JPS63130505A - Herbicidal composition - Google Patents
Herbicidal compositionInfo
- Publication number
- JPS63130505A JPS63130505A JP27414286A JP27414286A JPS63130505A JP S63130505 A JPS63130505 A JP S63130505A JP 27414286 A JP27414286 A JP 27414286A JP 27414286 A JP27414286 A JP 27414286A JP S63130505 A JPS63130505 A JP S63130505A
- Authority
- JP
- Japan
- Prior art keywords
- group
- substituted
- alkyl
- compound
- 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 abstract description 55
- 239000000203 mixture Substances 0.000 title abstract description 47
- -1 alpha- phenoxyphenylacetic acid ester Chemical class 0.000 claims abstract description 80
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 31
- 125000005843 halogen group Chemical group 0.000 claims abstract description 21
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000004480 active ingredient Substances 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- 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
- 150000001875 compounds Chemical class 0.000 abstract description 45
- 241000196324 Embryophyta Species 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 10
- 125000003342 alkenyl group Chemical group 0.000 abstract description 6
- 125000000304 alkynyl group Chemical group 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 abstract description 6
- 238000001228 spectrum Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 238000009333 weeding Methods 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract 2
- 150000003931 anilides Chemical class 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 230000001473 noxious effect Effects 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 36
- 239000004009 herbicide Substances 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 240000007594 Oryza sativa Species 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 235000007164 Oryza sativa Nutrition 0.000 description 17
- 235000009566 rice Nutrition 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000009472 formulation Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 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 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000008187 granular material Substances 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 150000002148 esters Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 8
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 7
- 125000001434 methanylylidene group Chemical group [H]C#[*] 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
- 230000001629 suppression Effects 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
- 241000218691 Cupressaceae Species 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 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
- 239000002994 raw material Substances 0.000 description 6
- 239000004094 surface-active agent 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 238000011282 treatment Methods 0.000 description 5
- 239000004563 wettable powder Substances 0.000 description 5
- 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
- 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
- 238000005259 measurement Methods 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
- 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
- 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
- 244000025254 Cannabis sativa Species 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 241000234646 Cyperaceae Species 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 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
- 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
- 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
- 238000012546 transfer Methods 0.000 description 3
- 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
- RHPUJHQBPORFGV-UHFFFAOYSA-N 4-chloro-2-methylphenol Chemical compound CC1=CC(Cl)=CC=C1O RHPUJHQBPORFGV-UHFFFAOYSA-N 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
- 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
- 241000234653 Cyperus Species 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 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
- 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
- 230000035784 germination Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 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
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 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
- 238000002156 mixing Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229910052573 porcelain Inorganic materials 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
- 238000011160 research 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CUOSYYRDANYHTL-UHFFFAOYSA-N 1,4-dioctoxy-1,4-dioxobutane-2-sulfonic acid;sodium Chemical compound [Na].CCCCCCCCOC(=O)CC(S(O)(=O)=O)C(=O)OCCCCCCCC CUOSYYRDANYHTL-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- RTIPTGMVQIIMKL-UHFFFAOYSA-N 1-bromo-4-chloro-2-methylbenzene Chemical compound CC1=CC(Cl)=CC=C1Br RTIPTGMVQIIMKL-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- XXXFZKQPYACQLD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl acetate Chemical compound CC(=O)OCCOCCO XXXFZKQPYACQLD-UHFFFAOYSA-N 0.000 description 1
- RMFCMEVNMFHDSL-UHFFFAOYSA-N 2-(3,4-dichlorophenyl)ethanimidamide Chemical compound NC(=N)CC1=CC=C(Cl)C(Cl)=C1 RMFCMEVNMFHDSL-UHFFFAOYSA-N 0.000 description 1
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- VURUNMWLBDYAMB-UHFFFAOYSA-N 2-butylnaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(CCCC)=CC=C21 VURUNMWLBDYAMB-UHFFFAOYSA-N 0.000 description 1
- FGEAOSXMQZWHIQ-UHFFFAOYSA-N 2-chloro-2-phenylacetyl chloride Chemical compound ClC(=O)C(Cl)C1=CC=CC=C1 FGEAOSXMQZWHIQ-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000001205 4-bromo-2-butynyl group Chemical group [H]C([H])(Br)C#CC([H])([H])* 0.000 description 1
- 125000004176 4-fluorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1F)C([H])([H])* 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000254032 Acrididae Species 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 240000000972 Agathis dammara Species 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 235000003840 Amygdalus nana Nutrition 0.000 description 1
- 244000296825 Amygdalus nana Species 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241001585533 Callitris endlicheri Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- OENWGFOIYZVJKJ-UHFFFAOYSA-N ClC=1C=C(C(=CC1)O)C.[Na] Chemical compound ClC=1C=C(C(=CC1)O)C.[Na] OENWGFOIYZVJKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004859 Copal Substances 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920002871 Dammar gum Polymers 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000782205 Guibourtia conjugata Species 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ITATYELQCJRCCK-UHFFFAOYSA-N Mandelic Acid, Methyl Ester Chemical compound COC(=O)C(O)C1=CC=CC=C1 ITATYELQCJRCCK-UHFFFAOYSA-N 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 241001076438 Oxya japonica Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000011432 Prunus Nutrition 0.000 description 1
- 244000184734 Pyrus japonica Species 0.000 description 1
- 241000208422 Rhododendron Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 240000004429 Tephrosia purpurea Species 0.000 description 1
- 235000017517 Tephrosia purpurea Nutrition 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 235000005324 Typha latifolia Nutrition 0.000 description 1
- 240000000260 Typha latifolia Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000011276 addition treatment Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009739 binding Methods 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- JTXUVYOABGUBMX-UHFFFAOYSA-N didodecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCC JTXUVYOABGUBMX-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- DWHOIYXAMUMQTI-UHFFFAOYSA-L disodium;2-[(1-sulfonatonaphthalen-2-yl)methyl]naphthalene-1-sulfonate Chemical compound [Na+].[Na+].C1=CC2=CC=CC=C2C(S(=O)(=O)[O-])=C1CC1=CC=C(C=CC=C2)C2=C1S([O-])(=O)=O DWHOIYXAMUMQTI-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical group [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000021374 legumes Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- FZERHIULMFGESH-UHFFFAOYSA-N methylenecarboxanilide Natural products CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 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
- 239000012053 oil suspension Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 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
- 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
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning 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
- 230000002265 prevention Effects 0.000 description 1
- 235000014774 prunus Nutrition 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
- 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
- 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
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 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
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar 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
- 238000005406 washing Methods 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置換酢
酸アニリド系化合物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 [Field of Industrial Application] The present invention relates to a herbicidal composition characterized by containing α-phenoxyphenylacetic acid ester and a substituted acetic acid anilide compound 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、畑地を対象とする除草剤として
H3
(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(Proc
eedings of the East Afric
a WeedControl Conference)
第5回(1974年))1CI!
