JPS63135302A - Herbicide composition - Google Patents
Herbicide compositionInfo
- Publication number
- JPS63135302A JPS63135302A JP27966086A JP27966086A JPS63135302A JP S63135302 A JPS63135302 A JP S63135302A JP 27966086 A JP27966086 A JP 27966086A JP 27966086 A JP27966086 A JP 27966086A JP S63135302 A JPS63135302 A JP S63135302A
- Authority
- JP
- Japan
- Prior art keywords
- group
- alkyl
- alkoxy
- formula
- general formula
- 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.)
- Pending
Links
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 239000004009 herbicide Substances 0.000 title abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 31
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 26
- 125000005843 halogen group Chemical group 0.000 claims abstract description 18
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical class NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004480 active ingredient Substances 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims abstract description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 6
- -1 α-phenoxyphenylacetic acid ester Chemical class 0.000 claims description 70
- 239000000126 substance Substances 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 125000005017 substituted alkenyl group Chemical group 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 125000004426 substituted alkynyl group Chemical group 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 abstract description 42
- 241000196324 Embryophyta Species 0.000 abstract description 26
- 238000001228 spectrum Methods 0.000 abstract description 8
- 150000002148 esters Chemical class 0.000 abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 abstract description 6
- 125000000304 alkynyl group Chemical group 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 229940126062 Compound A Drugs 0.000 abstract 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 44
- 238000006243 chemical reaction Methods 0.000 description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000002904 solvent Substances 0.000 description 18
- 240000007594 Oryza sativa Species 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 15
- 238000009472 formulation Methods 0.000 description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- ABUKMOCUMIPDHV-UHFFFAOYSA-N 2-phenoxy-2-phenylacetic acid Chemical class C=1C=CC=CC=1C(C(=O)O)OC1=CC=CC=C1 ABUKMOCUMIPDHV-UHFFFAOYSA-N 0.000 description 13
- 235000007164 Oryza sativa Nutrition 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 235000009566 rice Nutrition 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000008187 granular material Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 7
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 7
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 7
- 230000000379 polymerizing effect Effects 0.000 description 7
- 239000002689 soil Substances 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 239000004094 surface-active agent Substances 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
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 235000002597 Solanum melongena Nutrition 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 125000004185 ester group Chemical group 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 241000218691 Cupressaceae Species 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000002671 adjuvant Substances 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004563 wettable powder Substances 0.000 description 5
- 244000025254 Cannabis sativa Species 0.000 description 4
- 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 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 235000013312 flour Nutrition 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012433 hydrogen halide Substances 0.000 description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 238000009333 weeding Methods 0.000 description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 241000234653 Cyperus Species 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 244000184734 Pyrus japonica Species 0.000 description 3
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229940031826 phenolate Drugs 0.000 description 3
- 229940049953 phenylacetate Drugs 0.000 description 3
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CRZQGDNQQAALAY-UHFFFAOYSA-N Methyl benzeneacetate Chemical compound COC(=O)CC1=CC=CC=C1 CRZQGDNQQAALAY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 235000005324 Typha latifolia Nutrition 0.000 description 2
- 240000000260 Typha latifolia Species 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- KWABLUYIOFEZOY-UHFFFAOYSA-N dioctyl butanedioate Chemical compound CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC KWABLUYIOFEZOY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 2
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- XOIOYHPJZJLTGK-UHFFFAOYSA-N methyl 2-chloro-2-phenylacetate Chemical compound COC(=O)C(Cl)C1=CC=CC=C1 XOIOYHPJZJLTGK-UHFFFAOYSA-N 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
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- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000002420 orchard Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000020637 scallop Nutrition 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- IXYACKYHUWCLAM-UHFFFAOYSA-M sodium;2-ethylhex-1-ene-1-sulfonate Chemical compound [Na+].CCCCC(CC)=CS([O-])(=O)=O IXYACKYHUWCLAM-UHFFFAOYSA-M 0.000 description 1
- FGDMJJQHQDFUCP-UHFFFAOYSA-M sodium;2-propan-2-ylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=CC2=C(S([O-])(=O)=O)C(C(C)C)=CC=C21 FGDMJJQHQDFUCP-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000005309 thioalkoxy group Chemical group 0.000 description 1
- SFKTYEXKZXBQRQ-UHFFFAOYSA-J thorium(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Th+4] SFKTYEXKZXBQRQ-UHFFFAOYSA-J 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はα−フェノキシフェニル酢酸エステルとクロル
アセトアミド誘導体を有効成分とすることを特徴とする
除草剤組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a herbicidal composition characterized by containing α-phenoxyphenylacetic acid ester and a chloracetamide derivative as active ingredients.
〔従来の技術及び発明が解決しようとする問題点〕一般
に水田用除草剤として適用できるものは、主として下記
の4つの条件を満足する性質を有していなければならな
い。即ち、1つには水田に生育する雑草を枯死せしめる
に必要な殺草スペクトルを有すること、2つには稲に安
全であること、3つには漏水、落水、土壌吸着あるいは
微生物分解等を受けやすい条件下においても充分効果を
保つこと、4つには魚毒原生動物毒性等のないこと、で
ある。[Prior art and problems to be solved by the invention] In general, a herbicide that can be used as a herbicide for paddy fields must have properties that mainly satisfy the following four conditions. That is, one, it must have the herbicidal spectrum necessary to kill weeds growing in rice fields, two, it must be safe for rice, and three, it must prevent water leakage, water fall, soil adsorption, microbial decomposition, etc. It must remain sufficiently effective even under conditions that are susceptible to fish poisoning, and it must be free of protozoan toxicity.
一方、従来より畑地を対象とする除草剤として(プロシ
ーディングズ・オブ・ザ・イースト・アフリカ・ウィー
ド・コントロール・コンファレンス(Proceedi
ngs of the East Africa We
edControl Conference)第5回(
1974年))。On the other hand, conventional herbicides targeting upland fields (Proceedings of the East Africa Weed Control Conference)
ngs of the East Africa We
edControl Conference) 5th (
(1974)).
C]13
(***特許明細書第2458156号)等のα−フェノ
キシフェニル酢酸誘導体が知られている。α-phenoxyphenylacetic acid derivatives such as C]13 (West German Patent Specification No. 2458156) are known.
しかしながら、これらのα−フェノキシフェニル酢酸誘
導体は水田用除草剤として使用する場合、前記した条件
を充分満足するものではなかった。However, when these α-phenoxyphenylacetic acid derivatives are used as herbicides for paddy fields, they do not fully satisfy the above-mentioned conditions.
本発明者らは一連のα−フェノキシフェニル酢酸誘導体
の合成に成功し、これらの化合物の水田への適用性を鋭
意研究した結果、ある特定のα−フェノキシフェニル酢
酸エステルが前述した化合物よりもさらに水田雑草に対
する除草効果が高くかつ稲に安全であり、魚毒等の毒性
もない極めて優れた水田用除草剤となることを見い出し
て、既に提案した(特開昭60−113192号)。そ
して、更に上記α−フェノキシフェニル酢酸エステルと
他の化合物との組み合せによる除草作用について研究を
重ねた結果、酸α−フェノキシフェニル酢酸エステルと
特定のクロルアセトアミド誘導体を有効成分とする除草
剤組成物が、除草効果においてそれぞれ単独の性質から
は全く予期できない程の相乗作用を現わすこと、即ち、
低薬量で幅広い殺草スペクトルをもつことを見い出した
。本発明者らはこれらの新知見に基づき、本発明を完成
し提案するに至った。The present inventors succeeded in synthesizing a series of α-phenoxyphenylacetic acid derivatives, and as a result of intensive research into the applicability of these compounds to rice fields, certain α-phenoxyphenylacetic acid esters were found to be even more effective than the aforementioned compounds. It has been discovered that it is an extremely excellent herbicide for paddy fields that has a high weeding effect on paddy field weeds, is safe for rice plants, and has no toxicity such as fish poisoning, and has already proposed it (Japanese Patent Laid-Open No. 113192/1982). As a result of further research on the herbicidal effect of the combination of the above-mentioned α-phenoxyphenylacetate and other compounds, a herbicidal composition containing acid α-phenoxyphenylacetate and a specific chloracetamide derivative as active ingredients was discovered. , exhibiting a synergistic effect in herbicidal effect that could not be predicted from their individual properties, that is,
It was found that it has a wide herbicidal spectrum at low doses. Based on these new findings, the present inventors have completed and proposed the present invention.
本発明は一般式(1)
(但し、XIはハロゲン原子を示し、X2はアルキル基
又はアルコキシ基を示し、X3は水素原子、ハロゲン原
子、アルキル基又はアルコキシ基を示し、Rは非置換も
しくは置換のアルキル基、非置換もしくは置換のアルケ
ニル基、非置換もしくは置換のアルキニル基、又は非置
換もしくは置換の了り−ル基を示し、Yは酸素原子又は
イオウ原子を示す。)
で表わされるα−フェノキシフェニル酢酸エステルと一
般式(n)
〔但し、R8及びR2はアルキル基を示し、R3は水素
原子又はアルキル基を示し、R4はアルコキシ基、アル
コキシアルキル基、アルコキシカルキシ基、アルキルチ
オ基又はハロゲン原子を示す。)で表わされる基を示す
。〕
で示されるクロルアセトアミド誘導体
とを有効成分とすることを特徴とする除草剤組成物であ
る。The present invention is based on the general formula (1) (wherein, XI represents a halogen atom, X2 represents an alkyl group or an alkoxy group, X3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and R is unsubstituted or substituted. (Y represents an oxygen atom or a sulfur atom) Phenoxyphenylacetic acid ester and general formula (n) [However, R8 and R2 represent an alkyl group, R3 represents a hydrogen atom or an alkyl group, and R4 represents an alkoxy group, an alkoxyalkyl group, an alkoxycarxy group, an alkylthio group, or a halogen Indicates an atom. ) represents a group. ] A herbicidal composition characterized by containing a chloracetamide derivative represented by the following as an active ingredient.
本発明の除草剤組成物の一方の成分は、下記の−i式(
1)で示されるα−フェノキシフェニル酢酸エステルで
ある。One component of the herbicidal composition of the present invention is represented by the following formula -i (
This is α-phenoxyphenylacetic acid ester represented by 1).
(但し、X、はハロゲン原子を示し、Xzはアルキル基
又はアルコキシ基を示し、X、は水素原子、ハロゲン原
子、アルキル基又はアルコキシ基を示し、Rは非置換も
しくは置換のアルキル基、非置換もしくは置換のアルケ
ニル基、非置換もしくは置換のアルキニル基、又は非置
換もしくは置換のアリール基を示し、Yは酸素原子又は
イオウ原子を示す。)
上記一般式(1)中X、はハロゲン原子であることが本
発明のα−フェノキシフェニル酢酸エステルに特に高い
除草活性を付与するために必要である。また、X2はア
ルキル基又はアルコキシ基にすることにより水稲に極め
て安全な選択性を付与することができる。また、上記一
般式(1)中、Y−R基(但し、Rは非置換もしくは置
換のアルキル基、非置換もしくは置換のアルケニル基、
非゛置換もしくは置換のアルキニル基、又は非置換もし
くは置換のアリール基を示し、Yは酸素原子又はイオウ
原子を示す。)を結合させエステル型にすることにより
除草効果を高め、同時に漏水、落水、土壌吸着あるいは
微生物分解等を受けやすい水田条件下においても残効性
を長く保つ性質を付与することができる。(However, X represents a halogen atom, Xz represents an alkyl group or an alkoxy group, X represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and R represents an unsubstituted or substituted alkyl group, an unsubstituted or a substituted alkenyl group, an unsubstituted or substituted alkynyl group, or an unsubstituted or substituted aryl group, and Y represents an oxygen atom or a sulfur atom.) In the above general formula (1), X is a halogen atom. This is necessary in order to impart especially high herbicidal activity to the α-phenoxyphenylacetic acid ester of the present invention. Furthermore, by setting X2 to an alkyl group or an alkoxy group, extremely safe selectivity can be imparted to paddy rice. In addition, in the above general formula (1), a Y-R group (wherein R is an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group,
It represents an unsubstituted or substituted alkynyl group or an unsubstituted or substituted aryl group, and Y represents an oxygen atom or a sulfur atom. ) can be combined to form an ester type, thereby increasing the herbicidal effect and at the same time imparting properties that maintain long-term residual effectiveness even under paddy field conditions that are susceptible to water leakage, water fall, soil adsorption, microbial decomposition, etc.
上記一般式(1)中、X、及び×3で示されるハロゲン
原子は、フッ素、塩素、臭素、ヨウ素の各原子が挙げら
れるが、特に塩素原子が好適に使用される。In the above general formula (1), the halogen atoms represented by X and x3 include fluorine, chlorine, bromine, and iodine atoms, with chlorine atoms being particularly preferably used.
また上記一般式CI)中、X2及びX、で示されるアル
キル基は特に制限されず使用できるが、一般には炭素原
子数1〜12個、好ましくは1〜6個の直鎖状、分枝状
、又は環状のものが好適である。特に好適なアルキル基
の具体例を例示すると、メチル基、エチル基、n−プロ
ピル基、イソプロピル基り、n−ブチル基、イソブチル
基、t−ブチル基、n−ペンチル基、n−ヘキシル基、
n−オクチル基、n−ドデシル基、シクロプロピルメチ
ル基、シクロヘキシル基等が挙げられる。In the above general formula CI), the alkyl groups represented by X2 and , or a ring shape is preferable. Specific examples of particularly suitable alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group,
Examples include n-octyl group, n-dodecyl group, cyclopropylmethyl group, and cyclohexyl group.
