CN1061593A - 取代的吡咯烷-2-酮,其制备方法,及含有其作为除草活性成分的除草组合物 - Google Patents
取代的吡咯烷-2-酮,其制备方法,及含有其作为除草活性成分的除草组合物 Download PDFInfo
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- CN1061593A CN1061593A CN91109570A CN91109570A CN1061593A CN 1061593 A CN1061593 A CN 1061593A CN 91109570 A CN91109570 A CN 91109570A CN 91109570 A CN91109570 A CN 91109570A CN 1061593 A CN1061593 A CN 1061593A
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- Prior art keywords
- phenyl
- substituted
- pyrrolidin
- ethyl
- atom
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 68
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims description 19
- -1 4-ethyl-1-(substituted-phenyl)-3-(substituted-phenyl) pyrrolidin-2-one Chemical class 0.000 claims abstract description 44
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 43
- 235000009566 rice Nutrition 0.000 claims abstract description 40
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 5
- 125000001246 bromo group Chemical group Br* 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 55
- 241000196324 Embryophyta Species 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 230000006378 damage Effects 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 208000027418 Wounds and injury Diseases 0.000 claims description 11
- 208000014674 injury Diseases 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 241000209094 Oryza Species 0.000 claims 4
- 240000007594 Oryza sativa Species 0.000 abstract description 39
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 18
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical class NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 abstract description 11
- 239000000470 constituent Substances 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 63
- 239000000243 solution Substances 0.000 description 33
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
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- 239000012628 flowing agent Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
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- 239000002689 soil Substances 0.000 description 8
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- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 7
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- 244000025254 Cannabis sativa Species 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 244000058871 Echinochloa crus-galli Species 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