(***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。On the other hand, H3 (Proceedings of the East Africa Weed Control Conference (Proc.
eedings of the East Africa
a Weed Control Conference)
5th (1974)) 1CI! (West German Patent Specification No. 2458156) and other α-phenoxyphenylacetic acid derivatives 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
導体は前記した水田用除草剤としての条件を満足するも
のではなかった。However, these α-phenoxyphenylacetic acid derivatives did not satisfy the above-mentioned conditions as herbicides for rice fields.
本発明者らは一連のα−フェノキシフェニル酢酸?A
’4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
ルと他の除草作用を有する化合物との組み合せについて
研究を重ねた結果、該α−フェノキシフェニル酢酸エス
テルと特定の置換酢酸アニリド系化合物を有効成分とす
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 inventors discovered a series of α-phenoxyphenylacetic acids? A
As a result of the successful synthesis of ``4'' compounds and intensive research into the applicability of these compounds to rice fields, it was found that a certain α-phenoxyphenylacetic acid ester has a higher herbicidal effect on rice field weeds than the above-mentioned compounds, and has been shown to be effective against rice fields. It has been discovered that this is an extremely excellent herbicide for paddy fields that is safe and has no toxicity such as fish poison, and has already been proposed (Japanese Patent Application Laid-open No. 113192/1983). Further, as a result of repeated research on the combination of the above α-phenoxyphenylacetate and other compounds with herbicidal activity, a herbicide composition containing the α-phenoxyphenylacetate and a specific substituted acetic acid anilide compound as active ingredients was found. The fact that the substances exhibit a synergistic effect in terms of herbicidal effect that cannot be predicted from their individual properties;
In other words, it has been 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.
本発明は下記一般式(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、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下
記一般式(n)
(但し、Zは酸素原子又はイオウ原子、R,はアルキル
基、R2及びR3は同種又は異種の水素原子、アルキル
基又はハロゲン原子を示す。)で示される置換酢酸アニ
リド系化合物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 following general formula (1) (wherein, XI represents a halogen atom, X2 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 is an unsubstituted (Y represents an oxygen atom or a sulfur atom) α-phenoxyphenylacetic acid ester and the following general formula (n) (However, Z is an oxygen atom or a sulfur atom, R is an alkyl group, and R2 and R3 are the same or different hydrogen atoms, alkyl groups, or halogen atoms.) This is a herbicidal composition characterized by containing as an active ingredient a substituted acetate anilide compound represented by:
本発明の除草剤組成物の一方の成分は、下記の一般式(
1)で示されるα−フェノキシフェニル酢酸エステルで
ある。One component of the herbicide composition of the present invention has the following general formula (
This is α-phenoxyphenylacetic acid ester represented by 1).
(但し、X、はハロゲン原子を示し、X!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, X! represents an alkyl group or 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, represents a substituted 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.) In the above general formula (1), X is a halogen atom. Certain conditions are necessary in order to impart particularly high herbicidal activity to the α-phenoxyphenylacetic 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、Xl及びX3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 Xl and X3 include fluorine, chlorine, bromine, and iodine atoms, and chlorine atoms are particularly preferably used.
また上記一般式(1)中、X2及びX3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、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 (1), 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,
-octyl group, n-dodecyl group, cyclopropylmethyl group, cyclohexyl group, etc.
また前記一般式(I)中、X、及びX3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。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、t−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。In the general formula (I), the alkoxy groups represented by X and A shape or a ring shape is preferable. Specific examples of particularly suitable alkoxy groups include methoxy group, ethoxy group, n
-propoxy group, t-butoxy group, n-pentoxy group,
Examples include n-hexoxy group and cyclopropylmethoxy group.
また、前記一般式(1)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、X!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 (1), the unsubstituted alkyl group represented by R is not particularly limited, but X! The same alkyl groups as shown in the explanation of 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、アリール基、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X。For example, an alkoxy group, an aryl group, an alkoxy group, or a halogen atom. Among these substituents,
The alkoxy group or alkoxy group in the alkoxycarbonyl group is the above-mentioned X2 and X.
で述べたアルコキシ基と同様のものが好ましい。The same alkoxy groups as mentioned above are preferred.