また前記一般式CI)中、X2及びX、で示されるアル
コキシ基は特に制限されず使用できるが、一般には炭素
原子数1〜12個、好ましくは1〜6個の直鎖状、分枝
状又は環状のものが好適である。In the general formula CI), the alkoxy groups represented by X2 and Alternatively, a ring-shaped one is preferable.
特に好適なアルコキシ基の具体例を例示すると、メトキ
シ基、エトキシ基、n−プロポキシ基、を−ブトキシ基
、n−ペントキシ基、n−ヘキソキシ基、シクロプロピ
ルメトキシ基等が挙げられる。Specific examples of particularly preferred alkoxy groups include methoxy, ethoxy, n-propoxy, -butoxy, n-pentoxy, n-hexoxy, and cyclopropylmethoxy groups.
また、前記一般式CI)中、Rで示される非置換のアル
キル基としては、特に制限されないが、X2及びX、の
説明で示したアルキル基と同様のものが好適に使用され
る。Rで示される置換のアルキル基の置換基は特に制限
されるものではないが、好ましい置換基としては次のも
のを挙げることができる。Further, in the general formula CI), the unsubstituted alkyl group represented by R is not particularly limited, but the same alkyl groups as those shown in the explanation of X2 and X are preferably used. The substituents of the substituted alkyl group represented by R are not particularly limited, but preferred substituents include the following.
例えば、アルコキシ基、了り−ル基、アルコキ示される
基又はハロゲン原子等である。これらの置換基のうち、
アルコキシ基又はアルコキシカル゛ボニル基中のアルコ
キシ基は、前記X2及びX3で述べたアルコキシ基と同
様のものが好ましい。For example, it is an alkoxy group, an alkyl group, an alkoxy group, or a halogen atom. Among these substituents,
The alkoxy group in the alkoxy group or alkoxycarbonyl group is preferably the same as the alkoxy group described for X2 and X3 above.
れる基のnは1〜5であること特に1.3又は4である
ことが比較的安定な化合物を得ることができるために好
ましい。また、上記の置換基のうちのアリール基として
は、フェニル基、トリル基、キシリル基、ナフチル基が
好ましい。さらにまた、上記のハロゲン原子としては塩
素、フッ素、臭素、ヨウ素の各原子が採用される。これ
らの置換基が置換したアルキル基として、本発明で好適
に採用されるものを具体的に例示すると、次のとおりで
ある。It is preferable that n of the group is 1 to 5, particularly 1.3 or 4, since a relatively stable compound can be obtained. Among the above substituents, the aryl group is preferably a phenyl group, tolyl group, xylyl group, or naphthyl group. Furthermore, each of chlorine, fluorine, bromine, and iodine atoms is employed as the above-mentioned halogen atom. Specific examples of alkyl groups substituted with these substituents that are preferably employed in the present invention are as follows.
アルコキシ基置換のアルキル基としては、メトキシメチ
ル基、メトキシエチル基、エトキシメチル基、n−プロ
ポキシメチル基、t−ブトキシエチル基等が挙げられる
。また、アリール基置換のアルキル基としては、ベンジ
ル基、0−メチルベンジル基、p−イソプロピルベンジ
ル基、0−メトキシベンジル基、p−フルオロベンジル
基、m−ニトロベンジル基、フェネチル基等を挙げるこ
とができる。Examples of the alkyl group substituted with alkoxy group include methoxymethyl group, methoxyethyl group, ethoxymethyl group, n-propoxymethyl group, and t-butoxyethyl group. Further, examples of the alkyl group substituted with an aryl group include a benzyl group, 0-methylbenzyl group, p-isopropylbenzyl group, 0-methoxybenzyl group, p-fluorobenzyl group, m-nitrobenzyl group, phenethyl group, etc. I can do it.
次に、アルコキシカルボニル基置換のアルキル基として
は、−Cal□C00CIIs 、C1hCOOCJs
、CH,+
CH3CzHs C1h
る基が置換したアルキル基としてはエポキシメチル基、
テトラヒドロフルフリル基等が挙げられる。Next, as the alkyl group substituted with an alkoxycarbonyl group, -Cal□C00CIIs, C1hCOOCJs
, CH, + CH3CzHs C1h The alkyl group substituted with the group is an epoxymethyl group,
Examples include tetrahydrofurfuryl group.
さらにまた、ハロゲン原子置換のアルキル基としては、
クロルメチル基、ブロムメチル基、ブロムエチル基、フ
ルオロメチル基、2.2.2− )リフルオロエチル基
、2,2.2−)リクロルエチル基、2.2′−ジクロ
ルイソプロピル基、ジクロルシクロプロピルメチル基、
2−クロルヘキシルi、2−ブロムドデシル基等が挙げ
られる。Furthermore, as the alkyl group substituted with a halogen atom,
Chloromethyl group, bromomethyl group, bromoethyl group, fluoromethyl group, 2.2.2-)lifluoroethyl group, 2,2.2-)lychloroethyl group, 2.2'-dichloroisopropyl group, dichlorocyclopropylmethyl basis,
Examples include 2-chlorohexyl i, 2-bromdodecyl group, and the like.
前記一般式〔【〕中、Rで示されるアルケニル基は、特
に制限されず使用できるが、一般には炭素原子数2〜1
2個、好ましくは2〜6個の直鎖状、分枝状又は環状の
ものが好適である。特に好適なアルケニル基の具体例を
例示すると、ビニル基、アリル基、イソプロペニル基、
2−ブテニル基、3−ブテニル基、シクロへキセニル基
等が挙げられる。また、前記一般式CI)中、Rで示さ
れるアルキニル基は、特に制限されず使用できるが、−
aには炭素原子数2〜12個好ましくは2〜6個の直鎖
状、又は分枝状のものが好適である。In the general formula [[], the alkenyl group represented by R can be used without particular restriction, but generally has 2 to 1 carbon atoms.
2, preferably 2 to 6 linear, branched or cyclic ones are suitable. Specific examples of particularly suitable alkenyl groups include vinyl group, allyl group, isopropenyl group,
Examples include 2-butenyl group, 3-butenyl group, and cyclohexenyl group. In addition, in the general formula CI), the alkynyl group represented by R can be used without particular restriction, but -
It is preferable that a has 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, and is linear or branched.
特に好適なアルキニル基の具体例を例示すると、エチニ
ル基、2−プロピニル基、1.1−ジメチル−2−プロ
ピニル基、2.2−ジメチル−3−ブチニル基等が挙げ
られる。Specific examples of particularly suitable alkynyl groups include ethynyl group, 2-propynyl group, 1.1-dimethyl-2-propynyl group, and 2.2-dimethyl-3-butynyl group.
また、前記一般式(1)中、Rで示される了り−ル基は
、特に制限されず使用し得る。代表的なものを具体的に
例示すると、フェニル基、トリル基、キシリル基、ナフ
チル基等を挙げることができる。Furthermore, in the general formula (1), the oryl group represented by R may be used without particular limitation. Specific examples of representative groups include phenyl group, tolyl group, xylyl group, and naphthyl group.
上記したアルケニル基、アルキニル基及びアリール基の
置換基としては、特に制限されないが、代表的なものを
例示すると、ハロゲン原子、アル゛コキシ基、ニトロ基
及びシアノ基等が挙げられる。Substituents for the alkenyl, alkynyl, and aryl groups described above are not particularly limited, but representative examples include halogen atoms, alkoxy groups, nitro groups, and cyano groups.
これらの置換基で置換されたアルケニル基、アルキニル
基及びアリール基の代表的なものを具体的に示すと、次
のとおりである。置換アルケニル基としては、3−ブロ
ム−2−プロペニルi、3−クロル−3−ブロム−2−
プロペニルi、4−10ルー2−ブテニル基、3−メト
キシ−2−プロペニル基、4−メトキシ−3−ブチニル
L3−ニトロー2−ペンテニル基、2−シアノ−4−メ
チル−3−ペンテニル基等が挙げられる。Representative alkenyl groups, alkynyl groups and aryl groups substituted with these substituents are specifically shown below. Substituted alkenyl groups include 3-bromo-2-propenyl, 3-chloro-3-bromo-2-
propenyl i, 4-10-2-butenyl group, 3-methoxy-2-propenyl group, 4-methoxy-3-butynyl L3-nitro-2-pentenyl group, 2-cyano-4-methyl-3-pentenyl group, etc. Can be mentioned.
置換アルキニル基としては、4−ブロム−2−ブチニル
基、5−ヨード−3−ブチニルL4−エトキシー2−ブ
チニル基、4−ニトロ−2−ブチニル基、2−シアノ−
3−ヘキシニル基等が挙げられる。Examples of substituted alkynyl groups include 4-bromo-2-butynyl group, 5-iodo-3-butynyl L4-ethoxy-2-butynyl group, 4-nitro-2-butynyl group, 2-cyano-
Examples include 3-hexynyl group.
置換アリール基としては、p−メトキシフェニル基、p
−クロルフェニル基、0−ブロムフェニル5、m−1−
リフルオロメチルフェニルLp−シアノフェニル基、p
−ニトロフェニル基等を挙げることができる。Substituted aryl groups include p-methoxyphenyl group, p-methoxyphenyl group, p-methoxyphenyl group,
-Chlorphenyl group, 0-bromphenyl 5, m-1-
Lifluoromethylphenyl Lp-cyanophenyl group, p
-nitrophenyl group and the like.
前記一般式(1)で示される化合物のうち、X。Among the compounds represented by the general formula (1), X.
が塩素原子であり、X2がメチル基又はメトキシ基であ
り、X3が水素原子又は塩素原子であり、Rが炭素原子
数1〜6個の置換もしくは非置換のアルキル基、アルケ
ニル基、アルキニル基である化合物は除草効果が良好で
あり除草剤として好適に用いられる化合物である。該化
合物中、X、の塩素原子が4位に結合し、X2のメチル
基又はメトキシ基が2位又は3位に結合した化合物は、
特に水田″雑草に活性が高く優れた除草効果を有するば
かりでなく、従来のホルモン型除草剤に比較しても稲に
対して極めて安全であり、高い選択性を有している。is a chlorine atom, X2 is a methyl group or a methoxy group, X3 is a hydrogen atom or a chlorine atom, and R is a substituted or unsubstituted alkyl group, alkenyl group, or alkynyl group having 1 to 6 carbon atoms. Certain compounds have good herbicidal effects and are suitable for use as herbicides. Among these compounds, a compound in which the chlorine atom of X is bonded to the 4th position and the methyl group or methoxy group of X2 is bonded to the 2nd or 3rd position,
Not only is it highly active and has an excellent herbicidal effect on rice field weeds, it is also extremely safe and highly selective for rice plants compared to conventional hormone-type herbicides.
前記一般式(1)で示されるα−フェノキシフェニル酢
酸エステルの構造は、次の手段によって確認することが
できる。The structure of α-phenoxyphenylacetic acid ester represented by the general formula (1) can be confirmed by the following means.
(イ)赤外吸収スペクトル(IR)を測定することによ
り、3150〜2800cm−’付近にCH結合に基づ
く吸収、1660〜1760CI11−’付近にエステ
ル基のカルボニル結合に基づく特性吸収を観察すること
ができる。(b) By measuring the infrared absorption spectrum (IR), it is possible to observe an absorption based on the CH bond in the vicinity of 3150 to 2800 cm-' and a characteristic absorption based on the carbonyl bond of the ester group in the vicinity of 1660 to 1760 CI11-'. can.
(ロ)質量スペクトル(MS)を測定し、観察される各
ピーク(一般にはイオン質1@、mをイオンの荷電数e
で除したm/eで表わされる値)に相当する組成式を算
出することにより、測定に供した化合物の分子量ならび
に該分子内における各原子団の結合様式を知ることが出
来る。すなわち、測定に供した試料を一般式(I)
で表わした場合、−瓜に分子イオンピーク(以下MΦと
略記する)が分子中に含有されるハロゲン原子の個数に
応じて同位体存在比に従って強度比で観察されるため、
測定に供した化合物の分子量を決定することが出来る。(b) Measure the mass spectrum (MS), and each peak observed (generally, the ion quality is 1 @, m is the charge number of the ion, e
By calculating the composition formula corresponding to the value expressed by m/e divided by m/e, it is possible to know the molecular weight of the compound subjected to measurement and the bonding mode of each atomic group within the molecule. In other words, when the sample subjected to measurement is expressed by the general formula (I), the molecular ion peak (hereinafter abbreviated as MΦ) at -melon varies according to the isotope abundance ratio depending on the number of halogen atoms contained in the molecule. Since it is observed in the intensity ratio,
The molecular weight of the compound subjected to measurement can be determined.
さらに前記一般式(1)で示されるα−フェノキシフェ
ニル酢酸エステルについては
に相当する特徴的なピークが観察される。Furthermore, a characteristic peak corresponding to α-phenoxyphenylacetic acid ester represented by the general formula (1) is observed.