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- 239000008187 granular material Substances 0.000 description 6
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- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-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
- 239000002253 acid Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 240000000178 Monochoria vaginalis Species 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 239000012312 sodium hydride Substances 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- 229920005552 sodium lignosulfonate Polymers 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 241001529246 Platymiscium Species 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000002872 contrast media Substances 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
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- 229940031815 mycocide Drugs 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- HNJBEVLQSNELDL-YZRHJBSPSA-N pyrrolidin-2-one Chemical class O=C1CC[14CH2]N1 HNJBEVLQSNELDL-YZRHJBSPSA-N 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- CFQPVBJOKYSPKG-UHFFFAOYSA-N 1,3-dimethylimidazol-2-one Chemical compound CN1C=CN(C)C1=O CFQPVBJOKYSPKG-UHFFFAOYSA-N 0.000 description 2
- QXOGPTXQGKQSJT-UHFFFAOYSA-N 1-amino-4-[4-(3,4-dimethylphenyl)sulfanylanilino]-9,10-dioxoanthracene-2-sulfonic acid Chemical compound Cc1ccc(Sc2ccc(Nc3cc(c(N)c4C(=O)c5ccccc5C(=O)c34)S(O)(=O)=O)cc2)cc1C QXOGPTXQGKQSJT-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- KBUHMSHXBQYACH-UHFFFAOYSA-N 2-bromo-2-(3-chlorophenyl)acetyl chloride Chemical compound ClC(=O)C(Br)C1=CC=CC(Cl)=C1 KBUHMSHXBQYACH-UHFFFAOYSA-N 0.000 description 2
- XFJBGINZIMNZBW-CRAIPNDOSA-N 5-chloro-2-[4-[(1r,2s)-2-[2-(5-methylsulfonylpyridin-2-yl)oxyethyl]cyclopropyl]piperidin-1-yl]pyrimidine Chemical compound N1=CC(S(=O)(=O)C)=CC=C1OCC[C@H]1[C@@H](C2CCN(CC2)C=2N=CC(Cl)=CN=2)C1 XFJBGINZIMNZBW-CRAIPNDOSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 2
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- 244000085269 Scirpus juncoides Species 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
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- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
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- 239000012442 inert solvent Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- OBMBFSOIBAWLEJ-NSCUHMNNSA-N n-[(e)-but-2-enyl]aniline Chemical compound C\C=C\CNC1=CC=CC=C1 OBMBFSOIBAWLEJ-NSCUHMNNSA-N 0.000 description 2
