JPS6261026B2 - - Google Patents
Info
- Publication number
- JPS6261026B2 JPS6261026B2 JP4957580A JP4957580A JPS6261026B2 JP S6261026 B2 JPS6261026 B2 JP S6261026B2 JP 4957580 A JP4957580 A JP 4957580A JP 4957580 A JP4957580 A JP 4957580A JP S6261026 B2 JPS6261026 B2 JP S6261026B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- general formula
- group
- double bond
- derivative represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000003672 ureas Chemical class 0.000 claims description 14
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 claims description 11
- 230000002363 herbicidal effect Effects 0.000 claims description 11
- 239000004009 herbicide Substances 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 230000001035 methylating effect Effects 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000001448 anilines Chemical class 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical class O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 claims description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 claims 7
- 125000000217 alkyl group Chemical group 0.000 claims 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 6
- 150000001875 compounds Chemical class 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- -1 methanol and ethanol Chemical compound 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 10
- 239000012046 mixed solvent Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 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
- 235000019441 ethanol Nutrition 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000004927 clay Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 240000007594 Oryza sativa Species 0.000 description 6
- 239000000370 acceptor Substances 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 231100000674 Phytotoxicity Toxicity 0.000 description 3
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 241000209140 Triticum Species 0.000 description 3
- 235000021307 Triticum Nutrition 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000004563 wettable powder Substances 0.000 description 3
- DUDKKPVINWLFBI-ONEGZZNKSA-N (e)-1-chlorobut-1-ene Chemical compound CC\C=C\Cl DUDKKPVINWLFBI-ONEGZZNKSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 244000088415 Raphanus sativus Species 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 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
- 239000000969 carrier Substances 0.000 description 2
- 238000001103 continuous-wave nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000000887 hydrating effect Effects 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012022 methylating agents Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OBGFMRSXJROQDT-UHFFFAOYSA-N 1-methoxy-1-methylurea Chemical compound CON(C)C(N)=O OBGFMRSXJROQDT-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
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- QXSZJDPBWOLFFX-UHFFFAOYSA-N 3-(3-hydroxyphenyl)-1-methoxy-1-methylurea Chemical compound CON(C)C(=O)NC1=CC=CC(O)=C1 QXSZJDPBWOLFFX-UHFFFAOYSA-N 0.000 description 1
- FYUNLALTDJKUHL-UHFFFAOYSA-N 3-(4-hydroxyphenyl)-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=C(O)C=C1 FYUNLALTDJKUHL-UHFFFAOYSA-N 0.000 description 1
- KEAVUXZTSHFSMT-SWGQDTFXSA-N 4-[(e)-4-(4-chlorophenoxy)but-1-enoxy]aniline Chemical compound C1=CC(N)=CC=C1O\C=C\CCOC1=CC=C(Cl)C=C1 KEAVUXZTSHFSMT-SWGQDTFXSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- YIIMEMSDCNDGTB-UHFFFAOYSA-N Dimethylcarbamoyl chloride Chemical compound CN(C)C(Cl)=O YIIMEMSDCNDGTB-UHFFFAOYSA-N 0.000 description 1
- 239000005510 Diuron Substances 0.000 description 1
- 244000058871 Echinochloa crus-galli Species 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
- 241000282412 Homo Species 0.000 description 1
- VSNHCAURESNICA-UHFFFAOYSA-N Hydroxyurea Chemical class NC(=O)NO VSNHCAURESNICA-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000005733 Raphanus sativus var niger Nutrition 0.000 description 1
- 240000001970 Raphanus sativus var. sativus Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 240000000851 Vaccinium corymbosum Species 0.000 description 1
- 235000003095 Vaccinium corymbosum Nutrition 0.000 description 1
- 235000017537 Vaccinium myrtillus Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000021014 blueberries Nutrition 0.000 description 1
- 150000001714 carbamic acid halides Chemical class 0.000 description 1
- 239000004202 carbamide Substances 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
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- JOHLTMWXHJLNDE-UHFFFAOYSA-N methoxyurea Chemical compound CONC(N)=O JOHLTMWXHJLNDE-UHFFFAOYSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- BMLIZLVNXIYGCK-UHFFFAOYSA-N monuron Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C=C1 BMLIZLVNXIYGCK-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- MGLWZSOBALDPEK-UHFFFAOYSA-N simetryn Chemical compound CCNC1=NC(NCC)=NC(SC)=N1 MGLWZSOBALDPEK-UHFFFAOYSA-N 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、一般式〔〕
