1980-11-06 | Bayer Ag | PROCESS FOR THE MANUFACTURING OF 3- (ARYL-VINYL) -2,2-DIMETHYL-CYCLOPROPAN-1-CARBONIC ACID EASTERS AND NEW INTERMEDIATES THEREFORE |
| DE2916321A1 (en) * | 1979-04-23 | 1980-11-06 | Bayer Ag | PROCESS FOR THE MANUFACTURING OF STYRYLIC CYCLOPROPANE CARBONIC ACID ESTERS AND NEW INTERMEDIATE PRODUCTS THEREFORE |
| DE2916375A1 (en) * | 1979-04-23 | 1980-11-06 | Bayer Ag | METHOD FOR PRODUCING STYRYL-CYCLOPROPANE-CARBONIC ACID ESTERS AND NEW INTERMEDIATE PRODUCTS THEREFOR |
| DE2916358A1 (en) | 1979-04-23 | 1980-11-06 | Bayer Ag | SUBSTITUTED STYRYLCYCLOPROPANCARBONIC ACID ESTERS, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS INSECTICIDES AND ACARICIDES |
| DE2920947A1 (en) * | 1979-05-23 | 1980-12-04 | Bayer Ag | 2-PHENYL-ALKEN-1-YL-CYCLOPROPANE-CARBONIC ACID ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES AND INTERMEDIATE PRODUCTS FOR THEIR PRODUCTION |
-
1977
- 1977-02-08 NL NL7701321A patent/NL7701321A/en not_active Application Discontinuation
- 1977-02-14 DE DE19772706184 patent/DE2706184A1/en not_active Ceased
- 1977-02-15 FR FR7704227A patent/FR2341554A1/en active Granted
- 1977-02-16 IT IT20351/77A patent/IT1076892B/en active
- 1977-02-16 IL IL51466A patent/IL51466A/en unknown
- 1977-02-16 GB GB6501/77A patent/GB1570928A/en not_active Expired
- 1977-02-17 JP JP1663577A patent/JPS52100455A/en active Granted
- 1977-04-27 OA OA56153A patent/OA05647A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52100455A (en) | 1977-08-23 |
| FR2341554B1 (en) | 1980-02-08 |
| GB1570928A (en) | 1980-07-09 |
| OA05647A (en) | 1981-04-30 |
| NL7701321A (en) | 1977-08-19 |
| IT1076892B (en) | 1985-04-27 |
| DE2706184A1 (en) | 1977-08-18 |
| IL51466A0 (en) | 1977-04-29 |
| IL51466A (en) | 1979-09-30 |
| FR2341554A1 (en) | 1977-09-16 |
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