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
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- LJZQOHBPZABDNX-UHFFFAOYSA-N 1-(3-propan-2-ylphenyl)pyrrolidin-2-one Chemical class CC(C)C1=CC=CC(N2C(CCC2)=O)=C1 LJZQOHBPZABDNX-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- 241000738824 Hottonia palustris Species 0.000 description 1
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- 239000012448 Lithium borohydride Substances 0.000 description 1
- LVDRREOUMKACNJ-BKMJKUGQSA-N N-[(2R,3S)-2-(4-chlorophenyl)-1-(1,4-dimethyl-2-oxoquinolin-7-yl)-6-oxopiperidin-3-yl]-2-methylpropane-1-sulfonamide Chemical compound CC(C)CS(=O)(=O)N[C@H]1CCC(=O)N([C@@H]1c1ccc(Cl)cc1)c1ccc2c(C)cc(=O)n(C)c2c1 LVDRREOUMKACNJ-BKMJKUGQSA-N 0.000 description 1
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- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
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- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
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- 239000000039 congener Substances 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 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
- 238000010828 elution Methods 0.000 description 1
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- 239000003337 fertilizer Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- PGLTVOMIXTUURA-UHFFFAOYSA-N iodoacetamide Chemical compound NC(=O)CI PGLTVOMIXTUURA-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
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 229940093916 potassium phosphate Drugs 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000006476 reductive cyclization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- HONNWTDYWUAZJF-UHFFFAOYSA-N tert-butyl 4-[2-[4-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxyindol-1-yl]acetyl]piperazine-1-carboxylate Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC1=C2C=CN(C2=CC=C1)CC(=O)N1CCN(CC1)C(=O)OC(C)(C)C HONNWTDYWUAZJF-UHFFFAOYSA-N 0.000 description 1
- 244000082735 tidal marsh flat sedge Species 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 150000003953 γ-lactams Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/08—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by hetero atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Pyrrole Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷
-2-酮的3,4-顺式异构体,当与碱反应时,可有效地