(式中Xはハロゲン原子、アルキル基またはト
リフルオロメチル基を示し、nは0から3の整数
を示し、nが2または3の場合はXは同じでも相
異つてもよい。Rはメチル基またはメトキシ基を
示す。二重結合はトランス体を示す。)で表わさ
れる尿素誘導体、その製造法およびその化合物か
らなる選択性除草剤に関するものである。
本発明者等は作物類に対する安全性が高く、雑
草類に対する除草活性が高い、いわゆる高度な選
択性を有する除草剤を開発すべく鋭意研究した結
果、一般式〔〕で表わされる化合物が作物類と
雑草類の間に高度な選択性を示し、その上、人
畜、魚介類に対しては毒性の非常に低い等優れた
特色のある除草剤を見出し、本発明を完成した。
本発明化合物の構成の一部分である尿素系化合
物は除草剤として広く知られているが、尿素系誘
導体はその作用特性から作物類と雑草類の間に選
択性をもたせにくいことも広く知られている。
既に市販されている尿素系化合物としては例え
ば、N′−4−クロロフエニール−N,N−ジメ
チル尿素(一般名:モニユロン)、N′−3,4−
ジクロロフエニール−N,N−ジメチル尿素(一
般名:ジウロン)、N′−3,4−ジクロロフエニ
ール−N−メトキシ−N−メチル尿素(一般名:
リニユロン)等が知られている。しかし、これら
の除草剤は雑草類に対する効力が強い反面、作物
類に対する薬害もまぬがれえないため、実際の使
用に際しては限られた場面で特定の作物に対する
使用に限定せざるを得ないのが実状である。
また、トリアジン系化合物も除草剤として広く
知られているが、前記したような尿素系除草剤と
同様に、その作用特性から選択性が低いこともま
た広く知られている。例えば、2,4−ビス(エ
チルアミノ)−6−メチルチオ−1,3,5−ト
リアジン(一般名:シメトリン)はトリアジン系
除草剤の中では根からの吸収作用がゆるやかであ
るため、特に広葉雑草を対象に比較的広く使用さ
れている。しかし実際の使用に際しては相当な制
限を受け、十分な注意を必要とする。特に水田で
の使用に際しては、湛水条件と重つて高温時に薬
害を発生するので暖地での使用はかなり制約をう
ける。
一般式〔〕で表わされる本発明化合物は、試
験例において明らかな如く、処理法の如何を問わ
ず、栽培作物類に対しては殆んど薬害を示さず、
しかも雑草類に対しては極めて効力の強い除草活
性を示し、顕著な選択性除草作用を有する。
本発明の化合物である一般式〔〕で表わされ
る化合物は、すべて新規化合物であり以下に示す
方法で製造することができる。
1 一般式〔〕
(式中Xおよびnは前記と同一の意味を有し、
Yはハロゲン原子を示す。二重結合はトランス体
を示す。)で表わされるブテニールハライド誘導
体と一般式〔〕
(式中Rは前記と同一の意味を有する。)で表
わされる尿素誘導体を反応させることにより得ら
れる。反応は適当な溶媒中、適当な酸受容体を用
いることにより高収率で一般式〔〕で表わされ
る化合物が得られる。
こゝで言う溶媒とは、例えば炭化水素系のベン
ゼン、トルエン等、エーテル系のジエチルエーテ
ル、テトラヒドロフラン、ジオキサン等、アルコ
ール系のメタノール、エタノール等、クロロホル
ム、醋酸エチルエステル、ジメチルホルムアミド
等の有機溶媒およびこれらの混合溶媒または必要
に応じ水あるいは水との混合溶媒も使用すること
ができる。
酸受容体としては、例えばピリジン、トリエチ
ルアミン等の有機化合物、カ性ソーダ、カ性カ
リ、炭酸ソーダ等の無機化合物が用いられる。
反応温度は一般に室温で進行するが、条件によ
つては適宜冷却下または加温下で行われる。反応
時間は一般的に1〜8時間で完結する。反応終了
後は常法で生成物を分離・精製すると目的物が得
られる。
2 一般式〔〕
(式中Xおよびnは前記と同じ意味を示す。)
で表わされるフエノール誘導体と一般式〔〕
(式中YおよびRは前記と同じ意味を有する。
二重結合はトランス体を示す。)で表わされる尿
素誘導体を反応させることにより高収率で一般式
〔〕で表わされる化合物を得る。反応は適当な
溶媒または酸受容体を用いることにより行われ
る。
本反応を行う場合には、溶媒として例えば炭化
水素系のベンゼン、トルエン等、エーテル系のジ
エチルエーテル、エーテル、テトラヒドロフラ
ン、ジオキサン等、ハロゲン化炭化水素系のクロ
ロホルム等、アルコール系のメタノール、エタノ
ール等、エステル系の醋酸エチルエステル等およ
びジメチルホルムアミド等の有機溶媒またはこれ
らの混合溶媒、必要あれば水または水との混合溶
媒も使用できる。
酸受容体としては例えば、ピリジン、トリメチ
ルアミン等の有機化合物、カ性ソーダ、カ性カ
リ、炭酸ソーダ等の無機化合物が用いられる。
反応温度は室温で進行するが、場合によつては
冷却下あるいは加温下において行わせることによ
り、円滑に進行させることができる。反応時間は
適当な条件を選べば1〜8時間で完結する。反応
終了後、常法により分離・精製すると目的物が得
られる。
3 一般式〔〕
(式中Xおよびnは前記と同じ意味を有する。
二重結合はトランス体を示す。)で表わされるア
ニリン誘導体と一般式〔〕
(式中YおよびRは前記と同じ意味を示す。)
で表わされるカルバミン酸ハライド誘導体を反応
させることにより高収率で一般式〔〕で表わさ
れる化合物を得る。反応は適当な溶媒あるいは酸
受容体を用いることにより行われる。
本反応を行う場合には、溶媒とし例えば炭化水
素系のベンゼン、トルエン、キシレン等、ハロゲ
ン化炭化水素系のジクロロメタン、クロロホルム
等、エーテル系のジエチルエーテル、テトラヒド
ロフラン等およびジメチルホルムアミド等の溶媒
中あるいはこれらの混合溶媒中で行うと円滑に進
行する。
酸受容体としては例えばピリジン、トリエチル
アミン等の有機化合物、カ性ソーダ、カ性カリ、
炭酸ソーダ等の無機化合物を用いることにより高
収率で目的物を得る。
反応は室温において円滑に進行するが、場合に
よつては加温下で行うことにより反応を進行させ
ることができる。反応時間は条件の選定にもよる
が1〜8時間で完結する。反応終了後、常法によ
り分離・精製すると目的物が得られる。
4 一般式〔〕
(式中Xおよびnは前記と同じ意味を有する。
二重結合はトランス体を示す。)で表わされるフ
エニールイソシアネート誘導体と一般式〔〕
(式中Rは前記と同じ意味を有する。)で表わ
されるアミン誘導体を反応させることにより高収
率で一般式〔〕で表わされる化合物を得る。
本反応を行う場合には、溶媒として例えば炭化
水素系のベンゼン、トルエン等、ハロゲン化炭化
水素系のジクロロメタン、クロロホルム等、エー
テル系のジエチルエーテル、テトラヒドロフラ
ン、ジオキサン等およびジメチルホルムアミド等
の溶媒中あるいはこれらの混合溶媒中で行うと円
滑に進行する。
反応は室温において円滑に進行するが、場合に
よつては冷却下あるいは加温下で反応させること
により良い結果を得る。反応時間は条件の選定に
もよるが、1〜8時間である。反応終了後は常法
により分離・精製すると目的物が得られる。
5 一般式〔〕で表わされる化合物のうち、R
がメトキシ基である場合、一般式〔〕
(式中Xおよびnは前記と同じ意味を有する。
二重結合はトランス体を示す。)で表わされる尿
素誘導体をメチル化することにより高収率で一般
式〔〕で表わされる化合物を得る。
メチル化剤としては、例えばジメチル硫酸、沃
化メチル、ジアゾメタン等をあげることができ
る。
反応条件は例えば反応溶媒、反応補助剤、反応
温度、反応時間等各メチル化剤によつて異なる
が、広く知られている各メチル化剤によるメチル
化法の一般的方法で十分満足すべき結果を得る。
次に合成例を示し詳細に説明する。
合成例 1
水酸化カリウム0.78gとN′−4−ヒドロキシフ
エニール−N,N−ジメチル尿素1.8gを30mlの
エチルアルコールに溶かした溶液に4−(4−ク
ロロ−2−メチルフエニールオキシ)−2−トラ
ンス−ブテニールクロリド2.3gを加え、50〜60
℃で4時間撹拌下反応させたのち、水で稀釈し醋
酸エチルエステルで抽出した。減圧下溶媒を溜去
し、残渣をエタノールより再結晶すると、N′−
4−〔4−(4−クロロ−2−メチルフエニールオ
キシ)−2−トランス−ブテニールオキシ−フエ
ニール−N,N−ジメチル尿素3.1gを得た。融
点122〜123℃(化合物番号32)
元素分析値:C20H23ClN2O3(分子量374.87)
C H N
計算値(%) 64.08 6.18 7.47
実測値(%) 64.29 6.23 7.49
合成例 2
水酸化カリウム0.78gとN′−3−ヒドロキシフ
エニール−N−メチル−N−メトキシ尿素2.0g
を40mlのエチルアルコールに溶解し、この溶液に
4−(2,6−ジメチルフエニールオキシ)−2−
トランス−ブテニールクロリド2.1gを加えたの
ち、60〜70℃で5時間加熱・撹拌しながら反応さ
せ、反応終了後水で稀釈し、醋酸エチルエステル
で抽出する。減圧下、溶媒を溜去する。かくして
得られた油状物質をシリカゲルのカラムクロマト
グラフイーにかけ、クロロホルムを用いて目的物
を分離する。得られた主フラクシヨンをとり、溶
媒を減圧で溜去すると、N′−3−〔4−(2,6
−ジメチルフエニールオキシ)−2−トランス−
ブテニールオキシ〕−フエニール−N−メチル−
N−メトキシ尿素を油状物として3.0g得た。(化
合物番号138)
元素分析値:C21H26N2O4(分子量370.45)
C H N
計算値(%) 68.09 7.07 7.56
実測値(%) 68.33 7.15 7.40
NMR吸収スペクトル(δ.CDCl3中)
2.24(6H,s),3.14(3H,s),3.71
(3H,s),4.30(2H,m),4.53(2H,
m),6.05(2H,m),6.48〜7.31(7H),
7.65(1H,bs).
合成例 3
水酸化ナトリウム0.6gと2,4−ジクロロフ
エノール1.4gをメチルアルコール50mlに溶かし
た溶液に、N′−3−(4−クロロ−2−トランス
−ブテニールオキシ)−フエニール−N−メチル
−N−メトキシ尿素2.9gを加え、50℃で4時間
加熱・撹拌下反応させ、反応終了後水で稀釈し醋
酸エチルエステルで抽出した。減圧下溶媒を溜去
し、得られた残渣を醋酸エチル−n−ヘキサンの
混合溶媒から再結晶すると、N′−3−〔4−
(2,4−ジクロロフエニールオキシ)−2−トラ
ンス−ブテニールオキシ〕−フエニール−N−メ
チル−N−メトキシ尿素3.2gを得た。融点91〜
92℃(化合物番号98)
元素分析値:C19H20Cl2N2O4(分子量411.28)