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かで′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 it is possible to obtain a relatively stable compound. 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、 CH2COOCH3、CIl□C00Cztls
、CH2
C1hC00C411q、 CH−COOCzHs、
C3−COo−C−CHzl 1 1
CH3C2H,CI。Next, as the alkyl group substituted with alkoxycarbonyl group, CH2COOCH3, CIl□C00Cztls
, CH2 C1hC00C411q, CH-COOCzHs,
C3-COo-C-CHzl 1 1 CH3C2H, CI.
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。Examples of the alkyl group substituted with the group include 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
、2,2.2−1−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−クロルヘキシル基、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, 2,2.2-1-lichloroethyl group, 2,2'-dichloroisopropyl group, dichlorocyclopropyl group Examples include methyl group, 2-chlorohexyl group, 2-bromdodecyl group, and the like.
前記一般式(1)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(1)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、−
m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 (1), 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 (1), the alkynyl group represented by R can be used without particular restriction, but -
It is preferable that m 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CI)中、Rで示されるアリール基は
、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 CI), the aryl group represented by R can be used without any particular restriction. 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、アルキニル基及び了り−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
びシアノ尤等が挙げられる。Substituents for the alkenyl group, alkynyl group, and aryol group described above are not particularly limited, but typical examples include a halogen atom, an alkoxy group, a nitro group, and a cyano group.
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−プロペニル基、3−クロル−3−ブロム−2−
プロペニル!、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−ブテニル
基、3−ニトロ−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 group, 3-chloro-3-bromo-2-
Propenil! , 4-10-2-butenyl group, 3-methoxy-2-propenyl group, 4-methoxy-3-butenyl group, 3-nitro-2-pentenyl group, 2-cyano-4-
Examples include methyl-3-pentenyl group.
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!、4−エトキシ−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 and 5-iodo-3-butynyl! , 4-ethoxy-2-
Examples include butynyl group, 4-nitro-2-butynyl group, 2-cyano-3-hexynyl group, and the like.
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−ブロムフェニル基、m−トリ
フルオロメチルフェニル基、p−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 group, m-trifluoromethylphenyl group, p-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、Xlが塩素
原子であり、x2がメチル基又はメトキシ基であり、X
3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。In the compound represented by the general formula (1), Xl is a chlorine atom, x2 is a methyl group or a methoxy group, and
3 is a hydrogen atom or a chlorine atom, and R has 1 to 1 carbon atoms.
A compound having six substituted or unsubstituted alkyl, alkenyl, or alkynyl groups has a good herbicidal effect and is a compound suitably used as a herbicide. Among these compounds, compounds in which the chlorine atom of X is bonded to the 4-position and the methyl group or methoxy group of It is extremely safe for rice crops and has high selectivity compared to conventional hormonal 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C)l結合に基
づく吸収、1660〜1760cm−’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), an absorption based on the C) l bond is observed near 3150 to 2800 cm-', and a characteristic absorption based on the carbonyl bond of the ester group is observed near 1660 to 1760 cm-'. be able to.
(ロ)質量スペクトル(MS)を測定し、観察される各
ピーク(一般にはイオン質量数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CI)
で表わした場合、一般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) Measuring a mass spectrum (MS) and calculating the composition formula corresponding to each observed peak (generally a value expressed as m/e, which is the ion mass number m divided by the ion charge number e). Accordingly, 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 a sample subjected to measurement is expressed by the general formula CI), the molecular ion peak (hereinafter abbreviated as MΦ) generally has an intensity ratio according to the isotope abundance ratio depending on the number of halogen atoms contained in the molecule. Because it is observed,
The molecular weight of the compound subjected to measurement can be determined.
さらに前記一般式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 CI) 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CI)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 represented by the general formula CI)
- 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.
CHl
(f)
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(bl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。5.53ppm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
lによるものと帰属できる。A multiplet corresponding to 7 protons was observed in CHl (f), that is, 0.7 to 1.7 ppm, and this can be attributed to proton (a) in the butyl group. A singlet corresponding to 3 protons was observed at 2.27 ppm, and this can be attributed to the methyl group (bl) substituted at the 2-position of the phenyl group. A triplet corresponding to 2 protons was observed at 4.09 ppm. is recognized, and this is the methylene group (C) in the butyl group.
It can be attributed to 1 proton at 5.53 ppm
A singlet corresponding to individual segments was observed, which is a methine group (d
It can be attributed to l.
また6、5〜7.6 ppIll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)、 (f)によるものと帰属できる。Moreover, a multiplet corresponding to 8 protons was observed at 6.5 to 7.6 ppIll, and this can be attributed to protons (e) and (f) 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(I)中(7) X I+ X z、X :l、 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。In addition, α-phenoxyphenylacetic acid ester has the following formula (7) in the general formula (I):
Although its properties differ somewhat depending on the type of R and R, it is 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〔夏〕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 [Natsu] can be obtained by any method. The following three methods can be mentioned as typical manufacturing methods.
(i)α−フヱノキシフェニル酢酸ハロゲニドとアルコ
ール、フェノール、チオアルコール又ハチオフエノール
とを反応させる方法
(但し、式中X l+ X 2+ X 2+ 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.x、、y及びRは、前記一般
式([)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X I+ X !+ X 3+ Y及びR
は前記一般式(I)の場合と同じであり、Zはハロゲン
原子を示す。)
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、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。(i) A method of reacting α-phenoxyphenylacetic acid halide with alcohol, phenol, thioalcohol or thiophenol (however, in the formula, X l+ X 2+ X 2+ Y and R
is the same as in the above general formula (1), and Z represents a halogen atom. ) (ii) Phenol or alkali metal phenolate and α
- A method of reacting with halogenophenyl acetate (where x, , x2.x, , y and R are the same as in the above general formula ([), Z represents a halogen atom, and M represents Indicates a hydrogen atom or an alkali metal.) (iii
) A method of reacting an aryl halide with α-hydroxyphenylacetic acid ester (however, in the formula, X I+ X !+ X 3+ Y and R
is the same as in the above general formula (I), and Z represents a halogen atom. ) 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 two compounds to be charged may be appropriately determined as required, but it is common to use equimolar amounts or a slight 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ずる
。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9.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1−ン類;
アセトニトリルなどのニトリル類;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; diethyl ether, dioxane9. Ethers such as teratohydrofuran; keynes such as acetone and methyl ethyl ketone;
Nitriles such as acetonitrile; N,N such as N,N-dimethylformamide, N,N-diethylformamide, etc.