(ハ) IH−核磁気共鳴スペクトル(’H−NMR)
を測定することにより、前記一般式(1)で示されるα
−フェノキシフェニル酢酸エステル中に存在する水素原
子の結合様式を知ることができる。(c) IH-nuclear magnetic resonance spectrum ('H-NMR)
By measuring α shown in the general formula (1),
- The bonding mode of hydrogen atoms present in phenoxyphenylacetate can be known.
前記一般式(1)で示されるα−フェノキシフェニル酢
酸エステルの’H−NMR(δ−ppm :テトラメ
チルシラン基準、重クロロホルム溶媒中)の具体例とし
て、α−(2−メチル−4−クロルフェノキシ)フェニ
ル酢酸ブチルの’H−NMR図を第1図に記載したが、
その解析結果を示すと次のとおりである。As a specific example of 'H-NMR (δ-ppm: based on tetramethylsilane, in deuterated chloroform solvent) of α-phenoxyphenylacetic acid ester represented by the general formula (1), α-(2-methyl-4-chloro The 'H-NMR diagram of butyl phenoxy)phenylacetate is shown in Figure 1.
The analysis results are as follows.
HI
(fl
すなわち0.7〜1.7 ppmにプロトン7個分に相
当する多重線が認められ、これはブチル基中のプロトン
(a)によるものと帰属できる。2.27ppmにプロ
トン3個分に相当する一重線が認められ、これはフェニ
ル基の2位に置換したメチル基(b)によるものと帰属
できる。4.09ppmにプロトン2個分に相当する三
重線が認められ、これはブチル基中のメチレン基(C)
によるものと帰属できる。5.53ppI11にプロト
ン1個分に相当する一重線が認められ、これはメチン基
(d)によるものと帰属できる。HI (fl) In other words, a multiplet corresponding to 7 protons was observed at 0.7 to 1.7 ppm, and this can be attributed to proton (a) in the butyl group. A singlet corresponding to 2 protons was observed, and this can be attributed to the methyl group (b) substituted at the 2-position of the phenyl group.A triplet corresponding to 2 protons was observed at 4.09 ppm, and this can be attributed to the methyl group (b) substituted at the 2-position of the phenyl group. Methylene group (C) in the group
It can be attributed to A singlet corresponding to one proton was observed at 5.53 ppI11, and this can be attributed to the methine group (d).
また6、5〜7.6 ppmにプロトン8個分に相当す
る多重線が認められ、これはフェニル基に置換したプロ
トン(e)、 (flによるものと帰属できる。Further, a multiplet corresponding to 8 protons was observed at 6.5 to 7.6 ppm, and this can be attributed to protons (e) and (fl) substituted with phenyl groups.
前述の一般式(1)で示されるα−フェノキシフェニル
酢酸エステルの’H−NMRの特徴ヲ総括すると、5.
4〜5.8 ppm付近に一重線でα−位のメチン基の
プロトンに基づく吸収が認められ、また6、3〜7.8
ppmに2種類のベンゼン環に置換したプロトンに基
づく多重線が認められる。To summarize the 'H-NMR characteristics of α-phenoxyphenylacetic acid ester represented by the above-mentioned general formula (1), 5.
Absorption based on the proton of the methine group at the α-position was observed as a singlet near 4 to 5.8 ppm, and 6, 3 to 7.8 ppm
A multiplet based on protons substituted on two types of benzene rings is observed in ppm.
(ニ)元素分析によって炭素、水素、窒素及びハロゲン
、さらにイオウを含む場合にはイオウの各重量%を求め
、さらに認知された各元素の重量%の和を100から減
じることにより、酸素の重量%を算出することができ、
従って組成式を決定することができる。(iv) Determine the weight percent of carbon, hydrogen, nitrogen, halogen, and sulfur if it contains sulfur by elemental analysis, and then subtract the sum of the recognized weight percent of each element from 100 to determine the weight of oxygen. % can be calculated,
Therefore, the compositional formula can be determined.
またα−フェノキシフェニル酢酸エステルは、前記一般
式(1)中のXI、XlX3.Y及びRの種類によって
その性状が多少異なるが、一般に常温。Further, α-phenoxyphenylacetic acid ester is XI, XlX3. Its properties differ somewhat depending on the type of Y and R, but generally at room temperature.
常圧においては無色または淡黄色の粘稠液体または固体
であり、高沸点を有するものが多い。具体的には後述す
る合成例に示すが、上記化合物は一般の有機化合物と同
じように分子量が大きくなる程沸点が高くなる傾向があ
る。該化合物は、ベンゼン、エーテル、アルコール、ク
ロロホルム、四塩化炭素、アセトニトリル、N、N−ジ
メチルホルムアミド、ジメチルスルホキシドなどの一般
有機溶媒に可溶であるが、水にはほとんど溶けない。At normal pressure, it is a colorless or pale yellow viscous liquid or solid, and many have a high boiling point. More specifically, as shown in the synthesis examples described later, the boiling point of the above compound tends to increase as the molecular weight increases, like general organic compounds. The compound is soluble in common organic solvents such as benzene, ether, alcohol, chloroform, carbon tetrachloride, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide, but almost insoluble in water.
前記一般式CI)で示されるα−フェノキシフェニル酢
酸エステルは如何なる方法で得られたものでも使用でき
る。代表的な製造方法として以下の3つの方法を挙げる
ことができる。The α-phenoxyphenylacetic acid ester represented by the general formula CI) obtained by any method can be used. The following three methods can be mentioned as typical manufacturing methods.
(i)α−フェノキシフェニル酢酢酸ハローニドアルコ
ール、フェノール、チオアルコール又はチオフェノール
とを反応させる方法
(但し、式中X 、X z、X 3+ Y及びRは前記
一般式(1)の場合と同じであり、Zはハロゲン原子を
示す。)
(ii)フェノール又はアルカリ金属フェノラートとα
−ハロゲノフェニル酢酸エステルとを反応させる方法
(但し、式中X、、X2.X3.Y及びRは、前記一般
式(1)の場合と同じであり、Zはハロゲン原子を示し
、Mは水素原子又はアルカリ金属を示す。)(iii
)ハロゲン化アリールとα−ヒドロキシフェニル酢酸エ
ステルを反応させる方法
(但し、式中XI、X2.X3.Y及びRは前記一般式
〔1〕の場合と同じであり、Zはハロゲン原子を示す。(i) A method of reacting α-phenoxyphenylacetic acid halonide alcohol, phenol, thioalcohol, or thiophenol (wherein, the same, and Z represents a halogen atom.) (ii) Phenol or alkali metal phenolate and α
- A method of reacting with halogenophenyl acetate (however, in the formula, X, , X2, Indicates an atom or alkali metal.) (iii
) A method of reacting an aryl halide with an α-hydroxyphenylacetic acid ester (wherein XI, X2.X3.Y and R are the same as in the general formula [1] above, and Z represents a halogen atom.
)
本発明のα−フェノキシフェニル酢酸エステルを製造す
る方法のうち、前記(i)で示される反応〔以下、反応
(i)と略す。〕に於て、再化合物の仕込モル比は必要
に応じて適宜決定すればよいが、通常等モル又はアルコ
ール、フェノール、チオアルコールもしくはチオフェノ
ールをやや過剰モル使用するのが一般的である。またア
ルコールを大量に使用し、原料兼溶媒として使用するこ
とも可能である。) Among the methods for producing α-phenoxyphenylacetic acid ester of the present invention, the reaction shown in (i) above [hereinafter abbreviated as reaction (i)]. ], the molar ratio of the recompound to be charged may be appropriately determined as necessary, but it is common to use equimolar amounts or a slightly excess molar amount of alcohol, phenol, thioalcohol, or thiophenol. It is also possible to use a large amount of alcohol and use it as both a raw material and a solvent.
また、反応(i)においてはハロゲン化水素が副生する
。このハロゲン化水素は生成物の収率を低下させる原因
になるので、通常は反応系内にハロゲン化水素捕捉剤を
共存させることが好ましい。Further, in reaction (i), hydrogen halide is produced as a by-product. Since this hydrogen halide causes a decrease in the yield of the product, it is usually preferable to coexist a hydrogen halide scavenger in the reaction system.
該ハロゲン化水素捕捉剤は特に限定されず公知のものを
使用することが出来る。一般に好適に使用される該捕捉
剤としてトリメチルアミン、トリエチルアミン、トリプ
ロピルアミン等のトリアルキルアミン、ピリジン、ナト
リウムアルコラード、炭酸ナトリウム等が挙げられる。The hydrogen halide scavenger is not particularly limited, and any known one can be used. Examples of the scavenger that are generally suitably used include trialkylamines such as trimethylamine, triethylamine, and tripropylamine, pyridine, sodium alcoholade, and sodium carbonate.
前記反応(i)に際しては無溶媒でもよいが一般に有機
溶媒を用いるのが好ましい。該溶媒として好適に使用さ
れるものを例示すれば、ベンゼン、トルエン、キシレン
、ヘキサン、ヘプタン、石油エーテル、クロロホルム、
塩化メチレン、塩化エチレン等の脂肪族または芳香族の
炭化水素類あるいはハロゲン化炭化水素類;ジエチルエ
ーテル、ジオキサン、テラトヒドロフラン等のエーテル
類;アセトン、メチルエチルケトン等のケトン頻;アセ
トニトリルなどのニトリルI;N、N−ジメチルホルム
アミド、N、N−ジエチルホルムアミド等のN、N−ジ
アルキルアミド類;ジメチルスルホキシド等が挙げられ
る。Although reaction (i) may be carried out without a solvent, it is generally preferable to use an organic solvent. Examples of solvents preferably used include benzene, toluene, xylene, hexane, heptane, petroleum ether, chloroform,
Aliphatic or aromatic hydrocarbons or halogenated hydrocarbons such as methylene chloride and ethylene chloride; ethers such as diethyl ether, dioxane and teratohydrofuran; ketones such as acetone and methyl ethyl ketone; nitriles I such as acetonitrile; Examples include N,N-dialkylamides such as N,N-dimethylformamide and N,N-diethylformamide; dimethylsulfoxide and the like.
前記反応における原料の添加順序は特に限定されないが
、一般には溶媒にアルコール、フェノ−Jし、チオアル
コール
解して反応器に仕込み溶媒に溶解したαーフェノキシフ
ェニル酢酢酸ハローニド攪拌下に添加するのがよい。勿
論連続的に反応系に原料を添加し生成した反応物を連続
的に該反応系から取出すことも出来る。The order of addition of the raw materials in the reaction is not particularly limited, but generally, alcohol and pheno-J are added to the solvent, thioalcohol is dissolved, and α-phenoxyphenyl acetic acid halonide dissolved in the solvent is added under stirring. Good. Of course, it is also possible to continuously add raw materials to the reaction system and take out the produced reactants continuously from the reaction system.
前記反応における温度は広い範囲から選択出来、一般に
は−20℃〜150℃、好ましくはO℃〜120℃の範
囲から選べば十分である。反応時間は原料の種類によっ
てもちがうが、通常5分〜10日間、好ましくは1〜4
0時間の範囲から選べば十分である。また反応中におい
ては、撹拌を行うのが好ましい。The temperature in the reaction can be selected from a wide range, and generally it is sufficient to select it from the range of -20°C to 150°C, preferably 0°C to 120°C. The reaction time varies depending on the type of raw material, but is usually 5 minutes to 10 days, preferably 1 to 4 days.
It is sufficient to select from the range of 0 hours. Further, during the reaction, it is preferable to perform stirring.
また、前記( ii )で示される反応〔以下、反応(
ii)と略す〕に於いて、アルカリ金属フェノラートの
アルカリ金属としては、通常ナトリウム、カリウム、リ
チウム等が使用される。反応(ii)でフェノールとα
−ハロゲノフェニル酢酸エステルとを反応させる場合に
は、触媒を存在させることが好ましい。触媒としては、
トリエチルアミン、トリメチルアミン、トリエチレンジ
アミン、ジメチルパラトルイジン等の第3級アミン;ピ
リジン、ピコリン、コリジン、ピラジン等の含窒素芳香
族塩基等が好ましく用いられる。In addition, the reaction shown in (ii) above [hereinafter referred to as reaction (
(abbreviated as ii)], sodium, potassium, lithium, etc. are usually used as the alkali metal of the alkali metal phenolate. In reaction (ii), phenol and α
- When reacting with halogenophenyl acetate, it is preferable to have a catalyst present. As a catalyst,
Tertiary amines such as triethylamine, trimethylamine, triethylenediamine, and dimethyl para-toluidine; nitrogen-containing aromatic bases such as pyridine, picoline, collidine, and pyrazine are preferably used.
反応( ii )において両化合物の仕込モル比は必要
に応じて適宜決定すればよいが、通常等モル又はフェノ
ール若しくはアルカリ金属フェノラートをやや過剰モル
使用するのが一般的である。In reaction (ii), the molar ratio of both compounds to be charged may be determined as appropriate, but it is common to use equimolar amounts or a slightly excess molar amount of phenol or alkali metal phenolate.
また反応( ii )は一般に有機溶媒を用いるのが好
ましい。該溶媒としては前記した反応(i)で説明した
溶媒が何ら制限されずに使用し得る。Further, it is generally preferable to use an organic solvent in reaction (ii). As the solvent, the solvents described in reaction (i) above can be used without any restriction.