C H N
計算値(%) 55.49 4.90 6.81
実測値(%) 55.53 4.90 6.70
合成例 4
4−〔4−(4−クロロフエニールオキシ)−2
−トランス−ブテニールオキシ〕−アニリン2.7g
とトリエチルアミン1.2gをテトラヒドロフラン
30mlに溶かした溶液を氷冷し、撹拌しながらジメ
チル−カルバミン酸クロリド1.3gをゆつくり滴
下した。滴下終了後30分間撹拌した後室温で2時
間更に撹拌を続けた。次いでトリエチルアミン塩
酸塩を別し、減圧下溶媒を溜去した。得られた
残渣をエーテルで再結晶すると、N′−4−〔4−
(4−クロロフエニールオキシ)−2−トランス−
ブテニールオキシ〕−フエニール−N,N−ジメ
チル尿素3.0gを得た。融点144〜145℃(化合物
番号4)
元素分析値:C19H21ClN2O3(分子量360.84)
C H N
計算値(%) 63.24 5.88 7.76
実測値(%) 63.18 5.92 7.88
合成例 5
3−〔4−(4−クロロ−2−メチルフエニール
オキシ)−2−トランス−ブテニールオキシ〕−フ
エニールイソシアネート3.3gを30mlのテトラヒ
ドロフラン中に溶かし、この溶液を氷冷撹拌下、
1gのジメチルアミン50%水溶液に滴下する。滴
下終了後、30分間そのまゝ氷冷撹拌を続けた。そ
の後室温で更に2時間撹拌したのち、減圧下に溶
媒を溜去する。得られた残渣を醋酸エチルエステ
ル−n−ヘキサン混合溶媒より再結晶すると、
N′−3−〔4−(4−クロロ−2−メチルフエニ
ールオキシ)−2−トランス−ブテニール−オキ
シ〕−フエニール−N,N−ジメチル尿素2.9gを
得た。融点116〜118℃(化合物番号80)
元素分析値:C20H23ClN2O3(分子量374.87)
C H N
計算値(%) 64.08 6.18 7.47
実測値(%) 63.97 6.21 7.51
合成例 6
3−〔4−(2,4−ジメチルフエニールオキ
シ)−2−トランス−ブテニールオキシ〕−フエニ
ールイソシアネート3.1gを10mlの塩化メチレン
に溶かした溶液を0.8gのヒドロキシルアミン塩
酸塩と0.5g水酸化ナトリウムを溶解した水溶液
中に氷冷・撹拌下滴下する。滴下終了後、その
まゝ30分間撹拌したのち室温に戻しながら更に2
時間撹拌を続ける。反応終了後水で稀釈し、得ら
れた析出物を過乾燥する。このようにして得ら
れたヒドロキシル尿素誘導体をベンゼン−メタノ
ール(1:1)の混合溶媒50mlに溶解し、10N水
酸化ナトリウム水溶液1mlと硫酸ジメチル1.3g
を氷冷・撹拌下滴下する。滴下終了後30分間撹拌
したのち、室温に戻しながら更に2時間撹拌を続
ける。反応終了後水で稀釈したのちベンゼンで抽
出する。減圧下溶媒を溜去し、得られた残渣を醋
酸エチルエステル−n−ヘキサン混合溶媒から再
結晶すると、N′−3−〔4−(2,4−ジメチル
フエニールオキシ)−2−トランス−ブテニール
オキシ〕−フエニール−N−メチル−N−メトキ
シ尿素2.6gを得た。融点84.5〜85℃(化合物番
号104)
元素分析値:C21H26N2O4分子量370.45
C H N
計算値(%) 68.09 7.07 7.56
実測値(%) 68.33 7.15 7.40
次に、かくして得られた前記一般式〔〕で表
わされる本発明化合物の代表例を第1表に示す。
なお、本発明はこれらの例示化合物のみに限定さ
れるものではない。
第1表において、置換基Xの欄の2〜6は、前
記一般式〔〕で表わされる化合物のベンゼン環
上の置換位置を示し、結合位置欄は前記一般式
〔〕で表わされる化合物の
The present invention is based on the general formula [] (In the formula, The present invention relates to a urea derivative represented by (or a methoxy group; a double bond indicates a trans isomer), a method for producing the same, and a selective herbicide comprising the compound. The present inventors conducted intensive research to develop a so-called highly selective herbicide that is highly safe for crops and has high herbicidal activity against weeds. As a result, the compound represented by the general formula [] The present invention has been completed by discovering a herbicide with excellent characteristics, such as showing a high degree of selectivity between weeds and weeds, and having extremely low toxicity to humans, livestock, and fish and shellfish. The urea compounds that are part of the composition of the compounds of the present invention are widely known as herbicides, but it is also widely known that urea derivatives are difficult to select between crops and weeds due to their action characteristics. There is. Examples of urea-based compounds that are already commercially available include N'-4-chlorophenyl-N,N-dimethylurea (common name: Monyuron), N'-3,4-
Dichlorophenyl-N,N-dimethylurea (generic name: diuron), N'-3,4-dichlorophenyl-N-methoxy-N-methylurea (generic name:
Linyuron) etc. are known. However, while these herbicides are highly effective against weeds, they can also be harmful to crops, so in reality, their use must be limited to specific crops in limited situations. It is. Further, triazine compounds are also widely known as herbicides, but like the urea herbicides mentioned above, it is also widely known that they have low selectivity due to their action characteristics. For example, 2,4-bis(ethylamino)-6-methylthio-1,3,5-triazine (common name: simetrine) is a triazine herbicide that is absorbed slowly through the roots, so it is especially effective against broadleaf herbicides. It is relatively widely used to target weeds. However, in actual use, it is subject to considerable limitations and requires sufficient caution. Particularly when used in rice paddies, chemical damage occurs at high temperatures combined with flooding conditions, so use in warm regions is severely restricted. As is clear from the test examples, the compound of the present invention represented by the general formula [] shows almost no phytotoxicity to cultivated crops, regardless of the treatment method.
Furthermore, it exhibits extremely strong herbicidal activity against weeds and has remarkable selective herbicidal activity. The compounds of the present invention represented by the general formula [] are all new compounds and can be produced by the method shown below. 1 General formula [] (In the formula, X and n have the same meanings as above,