转化成其3,4-反式异构体,该反式异构体具有高除
草活性并被用作除草组合物的有效成分。而且,由式
(III)代表的3,4-反-4-乙基-1-(取代苯基)-3-(取
代苯基)吡咯烷-2-酮化合物
(其中R2为异丙基,X为在3-位取代的氟原子,
氯原子或溴原子,或在3-和4-位或3-和5-位取代
的氟原子)具有极高活性,尤其是作为用于水稻田的
除草组合物的除草活性成分。
Description
本发明涉及3,4-反-4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮,其制备方法,以及含有它作为除草活性成分的水稻田除草组合物。
具有除草活性的某些类型的吡咯烷-2-酮衍生物已被公开,有关这方面的内容在美国专利4110105;4210589;4874422及欧洲专利公开387869等出版物中已有描述。而且,这些公开物中的一个典型化合物3-氯-4-氯甲基-1-(3-氟甲基苯基)-2-吡咯烷酮(俗名氟氯酮)为商品。而且在美国专利4960457中也公开了吡咯烷酮衍生物和除草组合物。
在用作除草组合物时,在上述美国专利4110105;4210589及4874422中所公开的化合物需用较大量,即,较高的施用比率。特别是当这些化合物用于水稻田时,有一个问题是它们对稻株有药物伤害作用,而水稻是有用的作物。
此外,当它们用于水稻田时,公开于欧洲专利公开387869或美国专利4960457实施例中的化合物具有对于处于生长期的杂草效力低的问题。
到现在为止,任何选择地和有效地制备具有除草活性的这些吡咯烷酮衍生物优选异构体,即,3,4-反式异构体的方法还未为人所知。因此,应用这些化合物作实用的除草组合物是非常困难的。
本发明鉴于上述常规的2-吡咯烷酮衍生物的各种问题而作了改进。
因此,本发明的一个目的是提供一种选择地和有效地制备作为除草组合物有效成分的,具有较高活性的异构体,即,3,4-反式异构体的方法。
本发明的另一目的是提供一种选择性的除草组合物,它在水稻田中对稻株没有伤害作用,在低施用比率时有效,并可用于从杂草的芽前期到长出的杂草的生长期这一期间。
为了达到这些目的,本发明人深入研究了有效制备具有高活性的反式异构体的技术,结果发现,当用碱与顺式异构体反应时,可以得到反式异构体。另外还发现,作为除草组合物,一些反式异构体化合物与其其它化合物相比优越得多,更好的是,它们对于有用作物稻株无伤害作用。结果,本发明在这些知识的基础上完成了。
根据本发明,可提供一种有效制备3,4-反式-4-乙基-1-(取代苯基)-3-(取代苯基)-吡咯烷-2-酮的方法,该类化合物用作除草组合物的有效成分。除草组合物含有3,4-反式-4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮衍生物,首先,3,4-反式-4-乙基-3-(取代苯基)-1-(3-异丙基苯基)吡咯烷-2-酮衍生物、它以低施用比率,在杂草芽前期至所出现的杂草的生长期的期限内,对水稻田中各种讨厌的杂草产生除草活性。另外,这些除草组合物对于稻株具有优良的选择性,因而可以安全使用。
本发明制备具有式(Ⅰ)代表的结构的4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮的3,4-反式异构体
(其中R1为氢原子,卤原子或甲基;R2为三氟甲基,具有1至3个碳原子的卤代烷氧基,具有1至3个碳原子的卤代烷硫基,具有1至4个碳原子的低级烷基,具有1至4个碳原子的烷氧基,硝基,氰基,苯氧基,羟基或卤原子;X为氢原子、卤原子、三氟甲基,具有1至3个碳原子的烷基、氰基或硝基;n等于1或2并指示由X代表的取代基的数目,当n=2时,基团X可以相同或不同)的方法包括碱与具有式(Ⅰ)所代表的结构的4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮的3,4-顺式异构体反应的步骤。
本发明的4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮的3,4-反式异构体可由式(Ⅲ)表示
(其中R2为异丙基,而X为在3-位取代的氟原子,氯原子或溴原子,或在3-和4-位或在3-和5-位取代的氟原子)。
本发明用于水稻田的除草组合物含有由式(Ⅲ)代表的4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮的3,4-反式异构体作为除草活性组分。
本发明的制备方法指出一种通过碱与或者式(Ⅰ)的4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮的3,4-顺式异构体或者其3,4-反式异构体和3,4-顺式异构体的混合物反应而高产率和高选择性地制备式(Ⅰ)4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮的3,4-反式异构体的方法。
在本发明的制备方法中,碱的使用是必不可少的。
可用碱的例子包括碱金属氢氧化物如氢氧化钠、氢氧化钾和氢氧化锂、碱土金属氢氧化物如氢氧化钙和氢氧化钡,无机酸的钠盐如碳酸钠、碳酸氢钠、磷酸钠、磷酸氢钠、亚硫酸钠、亚硫酸氢钠、亚硝酸钠、次氯酸钠、氰化钠和膦酸钠;无机酸钾盐如碳酸钾、碳酸氢钾、磷酸钾、磷酸氢钾、亚硫酸钾、亚硫酸氢钾、亚硝酸钾、次氯酸钾、氰化钾和膦酸钾;无机酸锂盐,碱金属如金属钠和金属钾;金属氢化物如氢化钠、二异丁基铝氢化物、氢化锂铝、氢化铝钠、硼氢化锂和硼氢化钠;醇盐如叔丁醇钾和甲醇钠;酚盐;氨;羧酸钠盐如乙酸钠、甲酸钠、草酸钠和苯甲酸钠;羧酸钾盐如乙酸钾、甲酸钾、草酸钾和苯甲酸钾;脂族胺如甲胺、乙胺、二甲胺、二乙胺和三乙胺;芳香胺如苯胺和N,N-二甲基苯胺;有机碱如吡啶、甲基吡啶、喹啉、1,8-二氮杂双环(5.4.0)十一碳-7-烯(DBU);冠醚;碱性离子交换树脂,和其混合物。在这些化合物中,优选的是便宜的氢氧化钠、氢氧化钾、碳酸钾、氢化钠和1,8-二氮杂双环(5.4.0)十一碳-7-烯(DBU)。