前記反応(11)における温度は広い範囲から選択出来
、一般には−20℃〜150℃好ましくは0℃〜120
℃の範囲から選べば十分である。反応時間は原料の種類
によってもちがうが、通常5分〜10日間、好ましくは
1〜50時間の範囲から選べば十分である。また反応中
においては、攪拌を行うのが好ましい。The temperature in the reaction (11) can be selected from a wide range, generally -20°C to 150°C, preferably 0°C to 120°C.
It is sufficient to choose from the range of ℃. The reaction time varies depending on the type of raw material, but it is usually sufficient if it is selected from the range of 5 minutes to 10 days, preferably 1 to 50 hours. It is also preferable to stir the reaction mixture during the reaction.
前記( iii )で示される反応〔以下反応( ii
i )と略す〕に於て、両化合物の仕込モル比は必要に
応じて適宜決定すればよいが、通常等モル使用するのが
一般的である。反応( iii )においてはアルカリ
金属、又はアルカリ金属水素化物等の存在下に反応させ
るのが一般的である。該アルカリ金属としては、ナトリ
ウム、カリウム、リチウム等が挙げられる。アルカリ金
属のかわりにアルカリ土類金属を用いても同様の反応を
行なうことができる。The reaction shown in (iii) above [hereinafter referred to as reaction (ii)
(abbreviated as i)), the molar ratio of both compounds to be charged may be appropriately determined as necessary, but it is common to use equimolar amounts. In reaction (iii), the reaction is generally carried out in the presence of an alkali metal or an alkali metal hydride. Examples of the alkali metal include sodium, potassium, and lithium. Similar reactions can be carried out using alkaline earth metals instead of alkali metals.
また反応( iii )は一般に有機溶媒を用いるのが
好ましいが、該溶媒としては、反応(i)に於て使用さ
れるものが好適に用いられる。反応( iii )に於
ては触媒を用いるのが好適である。該触媒としては、銅
、ヨウ化第−銅、臭化第一銅、塩化第一銅、酸化第一銅
、酸化第二銅等の金属鋼又は銅ハロゲン化物もしくは銅
酸化物のような銅化合物等が挙げられる。また前記反応
( iii )における反応温度、反応時間等の条件は
反応( ii )と同様である。Further, it is generally preferable to use an organic solvent in reaction (iii), and as the solvent, those used in reaction (i) are preferably used. It is preferable to use a catalyst in reaction (iii). The catalyst includes copper, metal steel such as cuprous iodide, cuprous bromide, cuprous chloride, cuprous oxide, cupric oxide, or copper compound such as copper halide or copper oxide. etc. Further, the conditions such as reaction temperature and reaction time in the reaction (iii) are the same as in the reaction (ii).
反応系から目的生成物すなわち前記一般式(1)で示さ
れるα−フェノキシフェニル酢酸エステルを単離生成す
る方法は特に限定されず公知の方法を採用できる。例え
ば反応(i)、 (iiL (iii)においては、反
応液から反応溶媒及び過剰の反応器・薬を留去した後、
残渣をクロロホルム、ベンゼン、エーテル等の有機溶媒
で抽出する。該有機層は、芒硝、塩化カルシウム等の乾
燥剤で乾燥した後、有機溶媒を留去し、残渣を真空蒸留
することにより、目的物を得ることができる。真空蒸留
により単離精製する他、クロマトグラフィによる精製、
あるいは生成物が固体である場合には再結晶することに
より精製することもできる。The method for isolating and producing the desired product, ie, α-phenoxyphenylacetic acid ester represented by the general formula (1), from the reaction system is not particularly limited, and any known method can be employed. For example, in reaction (i), (iiL (iii)), after distilling off the reaction solvent and excess reactor/drug from the reaction solution,
The residue is extracted with an organic solvent such as chloroform, benzene, or ether. The desired product can be obtained by drying the organic layer with a desiccant such as Glauber's salt or calcium chloride, then distilling off the organic solvent and vacuum distilling the residue. In addition to isolation and purification by vacuum distillation, purification by chromatography,
Alternatively, if the product is a solid, it can be purified by recrystallization.
本発明の前記一般式CI)で示されるα−フェノキシフ
ェニル酢酸エステルは、稲に対しては従来のホルモン型
除草剤に比較して極めて安全であり、水田雑草に高い除
草効果を発渾するが、特にクマガヤツリ、ホタルイ等の
カヤツリグサ科雑草、コナギ、アゼナキカシグサ等の広
葉雑草に対して、その発芽時だけでなく、生育期におい
ても極めて高い除草効果を有する優れた除草剤である。The α-phenoxyphenylacetic acid ester of the present invention represented by the general formula CI) is extremely safe for rice plants compared to conventional hormone-type herbicides, and exhibits high herbicidal effects on paddy field weeds. It is an excellent herbicide that has an extremely high herbicidal effect, especially against Cyperaceae weeds such as Cyperus japonica and bulrushes, and broad-leaved weeds such as Aspergillus spp.
本発明の除草剤組成物の他方の成分は次の一般式(II
)、
Rt
〔但し、R2及びR2はアルキル基を示し、R1は水素
原子又はアルキル基を示し、R4はアルコキシ基、アル
コキシアルキル基、アルコキシカルキシ基、チオアルコ
キシ基又はハロゲン原子を示す。)で表わされる基を示
す。〕
で表わされるクロルアセトアミド誘導体である。The other component of the herbicidal composition of the present invention has the following general formula (II
), Rt [However, R2 and R2 represent an alkyl group, R1 represents a hydrogen atom or an alkyl group, and R4 represents an alkoxy group, an alkoxyalkyl group, an alkoxycarxy group, a thioalkoxy group, or a halogen atom. ) represents a group. ] It is a chloracetamide derivative represented by
上記一般式(II)中、R,、R2及びR1で示される
アルキル基としては、その炭素数に特に限定されず、い
かなるものでも使用し得る。そのうち、炭素数が1〜4
のものが好適である。本発明に於いて好適なアルキル基
としては、メチル基、エチル基、n−プロピル基、i−
プロピル基、n−ブチル基、i−ブチル基、t−ブチル
基等が挙げられる。In the above general formula (II), the alkyl groups represented by R, R2 and R1 are not particularly limited in the number of carbon atoms, and any alkyl group can be used. Of these, the number of carbon atoms is 1 to 4
Preferably. Suitable alkyl groups in the present invention include methyl group, ethyl group, n-propyl group, i-
Examples include propyl group, n-butyl group, i-butyl group, and t-butyl group.
また、上記一般式(n)中、R4およびR4にれるアル
コキシ基としては、その炭素数は特に限定されないが、
炭素数が1〜6のものが好ましい。In addition, in the above general formula (n), the number of carbon atoms of the alkoxy group represented by R4 and R4 is not particularly limited, but
Those having 1 to 6 carbon atoms are preferred.
本発明に於いて好適なアルコキシ基としては、メトキシ
基、エトキシ基、n−プロポキシ基、i−プロポキシ基
、n−ブトキシ基、i−ブトキシ基、(−ブトキシ基、
n−ヘキソキシ基等が挙げられる。Suitable alkoxy groups in the present invention include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, (-butoxy group,
Examples include n-hexoxy group.
また、上記のR3で示されるアルキルチオ基は、特に限
定されず公知のものが使用出来るが、一般には炭素原子
数1〜6個の直鎖状または分枝状の飽和あるいは不飽和
基が好適である。好適に使用される該アルキルチオ基の
具体例を提示すると、メチルチオ基、エチルチオ基、n
−プロピルチオ基、t−ブチルチオ基、n−ペンチルチ
オ基、n−ヘキシルチオ基、アリルチオ基等が挙げられ
る。The alkylthio group represented by R3 above is not particularly limited and any known alkylthio group can be used, but in general, a linear or branched saturated or unsaturated group having 1 to 6 carbon atoms is preferred. be. Specific examples of the alkylthio group that are preferably used include methylthio group, ethylthio group, n
-propylthio group, t-butylthio group, n-pentylthio group, n-hexylthio group, allylthio group and the like.
また上記一般式(H)中、R4で示されるアルコキシア
ルキル基としては、その炭素数は特に限定されないが、
炭素数が1〜6のものが好ましい。In addition, in the above general formula (H), the number of carbon atoms in the alkoxyalkyl group represented by R4 is not particularly limited, but
Those having 1 to 6 carbon atoms are preferred.
本発明に於いて好適なアルコキシアルキル基としては、
メトキシメチル基、メトキシエチル基、エトキシメチル
基、−プロポキシメチル基、t−ブトキシエチル基等が
挙げられる。In the present invention, preferred alkoxyalkyl groups include:
Examples include methoxymethyl group, methoxyethyl group, ethoxymethyl group, -propoxymethyl group, and t-butoxyethyl group.
更に、上記一般式(II)中、R4で示されるアルコキ
シカルボニル基としてはその炭素数は特に限定されない
がアルコキシ部分の炭素数が1〜4のものが好ましい。Further, in the above general formula (II), the number of carbon atoms of the alkoxycarbonyl group represented by R4 is not particularly limited, but it is preferable that the alkoxy moiety has 1 to 4 carbon atoms.
本発明に於いて好適なアルコキシカルボニル基としては
、メトキシカルボニル基、エトキシカルボニル基、n−
プロポキシカルボニル基、i−プロポキシカルボニル基
、n−ブトキシカルボニル基、t−ブトキシカルボニル
基等が挙げられる。Suitable alkoxycarbonyl groups in the present invention include methoxycarbonyl groups, ethoxycarbonyl groups, n-
Examples include propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, and t-butoxycarbonyl group.
また上記一般式(II)中、R4において、れるハロゲ
ン原子としては、フッ素、塩素、臭素、ヨウ素の各原子
が挙げられる。Further, in the above general formula (II), examples of the halogen atom in R4 include fluorine, chlorine, bromine, and iodine atoms.
上記一般式(II)で示されるクロルアセトアミド誘導
体のうち、特に、R,、R2がエチル基でありR3が水
素原子でありR4がブトキシ基又はプロポキシメチル基
である化合物又はR,、R2がメで示されるR4のR3
がメトキシ基である化合物が薬害が少なく、除草活性が
高いため好適に使用される。Among the chloracetamide derivatives represented by the above general formula (II), compounds in which R, , R2 are ethyl groups, R3 is hydrogen atoms, and R4 is butoxy or propoxymethyl groups, or R, , R2 are R3 of R4 shown as
Compounds in which is a methoxy group are preferably used because they have little phytotoxicity and high herbicidal activity.
上記一般式〔■〕で示されるクロルアセトアミド誘導体
の製造方法としては、公知の製造方法が何ら制限されず
採用し得る。As a method for producing the chloracetamide derivative represented by the above general formula [■], any known production method can be employed without any restriction.
上記一般式(II)で示されるクロルアセトアミド誘導
体は、水田雑草全般にわたって幅広い殺草スペクトラム
を有しているが低薬量施用の場合あるいは雑草の葉期が
進んだ中期処理の場合においては一年生広葉雑草、オモ
ダカ、ウリカワ、クログワイ、ミズガヤツリ等の多年生
雑草に効果が弱いという性質を有している。The chloracetamide derivative represented by the above general formula (II) has a wide herbicidal spectrum for all paddy weeds, but when applied in low doses or in the case of mid-stage treatment when the leaf stage of the weeds has advanced, the annual broadleaf It has a property that it is weakly effective against perennial weeds such as weeds, Omodaka, Urikawa, Kurogwai, and Japanese cypress.
本発明の除草剤組成物にあっては、前記した−般式(J
)で示されるα−フェノキシフェニル酢酸エステルと一
般式(n)で示されるクロルアセトアミド誘導体とは広
い使用割合の範囲で夫々の単独からは予想できない優れ
た除草効果を発揮すると共に、巾広い殺草スペクトルを
有する。しかし、両者の使用割合は、α−フェノキシフ
ェニル酢酸エステル1重量部に対して、クロルアセトア
ミド誘導体が0.01〜50重量部の範囲であることが
一般的である。さらに好ましくは、α−フェノキシフェ
ニル酢酸エステル1重量部に対して、クロルアセトアミ
ド誘導体をO,1〜10重量部とすることにより、除草
効果はより優れたものとなる。In the herbicide composition of the present invention, the above-mentioned formula (J
) α-phenoxyphenylacetic acid ester represented by the formula (n) and the chloroacetamide derivative represented by the general formula (n) exhibit excellent herbicidal effects that cannot be expected from each alone in a wide range of usage ratios, and have a wide range of herbicidal effects. It has a spectrum. However, the ratio of the two used is generally in the range of 0.01 to 50 parts by weight of the chloracetamide derivative per 1 part by weight of α-phenoxyphenylacetate. More preferably, by using 1 to 10 parts by weight of the chloracetamide derivative per 1 part by weight of α-phenoxyphenylacetic acid ester, the herbicidal effect becomes even more excellent.
本発明の除草剤組成物の水田への施用量としては、一般
にα−フェノキシフェニル酢酸エステルが10アール当
り、2g〜2000g、好ましくは10g〜500gの
有効成分量となるように使用すれば良い。The herbicidal composition of the present invention may be applied to rice fields in an amount of 2 to 2000 g, preferably 10 to 500 g of the active ingredient per 10 ares of α-phenoxyphenylacetic ester.