Y represents a halogen atom. A double bond indicates a trans isomer. ) and the general formula [] (In the formula, R has the same meaning as above.) It can be obtained by reacting a urea derivative represented by the following formula. The reaction can be carried out in a suitable solvent using a suitable acid acceptor to obtain a compound represented by the general formula [] in high yield. The solvents mentioned here include, for example, hydrocarbons such as benzene and toluene, ethers such as diethyl ether, tetrahydrofuran, and dioxane, alcohols such as methanol and ethanol, and organic solvents such as chloroform, acetic acid ethyl ester, and dimethylformamide. A mixed solvent of these or water or a mixed solvent with water can also be used if necessary. As the acid acceptor, for example, organic compounds such as pyridine and triethylamine, and inorganic compounds such as caustic soda, caustic potash, and soda carbonate are used. The reaction generally proceeds at room temperature, but depending on the conditions, it may be carried out under cooling or heating as appropriate. The reaction time is generally completed in 1 to 8 hours. After the reaction is completed, the desired product can be obtained by separating and purifying the product using conventional methods. 2 General formula [] (In the formula, X and n have the same meanings as above.)
Phenol derivatives represented by and general formula [] (In the formula, Y and R have the same meanings as above.
A double bond indicates a trans isomer. ) The compound represented by the general formula [] is obtained in high yield by reacting the urea derivative represented by the formula []. The reaction is carried out using a suitable solvent or acid acceptor. When carrying out this reaction, the solvent may be, for example, hydrocarbons such as benzene and toluene, ethers such as diethyl ether, ether, tetrahydrofuran, dioxane, etc., halogenated hydrocarbons such as chloroform, alcohols such as methanol, ethanol, etc. Organic solvents such as ester-based acetic acid ethyl ester, dimethylformamide, etc., or mixed solvents thereof, and if necessary, water or a mixed solvent with water can also be used. As the acid acceptor, for example, organic compounds such as pyridine and trimethylamine, and inorganic compounds such as caustic soda, caustic potash, and soda carbonate are used. Although the reaction proceeds at room temperature, it can proceed smoothly by carrying out the reaction under cooling or heating as the case may be. The reaction time can be completed in 1 to 8 hours if appropriate conditions are selected. After the reaction is completed, the target product is obtained by separating and purifying it by conventional methods. 3 General formula [] (In the formula, X and n have the same meanings as above.
A double bond indicates a trans isomer. ) Aniline derivatives represented by the general formula [] (In the formula, Y and R have the same meanings as above.)
The compound represented by the general formula [] is obtained in high yield by reacting the carbamic acid halide derivative represented by the formula []. The reaction is carried out using a suitable solvent or acid acceptor. When carrying out this reaction, the solvent may be, for example, hydrocarbons such as benzene, toluene, xylene, etc., halogenated hydrocarbons such as dichloromethane, chloroform, etc., ethers such as diethyl ether, tetrahydrofuran, dimethylformamide, etc., or these solvents. The process proceeds smoothly when carried out in a mixed solvent. Examples of acid acceptors include organic compounds such as pyridine and triethylamine, caustic soda, caustic potash,
By using inorganic compounds such as soda carbonate, the desired product can be obtained in high yield. The reaction proceeds smoothly at room temperature, but in some cases the reaction can be carried out under heating. Although the reaction time depends on the selection of conditions, the reaction is completed in 1 to 8 hours. After the reaction is completed, the target product is obtained by separating and purifying it by conventional methods. 4 General formula [] (In the formula, X and n have the same meanings as above.
A double bond indicates a trans isomer. ) Phenyl isocyanate derivatives represented by the general formula [] By reacting the amine derivative represented by (wherein R has the same meaning as above), the compound represented by the general formula [] is obtained in high yield. When carrying out this reaction, the solvent may be, for example, hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, ethers such as diethyl ether, tetrahydrofuran, dioxane, dimethylformamide, etc., or these solvents. The process proceeds smoothly when carried out in a mixed solvent. Although the reaction proceeds smoothly at room temperature, better results can be obtained by carrying out the reaction under cooling or heating in some cases. The reaction time is 1 to 8 hours, depending on the selection of conditions. After the reaction is completed, the desired product can be obtained by separating and purifying it by conventional methods. 5 Among the compounds represented by the general formula [], R
When is a methoxy group, the general formula [] (In the formula, X and n have the same meanings as above.