-Dialkylamides; examples include dimethyl sulfoxide.
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、フェノール、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。Although the order of addition of the raw materials in the reaction is not particularly limited, it is generally preferable to dissolve alcohol, phenol, or thioalcohol in a solvent, charge the reactor, and add α-phenoxyphenyl acetic acid halonide dissolved in the solvent while stirring. 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比・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〜lO日間、好ましくは1〜
40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 has a selectivity within a wide range, and it is sufficient to select the temperature generally from -20°C to 150°C, preferably from 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 10 days.
It is sufficient to choose from a range of 40 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(i
i)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 (i)
(abbreviated as i)], 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 )において固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 the solid compound 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(ii)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 (ii) 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(iii
)と略す〕に於て、固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 (iii)
), the molar ratio of the solid compound to be charged may be appropriately determined as necessary, but it is common to use equimolar amounts. In reaction (iii), an alkali metal,
Alternatively, the reaction is generally carried out in the presence of an alkali metal hydride or the like. The alkali metals include sodium,
Examples include 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
化第二銅等の金属銅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(i
ii )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, metallic copper such as cuprous iodide, cuprous bromide, cuprous chloride, cuprous oxide, cupric oxide, or copper compounds such as copper halides or copper oxides. etc. Moreover, the reaction (i
Conditions such as reaction temperature and reaction time in ii) are as follows:
This is the same as 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)、 (ii)、 (iii)においては、
反応液から反応溶媒及び過剰の反応試薬を留去した後、
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 reactions (i), (ii), (iii),
After distilling off the reaction solvent and excess reaction reagent 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(1)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
草効果を発揮するが、特にクマガヤッリ、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 (1) 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 not only during germination but also during the growing season, especially against Cyperaceae weeds such as Cyperaceae and Cyperaceae, 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
)、
(但し、Zは酸素原子又はイオウ原子、R,はアルキル
基、R2及びR3は同種又は異種の水素原子、アルキル
基又はハロゲン原子を示す。)で示される置換酢酸アニ
リド系化合物である。The other component of the herbicidal composition of the present invention has the following general formula (II
), (where Z is an oxygen atom or a sulfur atom, R is an alkyl group, and R2 and R3 are the same or different hydrogen atoms, alkyl groups, or halogen atoms).
上記一般式(If)中、R,、R2及びR3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。就中、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、1so−
プロピル基、n−ブチル基、1so−ブチル基、5ec
−ブチル基、t−ブチル基等が挙げられる。In the above general formula (If), the alkyl groups represented by R, R2 and R3 are not particularly limited in number of carbon atoms, and any alkyl group can be used. Among these, those having 1 to 4 carbon atoms are preferred. Suitable alkyl groups in the present invention include methyl group, ethyl group, n-propyl group, 1so-
Propyl group, n-butyl group, 1so-butyl group, 5ec
-butyl group, t-butyl group, etc.
また、上記一般式(If)中、R2及びR3で示される
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 (If), examples of the halogen atoms represented by R2 and R3 include fluorine, chlorine, bromine, and iodine atoms.
上記一般式(I[)で示される置換酢酸アニリド系化合
物のうちR,がメチル基であり、R2及びR3が水素原
子である化合物が除草活性が高いため好適に使用される
。Among the substituted acetate anilide compounds represented by the above general formula (I[), compounds in which R, is a methyl group, and R2 and R3 are hydrogen atoms are preferably used because they have high herbicidal activity.
上記一般式(It)で示される置換酢酸アニリド系化合
物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 substituted acetate anilide compound represented by the above general formula (It), any known production method can be employed without any limitation.
上記一般式〔■〕で示される置換酢酸アニリド系化合物
は、水田の強害雑草であるノビエに対して優れた除草効
果を有しているが、−年生広葉雑草、及びウリカワ、ミ
ズガヤツリ等の多年生雑草に除草効果が小さいという性
質を有する。The substituted acetate anilide compound represented by the above general formula [■] has an excellent herbicidal effect against Japanese field weed, which is a harmful weed in rice fields, but it is also effective against annual broad-leaved weeds and perennial weeds such as Prunus spp. It has the property of having a small herbicidal effect on weeds.
本発明の除草剤組成物は、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と、前記一般式〔
■〕で示される置換酢酸アニリド系化合物との使用割合
の広い範囲で優れた除草効果が得られる。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、置換酢酸アニリド系化合物が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、置換酢酸アニリド系化合物を1〜20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。The herbicidal composition of the present invention comprises an α-phenoxyphenylacetic acid ester represented by the general formula CI) and the general formula [
Excellent herbicidal effects can be obtained in a wide range of usage ratios with the substituted acetate anilide compound shown in (2). However, the usage ratio of both is α-phenoxyphenylacetic ester 1
Based on the weight part, the substituted acetate anilide compound is 0.01
It is generally in the range of ~50 parts by weight. More preferably, by using 1 to 20 parts by weight of the substituted acetate anilide compound 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107−/l
z当り、2g〜2000g、好ましくは10g〜500
g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 is generally applied to rice fields in an amount of 107-/l of α-phenoxyphenylacetic ester.