碱的量取决于所选碱的种类,但一般在0.001至10当量的范围内,优选地基于1当量4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮为0.01至3当量。
碱的反应温度取决于所选碱的种类,但通常在0至200℃范围内,优选地为室温至100℃。
如果需要,反应可在减压或加压下进行,但这些压力条件没什么标准。通常,反应在大气压下进行。
在本发明的制备方法中,通常要用溶剂。对于溶剂没有特殊限制,只要对反应没有坏的影响。可用溶剂的例子包括水;醇如甲醇、乙醇、异丙醇和乙二醇;醚如二乙醚、四氢呋喃、乙二醇二甲醚和二甘醇二甲醚;腈如乙腈;酮如丙酮;酯如乙酸乙酯和乙酸正丁酯;烃如正己烷;卤代烃如二氯甲烷、氯仿和1,2-二氯乙烷;芳香烃如苯、甲苯、二甲苯和枯烯;非质子极性溶剂如N,N-二甲基甲酰胺、1,3-二甲基-2-咪唑啉酮、环丁砜(Sulfolane)、DMSO、DMAc和HMPA,和其混合物。
溶剂的量通常在0.3至30份重量的范围内,优选地基于1份重量的4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮为1至10份。
为了制备可用作本发明制备方法中的原料的4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮的顺式异构体或顺式异构体与反式异构体的混合物,有各种技术,例如,可用下面的方法(1)和方法(2)。
(1)N-(2-丁烯基)-N-(取代苯基)-2-卤-2-(取代苯基)乙酰胺的还原环化反应。
在此环化反应中有效的环化剂是以氢化三丁基锡为典型的氢化三烷基锡,一般说来,环化反应在芳香溶剂如苯、甲苯或二甲苯中进行。反应温度优选地为50至140℃,更优选地为60至90℃。反应过程中加入催化量的自由基产生剂如α,α-偶氮双异丁腈或过氧化苯甲酰到反应混合物中。光照也是使反应进行的有效手段。
N-(2-丁烯基)-N-(取代苯基)-2-卤-2-(取代苯基)乙酰胺可通过N-(2-丁烯基)苯胺与α-卤素苯基乙酰卤反应很容易地得到。
此反应在无溶剂或在惰性溶剂中进行,惰性溶剂的例子包括芳香溶剂如苯、甲苯、二甲苯、氯代苯和二氯代苯;卤代烃如二氯甲烷,氯仿和1,2-二氯乙烷;醚如二乙醚、四氢呋喃、乙二醇二甲醚、二甘醇二甲醚和二恶烷;腈如乙腈;酮如丙酮;酯如乙酸乙酯和乙酸正丁酯;烃如正己烷;及非质子极性溶剂如N,N-二甲基甲酰胺、1,3-二甲基-2-咪唑啉酮、环丁砜、DMSO、DMAc和HMPA。反应可在任意的温度如-20至140℃进行,而此反应可在碱如三乙胺、吡啶、N,N-二甲基苯胺、氢化钠、氢化钾、碳酸钠、碳酸钾和碳酸氢钠存在下进行。
N-(2-丁烯基)苯胺可用美国专利4132713中所述的方法制备,而α-卤素苯基乙酰卤可由扁桃酸衍生物或苯乙酸通过已知方法制备。
(2)4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮也可通过4-(α-卤代乙基)-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮〔可通过N-(2-丁烯基)-N-(取代苯基)-2-卤-2-(取代苯基)乙酰胺在过渡金属催化剂存在下环化而得到〕的脱卤化而制备。
这样得到的4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮是关于吡咯烷环的3-和4-位空间构象的反式异构体和顺式异构体混合物。
关于本发明方法中可用作原料的3,4-顺-4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮,勿用置言,可用分离出的顺式异构体,而且顺式异构体和反式异构体的混合物也可应用。
碱既可直接加入包括通过顺式异构体制备方法得到的顺式异构体的反应混合物中,也可加入通过反应混合物后处理所得的产品中。
由本发明的方法所得的3,4-反-4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮可用普通方法得出和收集。
由本发明的方法得到的3,4-反-4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮表现出优良的除草活性。另一方面,顺式异构体几乎不显示除草活性。
式(Ⅲ)化合物(以后称为“本发明化合物”)是新化合物,并且在式(Ⅰ)化合物当中,本发明化合物具有作为水稻田除草组合物的特别优良的特性。
当用于水稻田时,公开于美国专利4110105、4210589和4874422的化合物对稻株有药物伤害作用,因而它们不能用于此。
在美国专利4960457中,由式(Ⅱ)代表的化合物
(Ⅱ)
(其中m为1、2、3、4或5;n为0、1、2、3、4或5;R1为卤原子、三氟甲基、氰基、具有1至4个碳原子的烷基或具有1至4个碳原子的烷氧基,且当m大于1时,R1基团可以相同或不同;R2为氢原子或卤原子;R3为卤原子、三氟甲基、氰基,具有1至4个碳原子的烷基或具有1至4个碳原子的烷氧基,当n大于1时,R3基团可以相同或不同;R4为具有1至4个碳的烷基或被卤素取代的具有1至4个碳原子的烷基)
被要求保护,并且在该专利中叙述它们具有除草活性。
也就是说,美国专利4960457的上位概念覆盖了本发明化合物。这份美国专利要求的化合物范围极广,但有实施例的化合物是有限的。在此美国专利中,描述了R1的优选例子包括卤原子,三氟甲基和氰基。然而,在此美国专利的实施例中,三氟甲基、氰基、氯原子和氟原子只作为R1基团叙述,而没有其中烷基作为R1基团的实施例。