A double bond indicates a trans isomer. ) The compound represented by the general formula [] is obtained in high yield by methylating the urea derivative represented by the formula []. Examples of the methylating agent include dimethyl sulfate, methyl iodide, and diazomethane. Reaction conditions vary depending on each methylating agent, such as reaction solvent, reaction aid, reaction temperature, reaction time, etc., but satisfactory results can be obtained using general methylation methods using widely known methylating agents. get. Next, a synthesis example will be shown and explained in detail. Synthesis Example 1 Add 4-(4-chloro-2-methylphenyloxy) to a solution of 0.78 g of potassium hydroxide and 1.8 g of N'-4-hydroxyphenyl-N,N-dimethylurea dissolved in 30 ml of ethyl alcohol. -Add 2.3g of 2-trans-butenyl chloride and
After reacting at ℃ for 4 hours with stirring, the mixture was diluted with water and extracted with acetic acid ethyl ester. After distilling off the solvent under reduced pressure and recrystallizing the residue from ethanol, N′-
3.1 g of 4-[4-(4-chloro-2-methylphenyloxy)-2-trans-butenyloxy-phenyl-N,N-dimethylurea was obtained. Melting point 122-123℃ (Compound No. 32) Elemental analysis value: C 20 H 23 ClN 2 O 3 (molecular weight 374.87) C H N Calculated value (%) 64.08 6.18 7.47 Actual value (%) 64.29 6.23 7.49 Synthesis example 2 Hydroxylation Potassium 0.78g and N'-3-hydroxyphenyl-N-methyl-N-methoxyurea 2.0g
was dissolved in 40 ml of ethyl alcohol, and 4-(2,6-dimethylphenyloxy)-2-
After adding 2.1 g of trans-butenyl chloride, the reaction mixture was heated and stirred at 60 to 70°C for 5 hours, and after the reaction was completed, the mixture was diluted with water and extracted with acetic acid ethyl ester. The solvent is distilled off under reduced pressure. The oil thus obtained is subjected to silica gel column chromatography, and the target product is separated using chloroform. The main fraction obtained was taken and the solvent was distilled off under reduced pressure to give N′-3-[4-(2,6
-dimethylphenyloxy)-2-trans-
butenyloxy]-phenyl-N-methyl-
3.0 g of N-methoxyurea was obtained as an oil. (Compound No. 138) Elemental analysis value: C 21 H 26 N 2 O 4 (molecular weight 370.45) C H N Calculated value (%) 68.09 7.07 7.56 Actual value (%) 68.33 7.15 7.40 NMR absorption spectrum (δ. in CDCl 3 ) 2.24 (6H, s), 3.14 (3H, s), 3.71
(3H, s), 4.30 (2H, m), 4.53 (2H,
m), 6.05 (2H, m), 6.48-7.31 (7H),
7.65 (1H, bs). Synthesis Example 3 N′-3-(4-chloro-2-trans-butenyloxy)-phenyl-N- 2.9 g of methyl-N-methoxyurea was added, and the reaction mixture was heated and stirred at 50° C. for 4 hours. After the reaction was completed, the mixture was diluted with water and extracted with ethyl acetate. The solvent was distilled off under reduced pressure, and the resulting residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane to give N'-3-[4-
3.2 g of (2,4-dichlorophenyloxy)-2-trans-butenyloxy]-phenyl-N-methyl-N-methoxyurea was obtained. Melting point 91~
92℃ (Compound No. 98) Elemental analysis value: C 19 H 20 Cl 2 N 2 O 4 (molecular weight 411.28) C H N Calculated value (%) 55.49 4.90 6.81 Actual value (%) 55.53 4.90 6.70 Synthesis example 4 4-[ 4-(4-chlorophenyloxy)-2
-trans-butenyloxy]-aniline 2.7g
and 1.2 g of triethylamine in tetrahydrofuran.
The solution dissolved in 30 ml was cooled with ice, and 1.3 g of dimethyl-carbamic acid chloride was slowly added dropwise while stirring. After the dropwise addition was completed, the mixture was stirred for 30 minutes and then further stirred at room temperature for 2 hours. Then, the triethylamine hydrochloride was separated and the solvent was distilled off under reduced pressure. When the obtained residue is recrystallized with ether, N′-4-[4-
(4-chlorophenyloxy)-2-trans-
3.0 g of butenyloxy]-phenyl-N,N-dimethylurea was obtained. Melting point 144-145℃ (Compound No. 4) Elemental analysis value: C 19 H 21 ClN 2 O 3 (molecular weight 360.84) C H N Calculated value (%) 63.24 5.88 7.76 Actual value (%) 63.18 5.92 7.88 Synthesis example 5 3- 3.3 g of [4-(4-chloro-2-methylphenyloxy)-2-trans-butenyloxy]-phenyl isocyanate was dissolved in 30 ml of tetrahydrofuran, and the solution was stirred under ice cooling.
Add dropwise to 1 g of dimethylamine 50% aqueous solution. After the dropwise addition was completed, stirring under ice cooling was continued for 30 minutes. After that, the mixture was further stirred at room temperature for 2 hours, and then the solvent was distilled off under reduced pressure. When the obtained residue is recrystallized from acetic acid ethyl ester-n-hexane mixed solvent,
2.9 g of N'-3-[4-(4-chloro-2-methylphenyloxy)-2-trans-butenyl-oxy]-phenyl-N,N-dimethylurea was obtained. Melting point 116-118℃ (Compound No. 80) Elemental analysis value: C 20 H 23 ClN 2 O 3 (molecular weight 374.87) C H N Calculated value (%) 64.08 6.18 7.47 Actual value (%) 63.97 6.21 7.51 Synthesis example 6 3- A solution of 3.1 g of [4-(2,4-dimethylphenyloxy)-2-trans-butenyloxy]-phenyl isocyanate dissolved in 10 ml of methylene chloride was mixed with 0.8 g of hydroxylamine hydrochloride and 0.5 g of hydroxide. Add dropwise to an aqueous solution containing dissolved sodium while cooling with ice and stirring. After the addition was complete, stir for 30 minutes and then stir for 2 more minutes while returning to room temperature.