2g to 2000g, preferably 10g to 500g per z
It should be used so that the amount of active ingredient is 1.5 g.
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
、油懸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 suspensions, 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、アクパルジャイト群或いはジ
−クライト等で代表されるクレー頚;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, clay necks represented by kaolinite group, montmorillonite group, axpulgite group, or gicrite; 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
、テトラヒドロフラン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 tetrahydrofuran; acetone,
Ketones such as methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone; Esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate; methanol, n
-Alcohols such as 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ちの;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;パルミチン酸
、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もの;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
合付加させたちの;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
付加させたもの;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もの;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 palmitic 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、置換酢酸
アニリド系化合物6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溶かし、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 6 parts by weight of a substituted acetic acid anilide compound and 5 parts by weight of α-phenoxyphenylacetate 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、置換
酢酸アニリド系化合物10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, 10 parts by weight of a substituted acetic acid anilide compound, 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. There is a way to obtain an emulsion.
さらにまた、たとえば粒剤の具体的な一調製方法として
、置換酢酸アニリド系化合物6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, for example, as a specific method for preparing granules, 6 parts by weight of a substituted acetanilide compound, 5 parts by weight of α-phenoxyphenylacetic acid ester, a surfactant, and water are thoroughly kneaded, and then a carrier and an interface are kneaded. There is a method of obtaining granules by adding an active agent, stirring well, extruding to a predetermined particle size, and drying.
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置換酢酸ア
ニリド系化合物のいずれも、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
、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有する。さらに、ノビエ、
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。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 herbicidal composition of the present invention is effective against perennial weeds such as staghorn cyperus, black cypress, and weed, for which neither α-phenoxyphenylacetate nor substituted acetate anilide compounds 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. In addition, Nobie,
It has a synergistic effect against the harmful weeds of rice fields such as Japanese snail and Japanese cyperus, which cannot be expected from the properties of each component alone, and it can be used at the same or lower application rate than each component alone. It has a greater herbicidal effect 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
100ml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50m1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。Synthesis Example 1 5.7 g of α-chlorophenylacetic acid chloride was placed in a 100 ml eggplant-shaped flask, and 50 ml of methanol was gradually added dropwise while cooling with water. After stirring for an additional 2 days at room temperature, methanol was removed to obtain methyl α-chlorophenylacetate.
次に100m/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40m1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、
100mf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璽mHg)を得た。Next, 4.3 g of 2-methyl-4-chlorophenol, 1.2 g of sodium hydroxide, N
, add 40ml of N-dimethylformamide, and heat at room temperature for 2 hours.
After stirring for an hour, 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, add chloroform to the residue and transfer it to a separating funnel.
After washing with 100 mf of water, 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 56 g) of pale yellow liquid.
℃10.1 mHg) was obtained.
このものの赤外吸収スペクトルを測定した結果、300
0〜2900c+++−’にC−H結合に基づく吸収、
1730cm−’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%
、H5,’16%、CJ12.08%であって、組成式
〇+J+5C13(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 2900c+++-',
A strong absorption based on the carbonyl bond of the ester group was observed at 1730 cm-'. Its elemental analysis value is C66, 28%
, H5,'16%, CJ12.08%, which are calculated values for the composition formula 〇+J+5C13 (290,74), C 66.10%, H5, 20%, C112,19%
There was good agreement.
また質量スペクトルを測定したところ、m/e290.
292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。When the mass spectrum was measured, m/e290.
292 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。Furthermore, the results of 'H-NMR (δ: ppm' tetramethylsilane standard, deuterium chloroform solvent) were as follows.
(a)
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。(a) Shows a singlet for 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
)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
) was equivalent to the methine proton.
6.4〜7.6 ppm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 6.4 to 7.6 ppm, which corresponded 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
100mj!ナス型フラスコにマンデル酸メチル3.3
g、キシレン40m1、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及び銅粉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蒸留することによって淡黄色液体
1.4g(bp156℃10.l■■Hg)を得た。Synthesis example 2 100mj! 3.3 methyl mandelate in an eggplant-shaped flask
After adding 40 ml of xylene and 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 copper powder.
The mixture was heated to reflux for an hour. Next, after filtering the reaction solution, xylene was distilled off and the residue was distilled under reduced pressure to obtain 1.4 g of a pale yellow liquid (bp 156°C, 10.1 Hg).
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のものと一致した。収率は24
.2%であった。Infrared absorption spectrum, mass spectrum, 'H
-NMR was consistent with that of Compound No. 1. The yield is 24
.. It was 2%.
合成例3
100II+1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6.8gS N、N−ジメチルホルムアミ
ド40m1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80ffll
を加えて分液ロートに移し、100mj!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℃1
0.1■峠g)を得た。Synthesis Example 3 4.9 g of 2-methyl-4-chlorophenol sodium salt and 6.8 g of butyl α-chlorophenylacetate and 40 ml of S N,N-dimethylformamide were placed in a 100II+1 eggplant-shaped flask and heated on an oil bath at 120°C for 5 hours. The mixture was heated and stirred. Next, after removing N,N-dimethylformamide with an evaporator, 80ffll of chloroform was added to the residue.
Add and transfer to a separatory funnel, 100mj! Washed twice with 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 obtain 7.5 g of pale yellow liquid (bpl 60-162℃1
0.1μg) 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
I!10.51%であって組成式C,,11□、c t
i 03(332,83)に対する計算値であるC 6
B、 57%、86.36%、C110,65%に良
く一致した。Its elemental analysis values are C68.77%, H6.36%, C
I! 10.51% and composition formula C, 11□, c t
C 6 is the calculated value for i 03 (332, 83)
B, 57%, 86.36%, C110, 65% agreed well.