当用于水稻田时,美国专利4960457和欧洲专利公开387869中所述的化合物对于生长期的杂草不太有效。因此,使用这些化合物的时机只限于杂草的芽前期。
本发明化合物的特征在于3-异丙基苯基,特定的苯基和乙基分别被引入吡咯烷环的1-位、3-位和4-位。这些特定基团被排列的意义,特别是3-异丙苯基被引入吡咯烷环1-位的意义是重大的。这一变换的结果是,用作水稻田除草组合物的化合物的活性可被提高,而且化合物可在杂草的芽前期至长出的杂草的生长期显示高的除草活性。结果是本发明化合物可在更长期限内应用。
含有本发明化合物作为除草活性成分的水稻田除草组合物在大多数水稻田中对有害杂草具有优良的除草效果,例如,禾本科杂草如稗(Echinochloa)及其类似物,莎草科杂草如象莎草的水堇(Cyperus microiria),藨草属植物(Sirpus juncoides)等,和宽叶杂草如矮慈菇(Sagittaria Pygmaea)等。另一方面,此除草组合物对有用作物水稻(Oryza sativa)无伤害作用。而且,该除草组合物可有效地运用于所有施用如从杂草的芽前期至已长成杂草生长期的很长期限内水面下土壤施用,土壤施用和土壤混合。
本发明化合物通常与惰性液体载体或固体载体混合,配制成粉剂、粒剂、可湿性粉剂、乳剂、流动剂等,然后使用。在制剂中如果需要,可加入辅助剂。
载体可以是固态或液态,并且对载体没有特殊的限制,只要其可以通用于农业和园艺药剂中。固体载体的例子包括矿物粉如粘土,滑石、膨润土、碳酸钙、硅藻土和白碳,植物粉如大豆粉和淀粉,及高聚物如石油树脂,聚乙烯基醇和聚亚烷基二醇、尿素和蜡。而液体载体的例子包括各种有机溶剂如二甲苯、甲基萘和烷基苯,几种油如植物油,以及水。
辅助剂的例子包括用于农业和园艺药剂中的表面活性剂、粘合剂(例如,木素磺酸、藻酸、聚乙烯基醇、阿拉伯胶和羧甲基纤维素钠)以及稳定剂(例如,当酚类化合物、硫醇化合物或高级脂肪酸酯被用于防止氧化时,或当磷酸盐被用作pH调节剂时,也可使用光稳定剂)它们可单独使用也可混合使用。在一定情况下,工业杀菌剂或抗菌杀真菌剂可加入以控制细菌和真菌。
表面活性剂的例子包括非离子型,阳离子型、阴离子型和两性表面活性剂,可被合适地单独或混合使用。优选非离子型表面活性剂的例子可通过往烷基苯酚、高级醇、烷基萘酚、高级脂肪酸、脂肪酸酯或类似物中加入环氧乙烷(例如,X-77或Neugen EA80)或1,2-环氧丙烷而得到。阴离子表面活性剂优选的例子为烷基磺酸盐(例如,Neopelex),烷基硫酸酯盐,磷酸酯盐或烷基苯酚、烷基萘酚、高级醇、高级脂肪酸、脂肪酸酯的类似物或同类物。木素磺酸盐(例如,Sun Ekisu)或其类似物也是一个优选的例子。
在本发明除草组合物中,由式(Ⅰ)表示的化合物的含量取决于制剂的形态。一般地,在粉剂中为重量的0.01-20%,在可湿性粉剂中为重量的1-50%,粒剂中为重量的0.01-10%,乳剂中为重量的0.1-50%,流动剂中为重量的0.1-50%,干流动剂中为重量的1-50%。优选地为,粉剂重量的0.1-3%,可湿性粉剂中为重量的10-40%,粒剂中为重量的0.1-5%,在乳剂中为重量的1-30%,在流动剂中为重量的1-30%,在干流动剂中为重量的10-40%。
辅助剂的含量为重量的0-80%,而载体的含量为从重量100%中减去除草活性成分化合物的含量和辅助剂的含量所得的值。
不用说,由式(Ⅰ)代表的本发明除草组合物可与一种或多种其它除草组合物或农药如杀真菌剂、杀虫剂和植物生长调节剂,肥料、土壤改良剂等混合,在此除草组合物还可作成混合剂型。在某些情况下,这种组合可望产生协同效应。
本发明的制备方法和本发明化合物的制备方法将参考典型实施例进行描述。
实施例1
将35.1g(0.10mol)3,4-顺-4-乙基-3-(3-氟苯基)-1-(3-三氟甲基苯基)吡咯烷-2-酮溶于300ml甲醇中,然后在冷却下往其中加入20ml50%氢氧化钠水溶液。然后,将所得溶液在室温下放置5小时。此溶液用浓盐酸中和,减压蒸去大部分甲醇。将剩余物倾入500ml水中,然后用200ml乙酸乙酯提取两次。用饱和氯化钠水溶液洗涤,用无水硫酸钠干燥后,减压蒸去溶剂,得到34.6g3,4-反-4-乙基-3-(3-三氟苯基)-1-(3-三氟甲基苯基)吡咯烷-2-酮(化合物5)白色晶体。
经HPLC分析,反式异构体的纯度为96%。
实施例2
将17.6g(0.05mol)3,4-顺-4-乙基-3-(4-氟苯基)-1-(3-三氟甲基苯基)吡咯烷-2-酮和17.6g(0.05mol)3,4-反-4-乙基-3-(4-氟苯基)-1-(3-三氟甲基苯基)吡咯烷-2-酮溶于300ml无水四氢呋喃中,在室温、氮气流中搅拌下往里面加入5.0g60%氢化钠,然后将溶液保持30分钟。随后,将混合物倾入1000ml1%盐酸水溶液中,用200ml乙酸乙酯提取两次,接着用300ml饱和氯化钠水溶液洗涤。减压蒸去溶剂,得到33.3g3,4-反-4-乙基-3-(4-氟代苯基)-1-(3-三氟甲基苯基)吡咯烷-2-酮(化合物3)白色晶体。经HPLC分析,反式异构体纯度为94%。
实施例3
将23.2g(0.05mol)N-(2-丁烯基)-N-(4-氯-3-三氟甲基苯基)-2-溴-2-(3-氟苯基)乙酰胺溶于200ml甲苯中,在80-90℃,搅拌下往里面加入15ml氢化三丁基锡和痕量α,α-偶氮双异丁腈,接着加热搅拌1小时。溶液冷却至室温后,加入1.0ml1,8-二氮杂双环(5.4.0)十一碳-7-烯(DBU),将溶液保持1小时。接着,将溶液用100ml10%盐酸洗涤,然后蒸去甲苯。将无甲苯的溶液溶于300ml乙腈,然后用正己烷充分洗涤,蒸去乙腈得17.0g3,4-反-4-乙基-3-(3-氟苯基)-1-(4-氯-3-三氟甲基苯基)吡咯烷-2-酮(化合物33)白色晶体。经HPLC分析,反式异构体的纯度为95%。