Continue stirring for an hour. After the reaction is completed, it is diluted with water and the resulting precipitate is overdried. The hydroxylurea derivative thus obtained was dissolved in 50 ml of a mixed solvent of benzene-methanol (1:1), mixed with 1 ml of a 10N aqueous sodium hydroxide solution and 1.3 g of dimethyl sulfate.
Add dropwise while cooling on ice and stirring. After stirring for 30 minutes after completion of the dropwise addition, stirring was continued for an additional 2 hours while returning to room temperature. After the reaction is completed, the mixture is diluted with water and extracted with benzene. The solvent was distilled off under reduced pressure, and the resulting residue was recrystallized from a mixed solvent of acetic acid ethyl ester-n-hexane to give N'-3-[4-(2,4-dimethylphenyloxy)-2-trans- 2.6 g of butenyloxy]-phenyl-N-methyl-N-methoxyurea was obtained. Melting point: 84.5-85°C (compound number 104) Elemental analysis value: C 21 H 26 N 2 O 4 molecular weight 370.45 C H N Calculated value (%) 68.09 7.07 7.56 Actual value (%) 68.33 7.15 7.40 Next, the thus obtained Representative examples of the compounds of the present invention represented by the above general formula [] are shown in Table 1.
Note that the present invention is not limited only to these exemplified compounds. In Table 1, 2 to 6 in the substituent X column indicate the substitution positions on the benzene ring of the compound represented by the above general formula [], and the bond position column shows the substitution positions of the compound represented by the above general formula
【式】
基の結合位置を示す。
また、本発明化合物中、通常の分離・精製法を
用いて油状物質として得られた化合物について
は、そのNMR吸収スペクトル値を第2表に示
す。
なお、下記第1表中のEtは−C2H5、Prは−
C3H7、Buは−C4H9、Amは−C5H11を示す。[Formula] Indicates the bonding position of the group. Furthermore, among the compounds of the present invention, the NMR absorption spectrum values of the compounds obtained as oily substances using conventional separation and purification methods are shown in Table 2. In addition, Et in Table 1 below is −C 2 H 5 and Pr is −
C3H7 , Bu represents -C4H9 , and Am represents -C5H11 .
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
本発明の実施に当つては、一般式〔〕で表わ
される化合物の一種または二種以上の混合物を10
アール当り50〜2000g、好ましくは100〜1000g
の割合で使用するのが適当であるが、実施場面の
状況により薬量を調節し得ることは言うまでもな
い。
実際に使用する場合は、本発明化合物を直接そ
のまゝで使用することも可能であるが、使用目的
に応じて前記一般式〔〕で表わされる化合物の
一種または二種以上を液状担体に溶解するかある
いはこれを分散させるか、または適当な固体担体
(例えば稀釈剤、増量剤等)と混合するかあるい
はこれを吸着させ、所望の場合は更に乳化剤、分
散剤、懸濁剤、展着剤、浸透剤、安定剤等を添加
して水和剤、乳剤、粒剤、粉剤、錠剤等の剤型に
して使用する。
こゝで言う液体担体(溶剤)としては例えば、
アルコール類のメチルアルコール、エチルアルコ
ール、エチレングリコール等、ケトン類のアセト
ン、メチルエチルケトン等、エーテル類のジオキ
サン、テトラヒドロフラン、セルソルブ等、炭化
水素類のベンゼン、トルエン、キシレン、ヘキサ
ン、ケロシン、灯油、ナフサ、メチルナフタレン
等、エステル類の醋酸エチル、醋酸ブチル等、有
機塩基類のピリジン、ピコリン等、ジメチルホル
ムアミド、アセトニトリルなどの有機溶剤が適当
であり、これらの一種または二種以上の混合物を
使用する。
固体担体(稀釈剤、増量剤など)としては例え
ば、鉱物性粉末のカオリン、ベントナイト、酸性
白土、クレー、タルク、珪そう土、雲母粉等、植
物性粉末の大豆粉、小麦粉、木粉等、更にアルミ
ナ、活性炭等も使用することができ、これらの一
種または二種以上の混合物を使用する。乳化剤、
分散剤、浸透剤、展着剤として陰イオン性、陽イ
オン性、非イオン性および両性イオン性のいずれ
の界面活性剤も使用することができる。
また所望によつては、カゼイン、ゼラチン、澱
粉、アルギン酸ソーダ等を補助剤として使用する
ことができる。
本発明化合物の製剤化に際しては、有効成分比
率は自由にとることができるが、一般的には5〜
90%の含有率が適当である。
また、使用目的に応じて、本発明化合物を他の
除草剤、殺菌剤、殺虫剤、植物生長調節剤または
肥料等と併用することができる。
次に実施例をあげて説明するが、化合物、担
体、補助剤および使用割合は本実施例に限定され
るものではない。
なお、本実施例中の成分の構成比は重量部を示
す。
実施例1 (水和剤)
化合物番号32 50部
リグニンスルホン酸ナトリウム 1部
ポリオキシエチレンアルキルアリールエーテ
ル 4部
クレー 45部
これらの各成分を均一になるまで混和し、粉砕
して水和剤として用いる。
実施例2 (乳剤)
化合物番号102 20部
アルキルベンゼンスルホン酸塩 3部
ポリオキシエチレンアルキルアリールエーテ
ル 10部
キシロール 67部
これらの各成分を均一になるまで混和し、溶解
して乳剤として用いる。
実施例 3
(粒剤)
化合物番号4 6部
ベントナイト 30部
アルキル硫酸ソーダ 1.5部
クレー 62.5部
これらの各成分を均一になるまで混合し、練合
して通常の造粒方法で造粒し粒剤として用いる。
実施例4 (粉剤)
化合物番号24 7部
クレー 93部
これらの各成分を均一になるまで混和し、粉剤
として用いる。
次に本発明化合物の効果を試験例により説明す
る。
試験例 1
1/5000アールのポリエチレン製ポツトに水田土
壌(埴壌土)を充填し、ノビエ、タマガヤツリ、
広葉雑草の各種子を表層2cmに播種し、同時に2
葉期の水稲を2cmの深さに2本1株植として、3
cmに湛水した。雑草発芽と同時に、実施例1に準
じた処方により製した各供試化合物の水和剤の所
定量を秤量し、1ポツト当り10mlの水に稀釈して
水面に滴下処理した。その後ガラス室において育
成し、処理3週間後に除草効果および水稲薬害を
調査した。その結果を第3表に示す。
なお、表中の数値は水稲薬害および除草効果を
示すもので具体的には下記の通りである。[Table] In carrying out the present invention, one or a mixture of two or more of the compounds represented by the general formula
50-2000g per are, preferably 100-1000g
Although it is appropriate to use the drug at a ratio of 1, it goes without saying that the dosage can be adjusted depending on the circumstances of the actual situation. When actually used, the compound of the present invention can be used directly as it is, but depending on the purpose of use, one or more compounds represented by the above general formula [] may be dissolved in a liquid carrier. or by dispersing it or adsorbing it with a suitable solid carrier (e.g. diluent, filler, etc.) and, if desired, with an emulsifying agent, dispersing agent, suspending agent, or spreading agent. , a penetrating agent, a stabilizer, etc. are added to form a dosage form such as a wettable powder, emulsion, granule, powder, or tablet. Examples of the liquid carrier (solvent) mentioned here include:
Alcohols such as methyl alcohol, ethyl alcohol, and ethylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane, tetrahydrofuran, and cellosolve; hydrocarbons such as benzene, toluene, xylene, hexane, kerosene, kerosene, naphtha, and methyl Organic solvents such as naphthalene, esters such as ethyl acetate and butyl acetate, organic bases such as pyridine and picoline, dimethylformamide, and acetonitrile are suitable, and one or a mixture of two or more of these may be used. Examples of solid carriers (diluents, fillers, etc.) include mineral powders such as kaolin, bentonite, acid clay, clay, talc, diatomaceous earth, mica powder, etc., vegetable powders such as soybean powder, wheat flour, wood flour, etc. Furthermore, alumina, activated carbon, etc. can also be used, and one or a mixture of two or more of these can be used. emulsifier,
Anionic, cationic, nonionic, and amphoteric surfactants can be used as dispersants, penetrants, and spreading agents. If desired, casein, gelatin, starch, sodium alginate, etc. can be used as adjuvants. When formulating the compound of the present invention, the ratio of active ingredients can be set freely, but it is generally 5 to 5.