また質量スペクトルを測定したところ、m / C33
2,334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−NMR(δ;pprn
’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。In addition, when mass spectra were measured, m/C33
2,334 shows a peak corresponding to MΦ and each peak corresponding to m/e. Furthermore, 'H-NMR (δ; pprn
Fig. 2 shows the results of the measurements (based on tetramethylsilane, deuterated chloroform solvent).
その解析結果は次の通りであった。The analysis results were as follows.
(bl
C)13
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。(bl C) 13 0. A multiplet of 7 protons was shown at 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).
5.53ppmにプロトン1個分の一重線を示し、(d
lのメチンプロトンに相当した。6.5〜7.6 pp
m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 5.53 ppm, and (d
This corresponded to 1 methine proton. 6.5-7.6pp
The multiplet of 8 protons is shown in m, 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
100mj!ナス型フラスコに2−メチル−4−クロル
フェノール4.3g、?a粉砕した水酸化ナトリウム1
.2gS N、N−ジメチルホルムアミド501m1を
入れ、室温で1時間攪拌した後、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、100mf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℃/ 0.25 u+Hg)
を得た。Synthesis example 4 100mj! 4.3 g of 2-methyl-4-chlorophenol in an eggplant-shaped flask, ? a crushed sodium hydroxide 1
.. After adding 501 ml of 2 gS 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 mf of water, and the chloroform layer was dried over anhydrous sodium sulfate. Remove the chloroform and distill the residue under reduced pressure to obtain a pale yellow liquid6.
7g (bp160-162℃/0.25u+Hg)
I got it.
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、3060〜2930■−1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 material are as shown in Figure 3, and the C-H
Absorption based on the bond, and strong absorption based on the carbonyl bond of the ester group was shown at 1745 cm-'.
その元素分析値は、C68,69%、H5,34%であ
って、組成式c、、+1,7cxo、 (316,78
)に対する計算値であるC 68.25%、85.41
%に良く一致した。Its elemental analysis values are C68,69%, H5,34%, and the composition formula c, +1,7cxo, (316,78
) is the calculated value for C 68.25%, 85.41
% was in good agreement.
また質量スペクトルを測定したところ、m/e316.
318にMIB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;9pm”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.
A peak corresponding to MIB was shown at 318, a peak corresponding to m/e, and a peak corresponding to m/e 175. Furthermore, the results of 'H-NMR (δ; 9 pm'' tetramethylsilane standard, deuterated chloroform solvent) are shown in FIG. 4. The analysis results were as follows.
C)13
2、30 ppmにプロトン3個分の一重線を示しくa
)のメチルプロトンに相当した。4.5〜4.6 pp
m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fcl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
[d)のメチンプロトンに相当した。5.5〜6.1
ppmにプロトン1個分の多重線を示しくelのアリル
基内部のプロトンに相当した。6.5〜7.61)pf
fl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。C) Show the singlet of 3 protons at 13 2, 30 ppm a
) corresponded to the methyl proton. 4.5-4.6pp
A double line corresponding to two protons is shown in m, which corresponds to the methylene proton in b). A multiplet of two protons was observed at 4.9 to 5.3 ppm, which corresponded to the methylene proton of fcl. A singlet corresponding to one proton was shown at 5.56 ppm, which corresponded to the methine proton in [d). 5.5-6.1
A multiplet line corresponding to one proton in ppm is shown, and corresponds to the proton inside the allyl group of el. 6.5-7.61) pf
A multiplet line of 8 protons is shown in fl, which corresponds to the proton 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
100m!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!2.5g。Synthesis example 5 100m! α-(2-Methyl-4-chlorophenoxy)phenyl vinegar in an eggplant-shaped flask! 2.5g.
クロロホルム15 ml、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。After adding 15 ml of chloroform and 2.5 g of thionyl chloride and stirring at room temperature for 2 hours, the mixture was heated under reflux for 1 hour.
反応液を冷却後、揮撥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80nj!を加え、分液ロートに移
し100n+ 1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 (bp
l 90〜b
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
0cm−’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+qH+qC1Os(362
,81)に対する計算値であるC 62.90%、H5
,28%に良く一致した。After cooling the reaction solution, volatile components were removed, and 5 g of ethyl glycolate was gradually added dropwise to the remaining α-(2-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 the residue was mixed with 80 nj of chloroform. was added, transferred to a separatory funnel, and washed with 100n+1 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 (bp
l 90~b The result of measuring the infrared absorption spectrum of this product 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 observed at 0 cm-'. Its elemental analysis value is C62, 81%, H5
, 24% and the compositional formula C+qH+qC1Os (362
, 81), C 62.90%, H5
, 28%.
また質量スペクトルを測定したところ、m/e362に
MOに対応するピーク、m/e 231に応するピーク
を示した。さらに’H−NMR(δippm: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, when the mass spectrum was measured, a peak corresponding to MO at m/e 362 and a peak corresponding to m/e 231 were shown. Furthermore, the results of 'H-NMR (δippm: tetramethylsilane standard, deuterated chloroform solvent) were as follows.
(b)
H3
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
。(b) Shows the triplet of 3 protons at 1.15 ppm of H3, and (a
) corresponded to the methyl proton. 2.28ppm, Nifu.