本発明の除草剤組成物は、雑草の発芽前および発芽後に
処理しても効果を有し、土壌処理、茎葉処理においても
高い効果が得られる。施用場所としては水田はもちろん
のこと、各種穀類、マメ類、ワタ、そ菜類等の畑、果樹
園、芝生地、牧草地、茶園、桑園、森林地、非農耕地等
で広範囲に有用である。The herbicide composition of the present invention is effective even when treated before and after weed germination, and is also highly effective in soil treatment and foliage treatment. It is useful in a wide range of areas where it can be applied, including rice fields, fields of various grains, legumes, cotton, vegetable crops, orchards, lawns, pastures, tea gardens, mulberry gardens, forests, non-agricultural lands, etc. .
本発明の除草剤組成物は、原体そのものを撒布しても良
く、担体や必要に応じては他の補助剤と混合して調製し
た製剤として撒布しても良い。製剤形態は特に制限され
ず、従来公知の製剤形態が使用される。たとえば粉剤、
粗粉剤、微粒剤、粒剤、水和剤、乳剤、フロアブル製剤
、油Q濁剤等に調製して使用することが出来る。The herbicidal composition of the present invention may be sprayed as a raw material itself, or may be sprayed as a preparation prepared by mixing it with a carrier and, if necessary, other adjuvants. The formulation form is not particularly limited, and conventionally known formulation forms can be used. For example, powder
It can be prepared and used in coarse powders, fine granules, granules, wettable powders, emulsions, flowable preparations, oil Q clouding agents, etc.
本発明の除草剤組成物を製剤に調製するに際し、使用す
る適当な固体担体としては、従来公知のものが何ら制限
なく使用し得る。本発明に於て好適に使用される固体担
体を例示すると次のとおりである。例えばカオリナイト
群、モンモリロナイト群、アタパルジャイト群或いはシ
ータライト等で代表されるクレー類;タルク、雲母、葉
ロウ石、軽石、バーミキュライト、石こう、炭酸カルシ
ウム、ドロマイト、けいそう土、マグネシウム、石灰、
リン石灰、ゼオライト、無水ケイ酸、合成ケイ酸カルシ
ウム等の無機物質;大豆粉、タバコ粉、クルミ粉、小麦
粉、木粉、でんぷん、結晶セルロース等の植物性有機物
質;クマロン樹脂、石油樹脂、アルキド樹脂、ポリ塩化
ビニル、ポリアルキレングリコール、ケトン樹脂、エス
テルガム、コーパルガム、ダンマルガム等の合成または
天然の高分子化合物;カルナバロウ、蜜ロウ等のワック
ス類あるいは尿素等が挙げられる。When preparing the herbicidal composition of the present invention into a formulation, conventionally known solid carriers can be used without any limitations as suitable solid carriers. Examples of solid carriers preferably used in the present invention are as follows. For example, clays represented by kaolinite group, montmorillonite group, attapulgite group, or thetalite; talc, mica, phyllite, pumice, vermiculite, gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium, lime,
Inorganic substances such as phosphorous lime, zeolite, anhydrous silicic acid, and synthetic calcium silicate; Vegetable organic substances such as soybean flour, tobacco powder, walnut flour, wheat flour, wood flour, starch, and crystalline cellulose; Coumaron resin, petroleum resin, and alkyds Synthetic or natural polymer compounds such as resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gums, copal gums, and dammar gums; waxes such as carnauba wax and beeswax; and urea.
また、本発明に於いて使用される液体担体としては、従
来公知のものが何ら制限されずに使用し得る。本発明に
於て好適に使用される液体担体を例示すると次のとおり
である。ケロシン、鉱油、スピンドル油、ホワイトオイ
ル等のパラフィン系もしくはナフテン系炭化水素;ベン
ゼン、トルエン、キシレン、エチルベンゼン、クメン、
メチルナフタリン等の芳香族炭化水素;四塩化炭素、ク
ロロホルム、トリクロルエチレン、モノクロルベンゼン
、0−クロルトルエン等の塩素系炭化水素;ジオキサン
、テトラヒドロフラ〉′のようなエーテル類;アセトン
、メチルエチルケトン、ジイソブチルケトン、シクロヘ
キサノン、アセトフェノン、イソホロン等のケトン類;
酢酸エチル、酢酸アミル、エチレングリコールアセテー
ト、ジエチレングリコールアセテート、マレイン酸ジブ
チル、コハク酸ジエチル等のエステル類;メタノール、
n−ヘキサノール、エチレングリコール、ジエチレング
リコール等のアルコール類;エチレングリコールフェニ
ルエーテル、ジエチレングリコールエチルエーテル、ジ
エチレングリコールブチルエーテル等のエーテルアルコ
ール類;ジメチルホルムアミド、ジメチルスルホキシド
等の極性溶媒あるいは水等が挙げられる。Further, as the liquid carrier used in the present invention, conventionally known carriers can be used without any restriction. Examples of liquid carriers preferably used in the present invention are as follows. Paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil; benzene, toluene, xylene, ethylbenzene, cumene,
Aromatic hydrocarbons such as methylnaphthalene; Chlorinated hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, monochlorobenzene, 0-chlorotoluene; Ethers such as dioxane and tetrahydrofura; acetone, methyl ethyl ketone, diisobutyl ketone, Ketones such as cyclohexanone, acetophenone, isophorone;
Esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate; methanol,
Examples include alcohols such as n-hexanol, ethylene glycol, and diethylene glycol; ether alcohols such as ethylene glycol phenyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether; polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
また、本発明に於ける製剤の調製には、乳化、分散、湿
潤、拡展、結合、崩壊性調節、有効成分安定化、流動性
改良、防錆等の目的で従来公知の界面活性剤が何ら制限
されず使用し得る。界面活性剤としては、非イオン性、
陽イオン性、陰イオン性及び両イオン性のものが使用さ
れるが通常は非イオン性および(または)陰イオン性の
ものが好適に使用される。適当な非イオン性界面活性剤
としては、たとえば、ラウリルアルコール、ステアリル
アルコール、オレイルアルコール等の高級アルコールに
エチレンオキシドを重合付加させたもの;イソオクチル
フェノール、ノニルフェノール等のアルキルフェノール
にエチレンオキシドを重合付加させたもの;ブチルナフ
トール、オクチルナフトール等のアルキルナフトールに
エチレンオキシドを重合付加させたちの;バルミチン酸
、ステアリン酸、オレイン酸等の高級脂肪酸にエチレン
オキシドを重合付加させたちの;ステアリルりん酸、ジ
ラウリルりん酸、モノもしくはジアルキルりん酸にエチ
レンオキシドを重合付加させたちの;ドデシルアミン、
ステアリン酸アミド等のアミンにエチレンオキシドを重
合付加させたもの;ソルビタン等の多価アルコールの高
級脂肪酸エステルおよびそれにエチレンオキシドを重合
付加させたちの;エチレンオキシドとプロピレンオキシ
ドを重合付加させたちの;ジオクチルサクシネート等の
多価脂肪酸とアルコールとのエステル等があげられる。Furthermore, in the preparation of the formulation in the present invention, conventionally known surfactants are used for the purposes of emulsification, dispersion, wetting, spreading, binding, disintegration control, active ingredient stabilization, flowability improvement, rust prevention, etc. It can be used without any restrictions. As surfactants, nonionic,
Although cationic, anionic and amphoteric ones are used, nonionic and/or anionic ones are usually preferred. Suitable nonionic surfactants include, for example, those obtained by polymerizing and adding ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol; those obtained by polymerizing and adding ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol; Products obtained by polymerizing and adding ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol; products obtained by polymerizing and adding ethylene oxide to higher fatty acids such as valmitic acid, stearic acid, and oleic acid; stearyl phosphate, dilauryl phosphate, mono- or dialkyl Polymerized addition of ethylene oxide to phosphoric acid; dodecylamine;
Products obtained by polymerizing and adding ethylene oxide to amines such as stearic acid amide; products obtained by polymerizing and adding ethylene oxide to higher fatty acid esters of polyhydric alcohols such as sorbitan; products obtained by polymerizing and adding ethylene oxide and propylene oxide; dioctyl succinate, etc. Examples include esters of polyhydric fatty acids and alcohols.
適当な陰イオン性界面活性剤としては、たとえば、ラウ
リル硫酸ナトリウム、オレイルアルコール硫酸エステル
アミン塩等のアルキル硫酸エステル塩;スルホこはく酸
ジオクチルエステルナトリウム、2−エチルヘキセンス
ルホン酸ナトリウム等のアルキルスルホン酸塩;イソプ
ロピルナフタレンスルホン酸ナトリウム、メチレンビス
ナフタレンスルホン酸ナトリウム、リグニンスルホン酸
ナトリウム、ドデシルベンゼンスルホン酸ナトリウム等
のアリールスルホン酸塩;トリポリリン酸ソーダ等のリ
ン酸塩等があげられる。Suitable anionic surfactants include, for example, alkyl sulfate salts such as sodium lauryl sulfate and oleyl alcohol sulfate amine salt; alkyl sulfonate salts such as sodium sulfosuccinate dioctyl ester and sodium 2-ethylhexene sulfonate. ;Arylsulfonates such as sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfonate, sodium ligninsulfonate, and sodium dodecylbenzenesulfonate;phosphates such as sodium tripolyphosphate; and the like.
また、本発明に於ける製剤では、従来公知の補助剤が何
ら制限なく使用される。補助剤は、種々の目的で用いら
れるが、例えば粒剤の崩壊性等の性状を改善することに
より除草効果を高めようとする場合にも用いられる。本
発明に於いて好適に使用される補助剤を例示すると次の
とおりである。Furthermore, in the formulation of the present invention, conventionally known adjuvants can be used without any restrictions. Adjuvants are used for various purposes, and are also used, for example, when attempting to enhance the herbicidal effect by improving properties such as disintegration of granules. Examples of adjuvants suitably used in the present invention are as follows.
カゼイン、ゼラチン、アルブミン、ニカワ、アルギン酸
ソーダ、カルボキシメチルセルロース、メチルセルロー
ス、ヒドロキシエチルセルロース、ポリビニルアルコー
ル等の高分子化合物等が挙げられる。Examples include high molecular compounds such as casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and polyvinyl alcohol.
上記の担体、界面活性剤および補助剤は、製剤の剤型、
適用場面等を考慮して、目的に応じてそれぞれ単独にあ
るいは組合わせて適宜使用される。The above-mentioned carriers, surfactants and adjuvants are suitable for the dosage form of the preparation,
They are used individually or in combination as appropriate depending on the purpose, taking into consideration the application situation.
本発明に於ける製剤の調製方法は、特に限定されるもの
ではなく、従来公知の方法が使用される。The method for preparing the formulation in the present invention is not particularly limited, and conventionally known methods can be used.
例えば、水和剤の具体的な一調製方法として、クロルア
セトアミド誘導体2重量部とα−フェノキシフェニル酢
酸エステル5重量部を有機溶剤に熔かし、該溶液に界面
活性剤及び担体を加えよく粉砕混合した後、有機溶剤を
除去することにより水和剤を得る方法がある。For example, one specific method for preparing a wettable powder is to dissolve 2 parts by weight of a chloracetamide derivative and 5 parts by weight of α-phenoxyphenylacetic acid ester in an organic solvent, add a surfactant and a carrier to the solution, and grind thoroughly. There is a method of obtaining a wettable powder by removing the organic solvent after mixing.
また、たとえば乳剤の、具体的な一調製方法として、ク
ロルアセトアミド誘導体2重量部、α−フェノキシフェ
ニル酢酸エステル5重量部と界面活性剤15重量部をキ
シレン等の石油系溶剤によく混合して乳剤を得る方法が
ある。For example, as a specific method for preparing an emulsion, 2 parts by weight of a chloracetamide derivative, 5 parts by weight of α-phenoxyphenylacetic acid ester, and 15 parts by weight of a surfactant are thoroughly mixed in a petroleum solvent such as xylene to form an emulsion. There is a way to get it.
さらにまた、たとえば粒剤の具体的な一調製方法として
、クロルアセトアミド誘導体2重量部、α−フェノキシ
フェニル酢酸エステル5重量部、界面活性剤及び水をよ
く混練し、続いて、担体及び界面活性剤を加え、よくか
きまぜた後、所定の粒径に押し出し、乾燥することによ
り粒剤を得る方法がある。Furthermore, as a specific method for preparing granules, for example, 2 parts by weight of a chloracetamide derivative, 5 parts by weight of α-phenoxyphenylacetic acid ester, a surfactant and water are thoroughly kneaded, and then a carrier and a surfactant are mixed. There is a method of obtaining granules by adding, stirring well, extruding to a predetermined particle size, and drying.
〔効 果〕
以上に説明した本発明の除草剤組成物は、その各成分単
独の性質からは全く予想できない除草効果を示す。即ち
、α−フェノキシフェニル酢酸エステル及びクロルアセ
トアミド誘導体のいずれも、夫々単独で用いたのではあ
まり除草効果が期待できないミズガヤツリ、クログワイ
、オモダカ、ウリカワなどの多年生雑草に対して、本発
明の除草剤組成物は優れた除草効果を発揮する。従って
、本発明の除草剤組成物は、その構成成分単独の殺草ス
ペクトルよりも幅広い殺草スペクトルを存する。さらに
、オモダカ、ウリカワ、ミズガヤツリ等の水田の強害雑
草に対してはそれぞれの単独の性質からは全く予期でき
ない程の相乗作用を有しており、各成分単独の施用量と
同程度あるいはそれ以下の施用量でより大きい除草効果
を有し、しかも、作物に対しては安全である。[Effect] The herbicidal composition of the present invention described above exhibits a herbicidal effect that cannot be expected from the properties of each component alone. That is, the herbicide composition of the present invention can be used against perennial weeds such as cypress, cypress, omodaka, and weed, for which neither α-phenoxyphenylacetate nor chloracetamide derivatives can be expected to have much herbicidal effect when used alone. The product exhibits excellent weeding effects. Therefore, the herbicidal composition of the present invention has a broader herbicidal spectrum than that of its constituent components alone. Furthermore, it has a synergistic effect against the harmful weeds of paddy fields, such as Omodaka, Urikawa, and Cyperus japonica, in a way that could not be expected from the properties of each component alone, and the amount of application of each component alone is equal to or lower than that of each component alone. It has a greater herbicidal effect at an application rate of 1,000 ml, and is safe for crops.