A content of 90% is suitable. Furthermore, depending on the purpose of use, the compound of the present invention can be used in combination with other herbicides, fungicides, insecticides, plant growth regulators, fertilizers, and the like. Next, an explanation will be given with reference to examples, but the compounds, carriers, adjuvants, and proportions used are not limited to these examples. In addition, the composition ratio of the components in this example shows parts by weight. Example 1 (Wettable powder) Compound No. 32 50 parts Sodium lignin sulfonate 1 part Polyoxyethylene alkylaryl ether 4 parts Clay 45 parts These components were mixed until uniform, ground, and used as a wettable powder. . Example 2 (Emulsion) Compound No. 102 20 parts Alkylbenzene sulfonate 3 parts Polyoxyethylene alkylaryl ether 10 parts Xylol 67 parts These components are mixed until uniform, dissolved, and used as an emulsion. Example 3 (Granules) Compound No. 4 6 parts Bentonite 30 parts Sodium alkyl sulfate 1.5 parts Clay 62.5 parts These components were mixed until uniform, kneaded, and granulated using a normal granulation method to produce granules. used as Example 4 (Powder) Compound No. 24 7 parts Clay 93 parts These components are mixed until uniform and used as a powder. Next, the effects of the compounds of the present invention will be explained using test examples. Test example 1 A 1/5000 are polyethylene pot was filled with paddy soil (clay loam), and a field of wildflowers, snails,
Sow each broad-leaved weed seed 2 cm above the surface, and at the same time
Two paddy rice plants in the leaf stage were planted at a depth of 2 cm, and 3
flooded to cm. Simultaneously with weed germination, a predetermined amount of a hydrating powder of each test compound prepared according to the formulation according to Example 1 was weighed out, diluted in 10 ml of water per pot, and dropped onto the water surface. Thereafter, they were grown in a glass room, and three weeks after treatment, the herbicidal effect and paddy rice damage were investigated. The results are shown in Table 3. In addition, the numerical values in the table indicate paddy rice phytotoxicity and herbicidal effects, and are specifically as follows.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
試験例 2
1/5000アールのポリエチレン製ポツトに畑地土
壌(埴壌土)を充填し、イネ、コムギ、ヒエ、ダ
イコンおよびアオビユの種子を播種し、1cmの覆
土をしてガラス室において育成した。その後イネ
が2葉期、コムギが3葉期、ダイコンとアオビユ
が第1本葉を展開したときに、実施例1に準じた
処方により製した本発明化合物の水和剤の所定量
を秤量し、1ポツト当り2mlの水に稀釈し茎葉全
面に噴霧処理した。処理2週間後に各供試植物に
対する薬害および除草効果の程度を調査した。そ
の結果を第4表に示す。
なお、表中の数値は試験例1に示した解釈に準
ずる。[Table] Test Example 2 Fill a 1/5000 are polyethylene pot with upland soil (clay loam), sow seeds of rice, wheat, barnyard grass, radish, and blueberry, cover with 1 cm of soil, and grow in a glass room. did. Thereafter, when rice had developed its two-leaf stage, wheat had developed its three-leaf stage, and radish and Japanese radish had developed their first true leaves, a predetermined amount of the hydrating agent of the compound of the present invention prepared according to the formulation according to Example 1 was weighed. The mixture was diluted in 2 ml of water per pot and sprayed over the entire surface of the stems and leaves. Two weeks after the treatment, the degree of phytotoxicity and herbicidal effect on each test plant was investigated. The results are shown in Table 4. Note that the numerical values in the table conform to the interpretation shown in Test Example 1.