ロトン3個分の一重線を示しくb)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C)のメチレンプロトンに相当した。4.54
pp+w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くe)のメチン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
示しくf)のベンゼン環のプロトンに相当した。A singlet line corresponding to three rotons is shown and corresponds to the methyl proton in b). A quartet of two protons was shown at 4.08 ppm, which corresponded to the methylene proton in C). 4.54
A double line corresponding to two protons is shown at pp+w, which corresponds to the methylene proton in d). 1 proton at 5.62 ppm
This corresponds to the methine proton 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54.0%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 54.0%.
合成例6
100II11ナス型フラスコに2−クロル−4,5−
シメチルフエノール3.12g、水酸化ナトリウム0.
86g、α−クロルフェニル酢酸エチル4g1N、N−
ジメチルホルムアミド50mj?を入れ120℃の油浴
上15時間加熱攪拌した。次に溶媒を減圧で除去した一
重、残留物にクロロホルム80n+j!を加え、分液ロ
ートに移し100mj!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4.28 g
(bpl 65〜b/ 0.3 mmtlg、 mp
58〜59℃)を得た。Synthesis Example 6 2-chloro-4,5- in a 100II11 eggplant flask
Dimethylphenol 3.12g, sodium hydroxide 0.
86g, α-chlorophenylacetate ethyl 4g1N, N-
Dimethylformamide 50mj? was heated and stirred on a 120°C oil bath for 15 hours. Next, the solvent was removed under reduced pressure, and the residue was treated with chloroform 80n+j! Add and transfer to a separating funnel to 100mj! Washed with 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 of pale yellow liquid.
(bpl 65~b/0.3 mmtlg, mp
58-59°C).
このものの赤外吸収スペクトルを測定した結果3050
〜2900cm−’にC−H結合に基づく吸収、174
5cm−’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%、H5
,88%であって組成式C11119C12(h(31
8,80)に対する計算値であるC67.82%、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Meに対応するピー
ク、m/e245,247に各ピークを示した。さらに
’H−NMR(δ;ppIIl: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。The result of measuring the infrared absorption spectrum of this substance is 3050
Absorption based on C-H bond at ~2900 cm-', 174
A strong absorption based on the carbonyl bond of the ester group was observed at 5 cm-'. Its elemental analysis value is C67, 41%, H5
, 88% and has the composition formula C11119C12 (h(31
8,80) C67.82%, H6
,01%. When the mass spectrum was measured, peaks corresponding to Me were observed at m/e 318 and 320, and peaks at m/e 245 and 247 were observed. Furthermore, the results of 'H-NMR (δ; ppIIl: tetramethylsilane standard, 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
)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
) corresponded to the 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).
5.55pp+w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。6.63ppm、およ
び7.05ppa+にそれぞれプロトン1個分の一重線
をを示しそれぞれ(e)、 (f)のベンゼン環のプロ
トンに相当した。7.2〜7.7 ppn+にプロトン
5個分の多重線を示し、(aのベンゼン環のプロトンに
相当した。5. Show the singlet of one proton at 55pp+wd
) was equivalent to the methine proton. Singlets corresponding to one proton were shown at 6.63 ppm and 7.05 ppa+, respectively, and corresponded to the protons of the benzene ring in (e) and (f), respectively. A multiplet of 5 protons is shown at 7.2 to 7.7 ppn+, which corresponds to the proton of the benzene ring in (a).
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、置換酢酸アニリド系化合物は下記の記号
(〔A〕〜〔E〕)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 substituted acetate anilide compounds are represented by the following symbols ([A] to [E]).
以下余白
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〔A36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56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。The following margin formulation example 1 (granules) 4 parts by weight of the compound synthesized in synthesis example 1 (compound number 1),
Compound [36 parts by weight of A, 1 part by weight of dioctyl succinate, 3 parts by weight of sodium ligninsulfonate, 30 parts by weight of bentonite, and 56 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)4重量部、
化合物〔A36重量部、ポリオキシエチレンノニルフェ
ニルエーテル2重FJ!L部、H粉りレー40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) 4 parts by weight of the compound synthesized in synthesis example 3 (compound number 2),
Compound [A36 parts by weight, polyoxyethylene nonylphenyl ether double FJ! Part L, 40 parts by weight of H powder,
and 48 parts by weight of zicrite were thoroughly ground and mixed to obtain a wettable powder.
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90重量部に化合物(C)を5重量部、化合物(
3)を5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 (C) was added to 90 parts by weight of this granular material, and compound (
Granules were obtained by impregnating 5 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、クログワイ、ミズガヤツリの塊茎を埋め込
んだ。その後、約3 cm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
■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2表に示した
。Example 1 A porcelain pot equivalent to 1/8850 are was filled with paddy soil that had been mixed with water, and Japanese wild grass was sown on the surface layer of the soil, and tubers of Japanese cypress, Japanese cypress, and Japanese cypress were embedded. After that, the condition was set to approximately 3 cm of water, and the
Grow in a glass room at ℃, 7 days later (when the wildflowers are at about 0.8 leaf stage) and 14 days later (when the wildflowers are at about 2 leaf stage)
Next, a wettable powder prepared according to Formulation Example 1 was diluted with water and subjected to a predetermined dropwise addition treatment. 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 2.
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. .
二値■脱所
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(期待される活
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,Co1b
y+除草剤の組合わせの相乗および拮抗反応の計算rW
eedJ vol、 15 。Binary ■ Exclusion When the herbicidal activity when two types of active compounds are combined is greater than the simple sum of the activities of each of the two compounds (expected activity), this is called synergism. . 2
The expected activity of a particular combination of species herbicides can be calculated as follows. (S, R, Co1b
Calculation of synergistic and antagonistic reactions of y + herbicide combination rW
eedJ 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/アールの量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。20-22, 1967): X: Inhibition rate when herbicide A is treated in an amount of ag/are Y: Inhibition rate when herbicide B is treated in an amount of bg/are E: Weed control If the expected inhibition rate when using herbicide A at ag/are and herbicide B at bg/are, that is, the actual inhibition rate, is greater than the E value calculated above, the combined activity shows synergism. I can do it.