实施例4
将22.3g(0.05mol)N-(2-丁烯基)-N-(3-三氟甲基苯基)-2-溴-2-(3-氯苯基)乙酰胺溶于200ml甲苯中,然后往里面加入3.0g溴化亚铜和3.0ml二正丁基胺。将溶液在90-100℃搅拌30分钟。将所得反应混合物倒入20%盐酸中然后用甲苯提取。提取液用无水硫酸镁干燥,然后蒸去溶剂。进行硅胶色谱分离得19.0g4-(1-溴代乙基)-3-(3-氯苯基)-1-(3-三氟甲基苯基)吡咯烷-2-酮的空间异构体混合物。随后,将所有混合物溶于300ml用氢氯酸饱和的乙酸中,再加入100g锌粉,接着在90-110℃搅拌5小时。滤除不溶物,然后向其中倒入饱和氯化钠水溶液。用甲苯提取后,提取液再用饱和氯化钠水溶液充分洗涤。加入10.0ml1,8-二氮杂双环(5.4.0)十一碳-7-烯(DBU),再将溶液在室温放置1小时。用稀盐酸水溶液洗涤后,蒸去甲苯,得到10.9g3,4-反-4-乙基-3-(3-氯苯基)-1-(3-三氟甲基苯基)吡咯烷-2-酮(化合物11)白色晶体。经HPLC分析,反式异构体的纯度96%。
实施例5
将1.0g4-乙基-3-(3-氟苯基)-1-(4-氯-3-异丙苯基)-吡咯烷-2-酮,2.0ml甲酸和0.7g5%Pd/c加入10ml二甲基甲酰胺中,接着在回流温度下搅拌6小时。滤除Pd/c后,用甲苯提取。用无水硫酸镁干燥后,溶液用蒸发器浓缩,定量得到3,4-反-4-乙基-3-(3-氟苯基)-1-(3-异丙苯基)吡咯烷-2-酮(化合物58)。
实施例6
将1.5g N-(2-丁烯基)-N-(3-异丙苯基)-2-氯-2-(3-氯苯基)乙酰胺加入15ml甲苯中,并在回流搅拌下加入1.2g氢化三丁基锡和痕量α,α-偶氮二异丁腈(AIBN)。继续搅拌10分钟后,使溶液温度回落到室温,加入0.3ml DBU,接着再搅拌5分钟。反应溶液用蒸发器浓缩,然后进行硅胶色谱分离,得到0.9g3,4-反-4-乙基-3-(3-氯苯基)-1-(3-异丙苯基)吡咯烷-2-酮(化合物61)。
比较实施例1
将23.2g(0.05mol)N-(2-丁烯基)-N-(4-氯-3-三氟甲基苯基)-2-溴-2-(3-氟苯基)乙酰胺溶于200ml甲苯,在80-90℃搅拌下往里面加入15ml氢化三丁基锡和痕量α,α-偶氮二异丁腈,接着加热搅拌1小时。随后蒸去甲苯。将无甲苯的溶液溶于300ml乙腈再用正己烷充分洗涤,然后蒸去乙腈,得17.0g4-乙基-3-(3-氟苯基)-1-(4-氯-3-三氟甲基苯基)吡咯烷-2-酮异构体混合物。进行硅胶色谱分离,得9.2g3,4-反-4-乙基-3-(3-氟苯基)-1-(4-氯-3-三氟甲基苯基)吡咯烷-2-酮和3.5g3,4-顺-4-乙基-3-(3-氟苯基)-1-(4-氯-3-三氟甲基苯基)吡咯烷-2-酮。
比较实施例2
除了不加DBU之外,以与实施例2相同的步骤进行反应和处理,得到10.6g4-乙基-3-(3-氯苯基)-1-(3-三氟甲基苯基)吡咯烷-2-酮异构体混合物。然后硅胶色谱分离,得6.8g3,4-反-4-乙基-3-(3-氯苯基)-1-(3-三氟甲基苯基)吡咯烷-2-酮和3.3g3,4-顺-4-乙基-3-(3-氯苯基)-1-(3-三氟甲基苯基)吡咯烷-2-酮。
〔参考实施例〕
N-(2-丁烯基)-N-(取代苯基)-2-卤-2-(取代苯基)乙酰胺,N-(2-丁烯基)苯胺和α-卤代苯基乙酰卤的合成实施例将被描述为参考实施例。
参考实施例1
合成N-(2-丁烯基)-N-(3-三氟甲基苯基)-2-溴-2-(3-氯苯基)乙酰胺:
在大约室温,搅拌下,将3.0g 2-溴-2-(3-氯苯基)乙酰氯逐渐滴加到2.2g N-(2-丁烯基)-N-(3-三氟甲基苯基)胺的40ml甲苯溶液中。再搅20分钟后,滤除不溶沉淀,然后将溶液用甲苯稀释。甲苯溶液用饱和碳酸氢钠水溶液和饱和氯化钠水溶液充分洗涤。用无水硫酸钠干燥后蒸去溶剂,定量得到所需的油状产品。
参考实施例2
合成N-(2-丁烯基)-N-(3-三氟甲基苯基)胺:
将1.4g无水碳酸钾和1.0g1-氯-2-丁烯加入1.6g3-氨基三氟甲苯的30ml二甲基甲酰胺溶液中,接着在70-90℃搅拌2小时。然后滤除碳酸钾,加入100ml饱和氯化钠水溶液,然后用甲苯提取。用无水硫酸钠干燥后,蒸除溶剂,再进行硅胶色谱分离,得1.4g所需化合物。
参考实施例3
合成2-溴-2-(3-氯苯基)乙酰氯:
将14g亚硫酰氯加到17.1g3-氯苯基乙酸中,并在搅拌下往里面滴加18g溴,同时将溶液加热回流。加完后,继续加热回流30小时。冷却后,溶液用蒸发器浓缩,定量得到所需化合物。
参考实施例4
合成3,4-反-4-乙基-3-(3-氟苯基)-1-(4-氯-3-异丙苯基)吡咯烷-2-酮(中间化合物58):
将2.0g N-(2-丁烯基)-N-(4-氯-3-异丙苯基)-2-氯-2-(3-氟苯基)乙酰胺加到15ml甲苯中,再在回流温度搅拌下加入1.8g氢化三丁基锡和痕量α,α-偶氮二异丁腈(AIBN)。继续搅拌10分钟后,将溶液温度降到室温,往里面加入0.3ml DBU,接着再搅拌5分钟。反应溶液用蒸发器浓缩,然后进行硅胶色谱分离,得1.4g所需化合物。
IR ν净(cm-1):1702
NMR(CDCl3)δppm:0.97(3H,t,J=7.2Hz),1.21-1.27(6H,m),1.50-1.60(1H,m),1.70-1.80(1H,m),2.40-2.50(1H,m),3.35-3.45(1H,m),3.48(1H,d,J=10.4Hz),3.54(1H,t,J=8.8Hz),3.99(1H,t,J=8.8Hz),6.96-7.06(3H,m),7.26-7.37(3H,m),7.76(1H,s).