従って、本発明の除草剤組成物は、除草剤に要求される
性質を十分に満たすものであって、その有用性は極めて
大きいものである。Therefore, the herbicidal composition of the present invention fully satisfies the properties required of a herbicide, and is extremely useful.
以下に、本発明を実施例で具体的に説明するが、本発明
は、これらの実施例に限定されるものではない。EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.
合成例1
100nlナス型フラスコにα−クロルフェニル酢酸ク
ロリド5.7gを入れ、水冷下メタノール50mj!を
徐々に滴下した。室温でさらに2日間攪拌した後、メタ
ノールを除去し、α−クロルフェニル酢酸メチルを得た
。次に10On!!ナス型フラスコに2−メチル−4−
クロルフェノール4.3g、水酸化ナトリウム1.2g
、N、N−ジメチルホルムアミド40m1lを入れ、室
温で2時間攪拌した後、α−クロルフェニル酢酸メチル
を加え、120℃の油浴上5時間加熱攪拌した。溶媒を
除去した後、残留物にクロロホルムを加え分液ロートに
移し、100mAの水で水洗した後、クロロホルム層を
無水硫酸ナトリウムで乾燥した。クロロホルムを除去し
残留物を減圧蒸留し淡黄色液体4.47 g (bpl
56℃10.1韻11g)を得た。Synthesis Example 1 5.7 g of α-chlorophenylacetic acid chloride was placed in a 100 nl eggplant flask, and 50 mj of methanol was added under water cooling. was gradually added dropwise. After stirring for an additional 2 days at room temperature, methanol was removed to obtain methyl α-chlorophenylacetate. Next is 10On! ! 2-methyl-4- in an eggplant-shaped flask
Chlorphenol 4.3g, sodium hydroxide 1.2g
, N,N-dimethylformamide (40 ml) was added thereto, and after stirring at room temperature for 2 hours, methyl α-chlorophenylacetate was added, and the mixture was heated and stirred on a 120° C. oil bath for 5 hours. After removing the solvent, chloroform was added to the residue and the mixture was transferred to a separating funnel, washed with 100 mA water, and the chloroform layer was dried over anhydrous sodium sulfate. Chloroform was removed and the residue was distilled under reduced pressure to give 4.47 g (bpl) of pale yellow liquid.
56° C. 10.1 rhymes (11 g) were obtained.
このものの赤外吸収スペクトルを測定した結果、300
0〜2900cm−’にC−H結合に基づく吸収、17
30cm−’にエステル基のカルボニル結合に基づく強
い吸収を示した。その元素分析値はC66、28%、H
5,16%、C112,08%であって、組成式C+6
H+s(J’03(290,74)に対する計算値であ
るC 66.10%、H5,20%、C112,19%
に良く一致した。As a result of measuring the infrared absorption spectrum of this material, 300
Absorption based on C-H bond from 0 to 2900 cm-', 17
A strong absorption based on the carbonyl bond of the ester group was observed at 30 cm-'. Its elemental analysis values are C66, 28%, H
5,16%, C112,08%, composition formula C+6
H+s (calculated values for J'03 (290,74) C 66.10%, H5, 20%, C112, 19%
There was good agreement.
またlスペクトルを測定したところ、m/e290.2
92にMΦに対応するピーク、m/eに対応する各ピー
クを示した。Also, when I measured the l spectrum, m/e290.2
92 shows the peak corresponding to MΦ and each peak corresponding to m/e.
さらに’H−NMR(δ;ppm:テトラメチルシラン
基準、重クロロホルム溶媒)を測定した結果は次の通り
であった。Further, 'H-NMR (δ; ppm: tetramethylsilane standard, deuterium chloroform solvent) was measured, and the results were as follows.
(al
I3
2.27ppmにプロトン3個分の一重線を示し、+a
lのメチルプロトンに相当した。(Al I3 shows a singlet of 3 protons at 2.27 ppm, +a
It corresponded to 1 methyl proton.
3.58ppmにプロトン3個分の一重線を示し、(b
lのメチルプロトンに相当した。A singlet for 3 protons is shown at 3.58 ppm, (b
It corresponded to 1 methyl proton.
5.51ppmにプロトン1個分の一重線を示し、(C
1のメチンプロトンに相当した。A singlet for one proton is shown at 5.51 ppm, and (C
This corresponded to 1 methine proton.
664〜7.6ppmにプロトン8個分の多重線を示し
、(dlのベンゼン環プロトンに相当した。A multiplet of 8 protons was shown at 664 to 7.6 ppm, corresponding to the benzene ring proton of (dl).
上記の結果から、単離生成物がα−(2−メチル−4−
クロルフェノキシ)フェニル酢酸メチル(化合物番号1
)であることが明らかとなった。From the above results, it is clear that the isolated product is α-(2-methyl-4-
Chlorphenoxy) methyl phenyl acetate (compound number 1
) was found to be.
収率は51.0%であった。The yield was 51.0%.
合成例2
100m/ナス型フラスコにマンデル酸メチル3.3g
、キシレン40m!!、水酸化ナトリウム0.5gを入
れ100℃の油浴上1時間加熱攪拌した後、2−ブロム
−5−クロルトルエン4.1g及び清粉2gを入れ24
時間加熱還流した。次に反応液をろ過した後、キシレン
を留去し残留物を減圧1留することによって淡黄色液体
1.4g(bp156℃10.11■Hg)を得た。Synthesis Example 2 3.3g of methyl mandelate in a 100m/Eggplant flask
, xylene 40m! ! After adding 0.5 g of sodium hydroxide and heating and stirring on a 100°C oil bath for 1 hour, add 4.1 g of 2-bromo-5-chlorotoluene and 2 g of refined powder.
The mixture was heated to reflux for an hour. Next, the reaction solution was filtered, xylene was distilled off, and the residue was vacuumed for one distillation to obtain 1.4 g of a pale yellow liquid (bp 156° C., 10.11 μHg).
このものの赤外吸収スペクトル、質量スペクトル、’H
−NMRは化合物番号1のものと一敗した。収率は24
.2%であった。Infrared absorption spectrum, mass spectrum, 'H
-NMR was inferior to that of compound number 1. The yield is 24
.. It was 2%.
合成例3
100mj2ナス型フラスコに2−メチル−4−クロル
フェノールナトリウム塩4.9g、α−クロルフェニル
酢酸ブチル6.8g、、N、N−ジメチルホルムアミド
40mJを入れ、120℃の油浴上で5時間加熱攪拌し
た。次にエバポレーターでN、N−ジメチルホルムアミ
ドを除去した後、残留物にクロロホルム80m1を加え
て分液ロートに移し、100n+42の水で2回水洗し
た。クロロホルム層を分離し無水硫酸ナトリウムで乾燥
した後、クロロホルムを除去し残留物を減圧蒸留して淡
黄色液体7.5 g (bpl 60〜162℃10.
1龍Hg)を得た。Synthesis Example 3 4.9 g of 2-methyl-4-chlorophenol sodium salt, 6.8 g of butyl α-chlorophenylacetate, and 40 mJ of N,N-dimethylformamide were placed in a 100 mj 2 eggplant flask and heated on an oil bath at 120°C. The mixture was heated and stirred for 5 hours. Next, after removing N,N-dimethylformamide using an evaporator, 80 ml of chloroform was added to the residue, which was then transferred to a separating funnel and washed twice with 100 N+42 of water. After separating the chloroform layer and drying it over anhydrous sodium sulfate, the chloroform was removed and the residue was distilled under reduced pressure to give 7.5 g of pale yellow liquid (bpl 60-162℃10.
1 dragon Hg) was obtained.
このものの赤外吸収スペクトルを測定した結果は第1図
に示す通りであり、3060〜2850cm−’にC−
H結合に基づく吸収、1750cm−’にエステル基の
カルボニル結合に基づく強い吸収を示した。The results of measuring the infrared absorption spectrum of this material are shown in Figure 1, and the C-
Absorption based on H bond and strong absorption based on carbonyl bond of ester group were shown at 1750 cm-'.
その元素分析値は、C68,77%、H6,36%、C
110,51%であって組成式Cl98ZICI 0s
(332,83)に対する計算値であるC 68.57
%、H6,36%、(J’10.65%に良く一致した
。Its elemental analysis values are C68.77%, H6.36%, C
110.51% and composition formula Cl98ZICI 0s
C 68.57 which is the calculated value for (332,83)
%, H6, 36%, (J'10.65%).
またIaffiスペクトルを測定したところ、m/e3
32.334にMΦに対応するピーク、m/eに対応す
る各ピークを示した。さらに’ H−N M R(δ;
ppm:テトラメチルシラン基準、重クロロホルム溶媒
)を測定した結果を第2図に示した。Also, when Iaffi spectrum was measured, m/e3
32.334 shows a peak corresponding to MΦ and each peak corresponding to m/e. Furthermore, 'H-N M R(δ;
The results of measuring ppm (based on tetramethylsilane, deuterated chloroform solvent) are shown in FIG.
その解析結果は次の通りであった。The analysis results were as follows.
(b)
lh
0.7〜1.7 ppmにプロトン7個分の多重線を示
し、(a)のプロトンに相当した。2.27ppmにプ
ロトン3個分の一重線を示し、(b)のメチルプロトン
に相当した。4.O4ppmにプロトン2個分の三重線
を示し、(C)のメチレンプロトンに相当した。(b) A multiplet of 7 protons was shown at lh 0.7 to 1.7 ppm, which corresponded to the protons in (a). A singlet corresponding to 3 protons was shown at 2.27 ppm, which corresponded to the methyl proton in (b). 4. A triplet line corresponding to two protons was shown at O4ppm, which corresponded to the methylene proton in (C).
5、53 ppmにプロトン1個分の一重線を示し、(
dlのメチンプロトンに相当した。6.5〜7.6 p
pmにプロトン8個分の多重線を示しくe)のベンゼン
環のプロトンに相当した。A singlet for one proton is shown at 5 and 53 ppm, (
It corresponded to the methine proton of dl. 6.5-7.6p
A multiplet of 8 protons is shown at pm, which corresponds to the proton of the benzene ring in e).
上記の結果から、単離生成物がα−(2−メチル−4−
クロルフェノキシ)フェニル酢酸ブチル(化合物番号2
)であることが明らかとなった。From the above results, it is clear that the isolated product is α-(2-methyl-4-
butyl chlorphenoxy)phenylacetate (compound number 2
) was found to be.
収率は75.1%であった。The yield was 75.1%.
合成例4
100nlナス型フラスコに2−メチル−4−クロルフ
ェノール4.3g、m粉砕した水酸化ナトリウム1.2
g、N、N−ジメチルホルムアミド501Tllを入れ
、室温で1時間撹拌した後、α−クロルフェニル酢酸ア
リル5.4gを加え、120℃の油浴上で5時間加熱攪
拌した。溶媒を除去した後、残留物にクロロホルムを加
え分液ロートに移し、100m1の水で水洗した後、ク
ロロホルム層を無水硫酸ナトリウムで乾燥した。クロロ
ホルムを除去し残留物を減圧蒸留し淡黄色液体6.7g
(bp160〜162℃10.25龍Hg)を得た。Synthesis Example 4 4.3 g of 2-methyl-4-chlorophenol was placed in a 100 nl eggplant flask, and 1.2 m of crushed sodium hydroxide was placed in a 100 nl eggplant flask.
After adding 501 Tll of g,N,N-dimethylformamide and stirring at room temperature for 1 hour, 5.4 g of allyl α-chlorophenylacetate was added, and the mixture was heated and stirred on a 120° C. oil bath for 5 hours. After removing the solvent, chloroform was added to the residue and the mixture was transferred to a separating funnel, washed with 100 ml of water, and the chloroform layer was dried over anhydrous sodium sulfate. After removing chloroform, the residue was distilled under reduced pressure to obtain 6.7 g of pale yellow liquid.
(bp 160-162°C, 10.25 dragon Hg) was obtained.
このものの赤外吸収スペクトルを測定した結果は第3図
に示す通りであり、3060〜2930cI11−霊に
C−H結合に基づく吸収、1745cm−’にエステル
基のカルボニル結合に基づく強い吸収を示した。The results of measuring the infrared absorption spectrum of this product are as shown in Figure 3, showing an absorption based on the C-H bond at 3060-2930cI11-, and a strong absorption based on the carbonyl bond of the ester group at 1745cm-'. .