第 3 表 の 1
第 3 表 の 2
第 3 表 の 3
実施例2
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、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
雑草種子を播種し、ウリカワ、クログワイ、ミズガヤツ
リの塊茎を埋め込んだ。Table 3 - 1 Table 3 - 2 Table 3 - 3 Example 2 A porcelain pot equivalent to 1/8850 are is filled with water-mixed paddy soil, and the surface layer of the soil is covered with grasshoppers, Japanese cypress, bulrushes, and Japanese grasshoppers. Seeds of broad-leaved weeds such as azalea and japonica were sown, and tubers of urikawa, cypress, and cypress were embedded.
さらに2.5葉期の稲苗(品種名:アキニシキ)を2c
mの深さに3本1株植とした。その後、約3 cmの湛
水条件とし、20〜25°Cのガラス室内で育成し、稲
移植7日後(ノヒエが約0.8葉期の時期)および14
日後(ノビエが約2葉期の時3tJl)に、配合例1に
準じて調製した水和剤を水に希釈し所定■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。In addition, 2 c of rice seedlings at the 2.5 leaf stage (variety name: Akinishiki)
Three plants were planted at a depth of m. Thereafter, the rice was submerged to a depth of about 3 cm and grown in a glass room at 20 to 25°C, and 7 days after transplanting (when Nohie was at about 0.8 leaf stage) and 14 days later.
After one day (3 tJl when the wildflowers were at about two leaf stage), the wettable powder prepared according to Formulation Example 1 was diluted with water and subjected to a predetermined dropwise treatment. Thereafter, the plants were grown in a glass room, and 21 days after chemical treatment, the weeding effect and chemical damage caused to paddy rice were investigated. The results are shown in Table 4.
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
察結果を−(正常)〜++(中古)の4段階で表示した
。The evaluation is in 6 stages, and the herbicidal efficacy is evaluated from 0 to 0 as shown below.
Represented by the number 5. Regarding the chemical damage to the transplanted rice, the observation results were displayed in four stages from - (normal) to ++ (used).
除草効果
0 ・・・・・・ 抑草率 0〜9%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
++・・・・・・中害Weeding effect 0... Weed suppression rate 0-9%1...
・Weed suppression rate 10-29%2 ・・・・・・ Weed suppression rate
30-49%3 ・・・・・・ Weed suppression rate 50-69%
4... Weed suppression rate 70-89%5...
・・Weed suppression rate 90-100% Transplanted rice chemical damage −・・・・ Normal ± ・・・・ Slightly small +・・・・Small ++・・・・・・Medium damage
第1図及び第2図は実施例3で、第3図及び第4図は実
施例4で得られたα−フェノギシフェニル6%Mエステ
ルの赤外吸収スペクトル及び’ II −核磁気共1(
5スペクトルを夫々示す。Figures 1 and 2 show Example 3, and Figures 3 and 4 show the infrared absorption spectrum and 'II-nuclear magnetic co-1 of α-phenogysiphenyl 6% M ester obtained in Example 4. (
5 spectra are shown 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、Zは酸素原子又はイオウ原子、R_1はアルキ
ル基、R_2及びR_3は同種又は異種の水素原子、ア
ルキル基又はハロゲン原子を示す。)で示される置換酢
酸アニリド系化合物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 alkoxy group, and X_3 represents a hydrogen atom, a halogen atom, an alkyl group, or an 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 ▲ Numerical formulas, chemical formulas, tables, etc. , an alkyl group or a halogen atom) as an active ingredient.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27414286A JPS63130505A (en) | 1986-11-19 | 1986-11-19 | Herbicidal composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27414286A JPS63130505A (en) | 1986-11-19 | 1986-11-19 | Herbicidal composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63130505A true JPS63130505A (en) | 1988-06-02 |
Family
ID=17537608
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP27414286A Pending JPS63130505A (en) | 1986-11-19 | 1986-11-19 | Herbicidal composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63130505A (en) |
-
1986
- 1986-11-19 JP JP27414286A patent/JPS63130505A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPS63130505A (en) | Herbicidal composition | |
JPS61145102A (en) | Herbicide composition | |
JPS63135302A (en) | Herbicide composition | |
JPS63132807A (en) | Herbicide composition | |
JPS61143308A (en) | Herbicide composition | |
JPS63132808A (en) | Herbicide composition | |
JPS63126807A (en) | Herbicide composition | |
JPS63122605A (en) | Herbicide composition | |
JPS61145105A (en) | Herbicide composition | |
JPS61140504A (en) | Herbicidal composition | |
JPS63166803A (en) | Herbicide composition | |
JPS61140502A (en) | Herbicidal composition | |
JPS61140506A (en) | Herbicidal composition | |
JPS63159301A (en) | Herbicide composition | |
JPH0615445B2 (en) | Herbicide composition | |
JPS58180403A (en) | Herbicide composition | |
JPS61271251A (en) | Alpha-phenoxyphenylacetic ester | |
JPS60218302A (en) | Herbicide composition | |
JPS61130202A (en) | Herbicidal composition | |
JPS63174904A (en) | Herbicide composition | |
JPS61122207A (en) | Herbicidal composition | |
JPH045282A (en) | New 2-hydrazinobenzothiazole derivative and herbicide comprising the same derivative as active ingredient | |
JPS61143306A (en) | Herbicide composition | |
JPS61148105A (en) | Herbicidal composition | |
JPH052642B2 (en) |