【表】【table】
【表】【table】
Claims (1)
リフルオロメチル基を示し、nは0から3の整数
を示し、nが2または3の場合はXは同じでも相
異つてもよい。Rはメチル基またはメトキシ基を
示す。二重結合はトランス体を示す。)で表わさ
れる尿素誘導体。 2 一般式 (式中Xはハロゲン原子、アルキル基およびト
リフルオロメチル基を示し、nは0から3の整数
を示し、nが2または3の場合はXは同じでも相
異つてもよい。Yはハロゲン原子を示す。二重結
合はトランス体を示す。)で表わされるブテニー
ルハライド誘導体と一般式 (式中Rはメチル基またはメトキシ基を示
す。)で表わされる尿素誘導体とを反応させるこ
とを特徴とする一般式 (式中X,nおよびRは前記と同じ意味を有す
る。二重結合はトランス体を示す。)で表わされ
る尿素誘導体の製造法。 3 一般式 (式中Xはハロゲン原子、アルキル基およびト
リフルオロメチル基を示し、nは0から3の整数
を示し、nが2または3の場合はXは同じでも相
異つてもよい。)で表わされるフエノール誘導体
と一般式 (式中Yはハロゲン原子を示し、Rはメチル基
またはメトキシ基を示す。二重結合はトランス体
を示す。)で表わされる尿素誘導体とを反応させ
ることを特徴とする一般式 (式中X,nおよびRは前記と同じ意味を有す
る。二重結合はトランス体を示す。)で表わされ
る尿素誘導体の製造法。 4 一般式 (式中Xはハロゲン原子、アルキル基またはト
リフルオロメチル基を示し、nは0から3の整数
を示し、nが2または3の場合はXは同じでも相
異つてもよい。二重結合はトランス体を示す。)
で表わされるアニリン誘導体と一般式 (式中Yはハロゲン原子を示し、Rはメチル基
またはメトキシ基を示す。)で表わされるカルバ
ミールハライド誘導体とを反応させることを特徴
とする一般式 (式中X,nおよびRは前記と同じ意味を有す
る。二重結合はトランス体を示す。)で表わされ
る尿素誘導体の製造法。 5 一般式 (式中Xはハロゲン原子、アルキル基またはト
リフルオロメチル基を示し、nは0から3の整数
を示し、nが2または3の場合はXは同じでも相
異つてもよい。二重結合はトランス体を示す。)
で表わされるフエニールイソシアネート誘導体と
一般式 (式中Rはメチル基またはメトキシ基を示
す。)で表わされるアミン誘導体を反応させるこ
とを特徴とする一般式 (式中X,nおよびRは前記と同じ意味を有す
る。二重結合はトランス体を示す。)で表わされ
る尿素誘導体の製造法。 6 一般式 (式中Xはハロゲン原子、アルキル基またはト
リフルオロメチル基を示し、nは0から3の整数
を示し、nが2または3の場合はXは同じでも相
異つてもよい。二重結合はトランス体を示す。)
で表わされる尿素誘導体をメチル化することを特
徴とする一般式 (式中X,nは前記と同じ意味を有する。Rは
メトキシ基を示す。二重結合はトランス体を示
す。)で表わされる尿素誘導体の製造法。 7 一般式 (式中Xはハロゲン原子、アルキル基またはト
リフルオロメチル基を示し、nは0から3の整数
を示し、nが2または3の場合はXは同じでも相
異つてもよい。Rはメチル基またはメトキシ基を
示す。二重結合はトランス体を示す。)で表わさ
れる尿素誘導体を有効成分として含有することを
特徴とする選択性除草剤。[Claims] 1. General formula (In the formula, X represents a halogen atom, an alkyl group, or a trifluoromethyl group, n represents an integer from 0 to 3, and when n is 2 or 3, X may be the same or different. or a methoxy group.The double bond indicates a trans isomer). 2 General formula (In the formula, X represents a halogen atom, an alkyl group, or a trifluoromethyl group, n represents an integer from 0 to 3, and when n is 2 or 3, X may be the same or different. (The double bond indicates the trans isomer.) and the general formula (In the formula, R represents a methyl group or a methoxy group.) A general formula characterized by reacting with a urea derivative represented by (In the formula, X, n and R have the same meanings as above. The double bond indicates a trans form.) A method for producing a urea derivative represented by the formula: 3 General formula (In the formula, X represents a halogen atom, an alkyl group, or a trifluoromethyl group, n represents an integer from 0 to 3, and when n is 2 or 3, X may be the same or different.) Phenol derivatives and general formula (In the formula, Y represents a halogen atom, R represents a methyl group or a methoxy group, and the double bond represents a trans form.) (In the formula, X, n and R have the same meanings as above. The double bond indicates a trans form.) A method for producing a urea derivative represented by the formula: 4 General formula (In the formula, X represents a halogen atom, an alkyl group, or a trifluoromethyl group, n represents an integer from 0 to 3, and when n is 2 or 3, X may be the same or different. (Indicates trans isomer.)
Aniline derivatives and general formula represented by (In the formula, Y represents a halogen atom and R represents a methyl group or a methoxy group.) (In the formula, X, n and R have the same meanings as above. The double bond indicates a trans form.) A method for producing a urea derivative represented by the formula: 5 General formula (In the formula, X represents a halogen atom, an alkyl group, or a trifluoromethyl group, n represents an integer from 0 to 3, and when n is 2 or 3, X may be the same or different. (Indicates trans isomer.)
Phenyl isocyanate derivatives represented by and general formula A general formula characterized by reacting an amine derivative represented by (wherein R represents a methyl group or a methoxy group) (In the formula, X, n and R have the same meanings as above. The double bond indicates a trans form.) A method for producing a urea derivative represented by the formula: 6 General formula (In the formula, X represents a halogen atom, an alkyl group, or a trifluoromethyl group, n represents an integer from 0 to 3, and when n is 2 or 3, X may be the same or different. (Indicates trans isomer.)
A general formula characterized by methylating a urea derivative represented by (In the formula, X and n have the same meanings as above. R represents a methoxy group. The double bond represents a trans form.) A method for producing a urea derivative represented by the formula: 7 General formula (In the formula, or a methoxy group.The double bond indicates a trans form.) A selective herbicide characterized by containing a urea derivative represented by the following as an active ingredient.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4957580A JPS56147758A (en) | 1980-04-17 | 1980-04-17 | Urea derivative, its preparation and selective herbicide consisting of the same |
US06/247,711 US4358309A (en) | 1980-04-17 | 1981-03-26 | Urea derivatives and highly selective herbicidal compositions containing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4957580A JPS56147758A (en) | 1980-04-17 | 1980-04-17 | Urea derivative, its preparation and selective herbicide consisting of the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS56147758A JPS56147758A (en) | 1981-11-16 |
JPS6261026B2 true JPS6261026B2 (en) | 1987-12-18 |
Family
ID=12835002
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4957580A Granted JPS56147758A (en) | 1980-04-17 | 1980-04-17 | Urea derivative, its preparation and selective herbicide consisting of the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS56147758A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01194141A (en) * | 1988-01-29 | 1989-08-04 | Matsushita Electric Ind Co Ltd | Optical pickup device |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0710976U (en) * | 1993-07-28 | 1995-02-14 | キンセキ株式会社 | Substrate resist coating structure |
-
1980
- 1980-04-17 JP JP4957580A patent/JPS56147758A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01194141A (en) * | 1988-01-29 | 1989-08-04 | Matsushita Electric Ind Co Ltd | Optical pickup device |
Also Published As
Publication number | Publication date |
---|---|
JPS56147758A (en) | 1981-11-16 |
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