その元素分析値は、C68,69%、H5,34%であ
って、組成式C+sll+、C103(316,78>
に対する計算値であるC 6 B、 25%、H5,4
1%に良く一致した。Its elemental analysis values are C68,69%, H5,34%, composition formula C+sll+, C103 (316,78>
Calculated value for C 6 B, 25%, H5,4
It was in good agreement with 1%.
また質量スペクトルを測定したところ、m/e316.
318にMΦに対応するピーク、m/e応するピーク、
m/e175に
を示した。さらに’H−NMR(δ:ppm:テトラメ
チルシラン基準、重クロロホルム溶媒)を測定した結果
を第4図に示した。その解析結果は次の通りであった。Moreover, when the mass spectrum was measured, m/e316.
318, a peak corresponding to MΦ, a peak corresponding to m/e,
m/e175 was shown. Furthermore, the results of 'H-NMR (δ:ppm: tetramethylsilane standard, deuterium chloroform solvent) are shown in FIG. The analysis results were as follows.
(a)
C11゜
2.30ppmにプロトン3個分の一重線を示しfa)
のメチルプロトンに相当した。4.5〜4.6 ppm
にプロトン2個分の二重線を示しくb)のメチレンプロ
トンに相当した。4.9〜5.3 ppmにプロトン2
個分の多重線を示しくC)のメチレンプロトンに相当し
た。5.56ppmにプロトン1個分の一重線を示しく
d)のメチンプロトンに相当した。5.5〜6.1 p
pmにプロトン1個分の多重線を示しくe)のアリル基
内部のプロトンに相当した。6.5〜7.6 ppmに
プロトン8個分の多重線を示し、(f)のベンゼン環の
プロトンに相当した。(a) Shows a singlet of 3 protons at C11゜2.30ppmfa)
corresponded to the methyl proton of 4.5-4.6 ppm
2 shows a double line for two protons, which corresponds to the methylene proton in b). 2 protons at 4.9-5.3 ppm
This corresponds to the methylene proton in C). A singlet corresponding to one proton was shown at 5.56 ppm, which corresponded to the methine proton in d). 5.5-6.1p
The multiplet line corresponding to one proton is shown at pm, which corresponds to the proton inside the allyl group in e). A multiplet of 8 protons was shown at 6.5 to 7.6 ppm, which corresponded to the protons of the benzene ring in (f).
上記の結果から、単離生成物がα−(2−メチル−4−
クロルフェノキシ)フェニル酢酸アリル(化合物番号3
)であることが明らかとなった。From the above results, it is clear that the isolated product is α-(2-methyl-4-
Chlorphenoxy) allyl phenyl acetate (compound number 3
) was found to be.
収率は70.8%であった。The yield was 70.8%.
合成例5
100n+42ナス型フラスコにα−(2−メチル−4
−クロルフェノキシ)フェニル酢酸2.5g、クロロホ
ルム15mf、塩化チオニル2.5gを入れ室温で2時
間攪拌した後、1時間加熱還流した。Synthesis Example 5 α-(2-methyl-4
2.5 g of -chlorophenoxy)phenylacetic acid, 15 mf of chloroform, and 2.5 g of thionyl chloride were added thereto, stirred at room temperature for 2 hours, and then heated under reflux for 1 hour.
反応液を冷却後、118分を除去し残留したα−(2−
メチル−4−クロルフェノキシ)フェニル酢酸クロリド
に水冷下グリコール酸エチル5gを徐々に滴下した。次
にトリエチルアミン1gを徐々に加え室温で3時間攪拌
した後50℃の油浴上1時間加熱攪拌した。次にこの反
応液から、未反応のグリコール酸エチルを減圧上除去し
残留物にクロロホルム80m1を加え、分液ロートに移
しLoom Nの水で水洗した。クロロホルム層を無水
硫酸ナトリウムで乾燥した後、クロロホルムを除去し残
留物を減圧蒸留し、淡黄色液体1.77 g (b、p
l 90〜192℃10.35鶴h)を得た。After cooling the reaction solution, 118 min was removed and the remaining α-(2-
5 g of ethyl glycolate was gradually added dropwise to methyl-4-chlorophenoxy)phenylacetic acid chloride under water cooling. Next, 1 g of triethylamine was gradually added, and the mixture was stirred at room temperature for 3 hours, and then heated and stirred on a 50° C. oil bath for 1 hour. Next, unreacted ethyl glycolate was removed from the reaction solution under reduced pressure, and 80 ml of chloroform was added to the residue, which was then transferred to a separating funnel and washed with Loom N water. After drying the chloroform layer with anhydrous sodium sulfate, the chloroform was removed and the residue was distilled under reduced pressure to obtain 1.77 g of pale yellow liquid (b, p
l 90-192°C 10.35 Tsuru h) was obtained.
このものの赤外吸収スペクトルを測定した結果3060
〜2970cm−’にC−H結合に基づく吸収、175
0c+r’にエステル基のカルボニル結合に基づく強い
吸収を示した。その元素分析値はC62,81%、H5
,24%であって組成式C+JLqC(l 01(36
2,81)に対する計算値であるC 62.90%、H
5,28%に良く一致した。The result of measuring the infrared absorption spectrum of this substance is 3060
Absorption based on C-H bond at ~2970 cm-', 175
A strong absorption based on the carbonyl bond of the ester group was shown at 0c+r'. Its elemental analysis value is C62, 81%, H5
, 24% and the composition formula C+JLqC(l 01(36
C 62.90%, H
There was a good agreement of 5.28%.
また質量スペクトルを測定したところ、m / C36
2にMΦに対応するピーク、m/e231に応するピー
クを示した。さらに’H−NMR(δ;ppm’テトラ
メチルシラン基準、重クロロホルム溶媒)を測定した結
果は次の通りであった。In addition, when mass spectra were measured, m/C36
2 shows a peak corresponding to MΦ and a peak corresponding to m/e231. Furthermore, the results of 'H-NMR (δ; ppm' based on tetramethylsilane, deuterated chloroform solvent) were as follows.
(bl
CH,3
1,15ppmにプロトン3個分の三重線を示し、(a
)のメチルプロトンに相当した。2.28ppmにフ。(bl CH,3 Triplet line of 3 protons is shown at 1.15 ppm, (a
) corresponded to the methyl proton. 2.28 ppm.
ロトン3個分の一重線を示しくblのメチルプロトンに
相当した。4.08 ppmにプロトン2個分の四重線
を示しくe)のメチレンプロトンに相当した。4.54
ppmにプロトン2個分の二重線を示しくd)のメチレ
ンプロトンに相当した。5.62ppmにプロトン1個
分の一重線を示しfe)のメチンプロトンに相当した。A singlet line corresponding to three rotons is shown and corresponds to the methyl proton of bl. A quartet of two protons was shown at 4.08 ppm, which corresponded to the methylene proton in e). 4.54
A double line corresponding to two protons is shown in ppm, which corresponds to the methylene proton in d). A singlet corresponding to one proton was observed at 5.62 ppm, which corresponded to the methine proton of fe).
6.5〜7.6 ppmにプロトン8個分の多重線を示
しくf)のベンゼン環のプロトンに相当した。A multiplet of 8 protons was shown at 6.5 to 7.6 ppm, which corresponded to the protons of the benzene ring in f).
上記の結果から、単離生成物がα−(2−メチル−4−
クロルフェノキシ)フェニル酢酸エトキシカルボニルメ
チル(化合物番号4)であることが明らかとなった。収
率は5.1.0%であった。From the above results, it is clear that the isolated product is α-(2-methyl-4-
It was revealed to be ethoxycarbonylmethyl chlorphenoxy)phenylacetate (compound number 4). The yield was 5.1.0%.
合成例6
100m1lナス型フラスコに2−クロル−4,5−ジ
メチルフェノール3.12g1水酸化すトリウム0.8
6g、α−クロルフヱニル酢酸エチル4g8N、N−ジ
メチルホルムアミド50m1を入れ120℃の油浴上1
5時間加熱撹拌した。次に溶媒を減圧で除去した後、残
留物にクロロホルム80m1を加え、分液ロートに移し
100m1の水で水洗した。クロロホルム層を無水硫酸
ナトリウムで乾燥した後、クロロホルムを除去し残留物
を減圧藩留し、淡黄色液体4.28 g (bpl 6
5〜167℃10.3■霞Hg、 mp58〜59℃)
を得た。Synthesis Example 6 2-chloro-4,5-dimethylphenol 3.12 g 1 thorium hydroxide 0.8 in a 100 ml eggplant flask
6 g, α-chlorophenyl ethyl acetate, 4 g, 8 N, N-dimethylformamide, 50 ml, and placed on an oil bath at 120°C.
The mixture was heated and stirred for 5 hours. Next, after removing the solvent under reduced pressure, 80 ml of chloroform was added to the residue, which was transferred to a separating funnel and washed with 100 ml of water. After drying the chloroform layer with anhydrous sodium sulfate, the chloroform was removed and the residue was distilled under reduced pressure to obtain 4.28 g (bpl 6) of a pale yellow liquid.
5-167℃ 10.3 ■ Haze Hg, mp58-59℃)
I got it.
このものの赤外吸収スペクトルを測定した結果3050
〜2900cm−IにC−H結合に基づく吸収、174
5ω−1にエステル基のカルボニル結合に基づく強い吸
収を示した。その元素分析値はC67,41%、85.
88%であって組成式C+aH+wC103(318,
80)に対する計算値であるC 67.82%、H6,
01%に良く一致した。また質量スペクトルを測定した
ところ、m/e318,320にMΦに対応するピーク
、m/c245,247に各ピークを示した。さらに’
H−NMR(δ; ppm :テトラメチルシラン基準
6、重クロロホルム溶媒)を測定した結果は次の通りで
あった。The result of measuring the infrared absorption spectrum of this substance is 3050
Absorption based on C-H bond at ~2900 cm-I, 174
A strong absorption based on the carbonyl bond of the ester group was observed at 5ω-1. Its elemental analysis value is C67, 41%, 85.
88% and has the composition formula C+aH+wC103 (318,
C 67.82%, H6, which is the calculated value for 80)
It was in good agreement with 0.01%. When the mass spectrum was measured, peaks corresponding to MΦ were shown at m/e 318 and 320, and peaks at m/c 245 and 247 were shown. moreover'
The results of H-NMR (δ; ppm: tetramethylsilane standard 6, deuterated chloroform solvent) were as follows.
(el C1
1、15ppmにプロトン3個分の三重線を示し、(a
lのメチルプロトンに相当した。2.llppmにプロ
トン6個分の一重線を示しくb)の2つのメチルプロト
ンに相当した。4.llppmにプロトン2個分の四重
線を示しくC)のメチレンプロトンに相当した。(el C1 shows a triplet line of 3 protons at 1.15 ppm, (a
It corresponded to 1 methyl proton. 2. A singlet line corresponding to 6 protons is shown at llppm, which corresponds to the two methyl protons in b). 4. A quartet of two protons is shown at llppm, which corresponds to the methylene proton in C).
5.55ppmにプロトン1個分の一重線を示しくdl
のメチンプロトンに相当した。6.6−3 ppm 、
および7、O5ppmにそれぞれプロトン1個分の一重
線をを示しそれぞれte)、 (f)のベンゼン環のプ
ロトンに相当した。7.2〜7.7ppn+にプロトン
5個分の多m線を示し、(幻のベンゼン環のプロトンに
相当した。Show the singlet of one proton at 5.55 ppm dl
corresponded to the methine proton. 6.6-3 ppm,
A singlet corresponding to one proton was shown at 7 and 5 ppm of O, respectively, which corresponded to the protons of the benzene ring in te) and (f), respectively. A polym line corresponding to 5 protons was shown at 7.2 to 7.7 ppn+ (corresponding to the proton of the phantom benzene ring).
上記の結果から、単離生成物がα−(2−クロル−4,
5−ジメチルフェノキシ)フェニル酢酸エチル(化合物
番号5)であることが明らかとなった。収率は67.5
%であった。From the above results, it is clear that the isolated product is α-(2-chloro-4,
It was found to be ethyl 5-dimethylphenoxy)phenylacetate (compound number 5). Yield is 67.5
%Met.
合成例7
合成例1〜4において詳細に記述したのと同様な方法に
より、第1表に記載したα−フェノキシフェニル酢酸エ
ステルを合成した。合成した化合物は無色または淡黄色
の粘稠液体または固体であり、赤外吸収スペクトルでは
1730〜1770cm−’にカルボニル結合に基づく
特性吸収を示した。第1表には得られた化合物の構造、
態様、物性値、カルボニル結合に基づく赤外吸収値元素
分析値をも併せて記載した。Synthesis Example 7 The α-phenoxyphenylacetic acid esters listed in Table 1 were synthesized by the same method as described in detail in Synthesis Examples 1-4. The synthesized compound was a colorless or pale yellow viscous liquid or solid, and its infrared absorption spectrum showed characteristic absorption based on carbonyl bonds at 1730 to 1770 cm-'. Table 1 shows the structure of the obtained compound,
Aspects, physical property values, infrared absorption values and elemental analysis values based on carbonyl bonds are also described.
次に、本発明の除草剤組成物の配合例及び実施例を示す
。尚、配合例及び実施例中、α−フェノキシフェニル酢
酸エステルは合成例中の化合物番号〔(1)〜(50)
)で表わし、クロルアセトアミド誘導体は下記の第2
表に示す記号(〔A〕〜〔I〕)で表わした。Next, formulation examples and examples of the herbicide composition of the present invention will be shown. In addition, in the formulation examples and examples, α-phenoxyphenylacetic esters are compound numbers [(1) to (50)] in the synthesis examples.
), and the chloracetamide derivative is represented by the second formula below.
It is represented by the symbols ([A] to [I]) shown in the table.
以下余白
第 2 表
配合例1 (粒剤)
合成例1で合成した化合物(化合物番号1)4重量部、
化合物〔A32重量部、ジオクチルサクシネート1重量
部、リグニンスルホン酸ソーダ3重量部、ベントナイト
30重量部、及びタルク60重量部をよく混合粉砕し、
水を加えて混練した後、造粒乾燥し、14〜32メツシ
ユに整粒して粒剤を得た。Below is the margin: Table 2 Formulation Example 1 (Granules) 4 parts by weight of the compound synthesized in Synthesis Example 1 (Compound No. 1),
Compound [32 parts by weight of A, 1 part by weight of dioctyl succinate, 3 parts by weight of sodium lignin sulfonate, 30 parts by weight of bentonite, and 60 parts by weight of talc were thoroughly mixed and ground;
After adding water and kneading, the mixture was granulated, dried, and sized to 14 to 32 meshes to obtain granules.
配合例2(水和剤)
合成例3で合成した化合物(化合物番号2)5重量部、
化合物〔035重量部、ポリオキシエチレンノニルフェ
ニルエーテル2 N ’lx 部、m +5)クレー4
0重量部、及びジ−クライト48重量部をよく粉砕混合
して水和剤を得た。Formulation example 2 (hydrating agent) 5 parts by weight of the compound synthesized in synthesis example 3 (compound number 2),
Compound [035 parts by weight, 2 N'lx parts of polyoxyethylene nonylphenyl ether, m +5) Clay 4
A wettable powder was obtained by thoroughly pulverizing and mixing 0 parts by weight and 48 parts by weight of gicrite.
配合例3 (乳剤)
合成例4で合成した化合物(化合物番号3)10重量部
、化合物CB)10重量部、キシレン70重量部、ポリ
オキシエチレンアルキルアリルエーテル5重量部、及び
アルキルベンゼンスルホン酸ソーダ5重量部を混合溶解
して乳剤を得た。Formulation Example 3 (Emulsion) 10 parts by weight of the compound synthesized in Synthesis Example 4 (compound number 3), 10 parts by weight of compound CB), 70 parts by weight of xylene, 5 parts by weight of polyoxyethylene alkyl allyl ether, and 5 parts by weight of sodium alkylbenzenesulfonate. Parts by weight were mixed and dissolved to obtain an emulsion.
配合例4
ベントナイト40重量部、タルク55重量部、およびト
リポリリン酸ソーダ5重量部を粉砕混合し、加水、混練
後造粒乾燥し、活性成分を含まない粒状物を作る。この
粒状物87重量部に化合物(G)を5重量部、化合物(
3)を8重量部を含浸させ粒剤を得た。Formulation Example 4 40 parts by weight of bentonite, 55 parts by weight of talc, and 5 parts by weight of sodium tripolyphosphate are ground and mixed, added with water, kneaded, and then granulated and dried to produce granules containing no active ingredient. 5 parts by weight of compound (G) was added to 87 parts by weight of this granular material.
Granules were obtained by impregnating 8 parts by weight of 3).
実施例1
8850分の1アール相当の磁製ポットに、加水混練し
た水田土壌を充填し、土壌表層にノビエを播種し、さら
にウリカワ、オモダカ、ミズガヤツリの塊茎を埋め込ん
だ。その後、約3印の湛水条件とし、20〜25℃のガ
ラス室内で育成し、7日後(ノビエが約0.8葉期の時
3tIl)および14日後(ノビエが約2葉期の時11
Ji)に、配合、t+ 1に準じて調製した水和剤を水
に希釈し所定量滴下処理した。その後ガラス室内で育成
し、薬剤処理後21日目に除草効果を調査した結果を第
3表に示した。Example 1 A porcelain pot equivalent to 1/8850 are was filled with watered and kneaded paddy soil, and Japanese wild grass was sown on the surface layer of the soil, and tubers of Urticaria, Omodaka, and Cyperus japonica were embedded. Thereafter, the condition was set to about 3 marks, and the plants were grown in a glass room at 20 to 25°C, and after 7 days (3tIl when the wildflowers were at about 0.8 leaf stage) and 14 days later (11 when the wildflowers were at about 2 leaf stage).
A wettable powder prepared according to the formulation and t+1 was diluted with water and added dropwise in a predetermined amount to Ji). Thereafter, the plants were grown in a glass room, and the herbicidal effect was investigated on the 21st day after the chemical treatment. The results are shown in Table 3.
除草効果は薬剤処理区の地上部生草重および無処理区の
地上部生草重を測定して下記の式により抑制率(%)を
算出した。The herbicidal effect was determined by measuring the above-ground grass weight in the chemically treated area and the above-ground grass weight in the untreated area, and calculating the suppression rate (%) using the following formula.
また、本発明の除草剤組成物はそれぞれの単独の除草剤
からは考えられない相乗効果を有しているが、特にその
効果の著しい雑草についてE値を計算した結果を第3表
に示した。In addition, the herbicide composition of the present invention has a synergistic effect that cannot be expected from each herbicide alone, and Table 3 shows the results of calculating the E value for weeds for which the effect is particularly remarkable. .
旦値二■所
2種の活性化合物を組合わせた場合の除草活性が、その
2種の化合物の各々の活性の単純な合計(M待される活
性)よりも大きくなる場合にこれを相乗作用という。2
種の除草剤の特定組合わせにより期待される。活性は、
次の様にして計算することができる。(S、R,Co1
by、除草剤の組合わせの相乗および拮抗反応の計算r
WeedJ vol、 15 。When the herbicidal activity when two types of active compounds are combined is greater than the simple sum of the respective activities of the two types of compounds (the expected activity), this is called synergism. That's what it means. 2
Expected by specific combinations of species herbicides. The activity is
It can be calculated as follows. (S, R, Co1
by, calculation of synergistic and antagonistic reactions of herbicide combinations
WeedJ vol, 15.
20〜22頁、1967年を参照):
X:除草剤Aをag/アールの量で処理した時の抑制率
Y:除草剤Bをbg/アールの計で処理した時の抑制率
E:除草剤Aをag/アール、除草剤Bをbg/アール
で使用した場合に期待される抑制率即ち、実際抑制率が
上記計算のE値より大きいならば、組合わせによる活性
は相乗作用を示すということができる。(See pages 20-22, 1967): X: Inhibition rate when herbicide A is treated in ag/are amount Y: Inhibition rate when herbicide B is treated in bg/are amount E: Weed control If the expected inhibition rate, that is, the actual inhibition rate when using agent A at ag/are and herbicide B at bg/are, is greater than the E value calculated above, the combined activity is said to exhibit a synergistic effect. be able to.
以下余白
第 3 表 の 1
第 3 表 の 3
第 3 表 の 4
実施例2
8850分の1アール相当のEeL袈ポットに、加水混
練した水田土壌を充填し、土壌表層にノビエ、クマガヤ
ツリ、ホタルイおよびコナギ、アゼナ、キカシグサ等の
広葉雑草種子をtI種し、ウリカワ、ミズガヤツリの塊
茎を埋め込んだ。さらに2.5葉期の稲苗(品種名:ア
キニシキ)を2cmの深さに3本1株植とした。その後
、約3Cfflの温水条件とし、20〜25℃のガラス
室内で育成し、稲移植7日後(ノビエが約0.8葉期の
時期)および14日後(ノビエが約2葉期の時期)に、
配合例1に準じて調製した水和剤を水に希釈し所定量滴
下処理した。その後ガラス室内で育成し、薬剤処理後2
1日ロー除草効果および水稲におよぼす薬害を調査した
。その結果は第4表に示した。評価は6段階とし、除草
効力の評価は下記のように0〜5の数字で表わした。ま
た移植イネの薬害に関しては観奈結果を−(正常)〜+
+(中吉)の4段階で表示した。The following margins are Table 3-1 Table 3-3 Table 3-4 Example 2 An EeL pedestal pot with an area equivalent to 1/8850 are was filled with water-mixed paddy soil, and the surface layer of the soil was filled with grasshoppers, Japanese cypress, bulrushes, and scallops. Seeds of broad-leaved weeds such as Japanese apricot, Japanese azalea, and Kikashigusa were seeded with tI seeds, and tubers of Urikawa and Japanese cypress were embedded. Furthermore, three rice seedlings (variety name: Akinishiki) at the 2.5-leaf stage were planted at a depth of 2 cm. Thereafter, the rice was grown in a glass room at 20 to 25°C under warm water conditions of about 3 Cffl, and 7 days after transplanting the rice (when the wildflowers were at about 0.8 leaf stage) and 14 days later (when the wild grass was at about 2 leaf stage). ,
A wettable powder prepared according to Formulation Example 1 was diluted with water and a predetermined amount was dropped. After that, they were grown in a glass room and treated with chemicals.
The weeding effect of one-day low and the chemical damage caused to paddy rice were investigated. The results are shown in Table 4. The evaluation was on a 6-level scale, and the herbicidal efficacy was expressed as a number from 0 to 5 as shown below. Regarding chemical damage to transplanted rice, the results are - (normal) to +
Displayed in 4 levels: + (Nakayoshi).
除草効果
0 ・・・・・・ 抑草率 O〜 9%1 ・・・・
・・ 抑草率 10〜29%2 ・・・・・・ 抑草率
30〜49%3 ・・・・・・ 抑草率 50〜69
%4 ・・・・・・ 抑草率 70〜89%5 ・・・
・・・ 抑草率 90〜100%移植イネ薬害
−・・・・・・正常
± ・・・・・・ 僅小書
+・・・・・・小書
十+・・・・・・中害Weeding effect 0... Weed suppression rate 0 ~ 9%1...
...Weed control rate 10-29%2 ...Weed control rate 30-49%3 ...Weed control rate 50-69
%4 ・・・・・・ Weed suppression rate 70-89%5 ・・・
... Weed suppression rate 90-100% Transplanted rice chemical damage - ... Normal ± ... ... Slightly small + ... ... Small 10 + ... Medium damage
第1図及び第2図は実施例3で、第3図及び第N2Jは
実施例4で得られたα−フェノキシフェニル酢酸エステ
ルの赤外吸収スペクトル及び1■]−核磁気共鳴スペク
トルを夫々示す。Figures 1 and 2 show Example 3, and Figures 3 and N2J show the infrared absorption spectrum and 1■]-nuclear magnetic resonance spectrum of α-phenoxyphenylacetate obtained in Example 4, respectively. .
Claims (1)
ル基又はアルコキシ基を示し、X_3は水素原子、ハロ
ゲン原子、アルキル基又はアルコキシ基を示し、Rは非
置換もしくは置換のアルキル基、非置換もしくは置換の
アルケニル基、非置換もしくは置換のアルキニル基、又
は非置換もしくは置換のアリール基を示し、Yは酸素原
子又はイオウ原子を示す。) で表わされるα−フェノキシフェニル酢酸エステルと一
般式 ▲数式、化学式、表等があります▼ 〔但し、R_1及びR_2はアルキル基を示し、R_3
は水素原子又はアルキル基を示し、R_4はアルコキシ
基、アルコキシアルキル基、アルコキシカルボニル基又
は▲数式、化学式、表等があります▼(ここでR_5は
アルコキシ基、アルキルチオ基又はハロゲン原子を示す
。)で表わされる基を示す。〕 で示されるクロルアセトアミド誘導体とを有効成分とす
ることを特徴とする除草剤組成物。[Claims] General formula▲ Numerical formula, chemical formula, table, etc.▼ (However, X_1 represents a halogen atom, X_2 represents an alkyl group or an alkoxy group, and group, R represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, or an unsubstituted or substituted aryl group, and Y represents an oxygen atom or a sulfur atom. ) α-phenoxyphenylacetic acid ester represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R_1 and R_2 represent an alkyl group, and R_3
represents a hydrogen atom or an alkyl group, and R_4 is an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, or a numerical formula, a chemical formula, a table, etc. (here, R_5 represents an alkoxy group, an alkylthio group, or a halogen atom). Indicates the group represented. ] A herbicidal composition comprising a chloracetamide derivative represented by the following as an active ingredient.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27966086A JPS63135302A (en) | 1986-11-26 | 1986-11-26 | Herbicide composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27966086A JPS63135302A (en) | 1986-11-26 | 1986-11-26 | Herbicide composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63135302A true JPS63135302A (en) | 1988-06-07 |
Family
ID=17614082
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP27966086A Pending JPS63135302A (en) | 1986-11-26 | 1986-11-26 | Herbicide composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63135302A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6048893A (en) * | 1995-01-27 | 2000-04-11 | Rhone-Poulenc Rorer Limited | Substituted phenyl compounds with a substituent having A 1,3-benzodioxole ring |
-
1986
- 1986-11-26 JP JP27966086A patent/JPS63135302A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6124343A (en) * | 1919-01-27 | 2000-09-26 | Rhone-Poulenc Rorer Limited | Substituted phenyl compounds with a substituent having a thienyl ring |
US6048893A (en) * | 1995-01-27 | 2000-04-11 | Rhone-Poulenc Rorer Limited | Substituted phenyl compounds with a substituent having A 1,3-benzodioxole ring |
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