用与参考实施例4相同的步骤来合成如下吡咯烷衍生物。这样得到的衍生物具有如下物理性质:
3,4-反-4-乙基-3-(3,5-二氟苯基)-1-(4-氯-3-异丙苯基)吡咯烷-2-酮(中间化合物59)
IR ν 净(cm-1):1702
nD22.2℃:1.5398
3,4-反-4-乙基-3-(3,4-二氟苯基)-1-(4-氯-3-异丙苯基)吡咯烷-2-酮(中间化合物60)
IR ν 净(cm-1):1701
nD23.1℃:1.5670
参考实施例5
合成N-(2-丁烯基)-N-(4-氯-3-异丙苯基)-2-氯-2-(3-氟苯基)乙酰胺:
在20-30℃搅拌下,将2.6g2-氯-2-(3-氟苯基)乙酰氯逐渐滴加到2.2g N-(2-丁烯基)-N-(4-氯-3-异丙苯基)胺和2.0g无水碳酸钾的40ml N,N-二甲基甲酰胺溶液中。继续搅拌20分钟后,滤除碳酸钾,再用甲苯提取。用无水硫酸钠干燥后,将反应溶液用蒸发器浓缩,定量得到所需油状产物。
IR ν 净(cm-1):1679
nD32.1℃:1.5502
用与参考实施例5相同的步骤合成其它酰胺衍生物。这样得到的衍生物具有如下物理性质:
N-(2-丁烯基)-N-(4-氯-3-异丙苯基)-2-氯-2-(3,5-二氟苯基)乙酰胺:
IR ν 净(cm-1):1680
nD24.6℃:1.5175
N-(2-丁烯基)-N-(4-氯-3-异丙苯基)-2-溴-2-(3,4-二氟苯基)乙酰胺:
IR ν 净(cm-1):1677
nD24.2℃:1.5497
N-(2-丁烯基)-N-(3-异丙苯基)-2-氯-2-(3-氯苯基)乙酰胺:
IR ν 净(cm-1):1676
nD21.4℃:1.5617
参考实施例6
合成N-(2-丁烯基)-N-(4-氯-3-异丙苯基)胺:
将2.8g无水碳酸钾和2.0g1-氯-2-丁烯加到3.2g4-氯-3-异丙基苯胺的15ml N,N-二甲基甲酰胺溶液中,接着在70-90℃搅拌1小时。滤除碳酸钾后,加入100ml水,然后用甲苯提取。用无水硫酸钠干燥后,将反应溶液用蒸发器浓缩,进行硅胶色谱分离,得1.5g所需化合物。
IR ν 净(cm-1):3418
nD23.0℃:1.5145
还可用同样方法合成N-(2-丁烯基)-N-(3-异丙苯基)胺。
IR ν 净(cm-1):3413
nD21.4℃:1.5303
参考实施例7
合成3,4-顺-4-乙基-3-(3-氯苯基)-1-(3-异丙苯基)吡咯烷-2-酮(比较化合物E):
将2.0g N-(2-丁烯基)-N-(3-异丙苯基)-2-氯-2-(3-氯苯基)乙酰胺加入15ml甲苯中,并在回流温度搅拌下将1.7g氢化三丁基锡和痕量α,α-偶氮二异丁腈(AIBN)加到溶液中。继续搅拌10分钟后,溶液温度回落至室温,将反应溶液用蒸发器浓缩,然后进行柱色谱分离,得0.9g第一洗脱化合物,3,4-反-4-乙基-3-(3-氯苯基)-1-(3-异丙苯基)吡咯烷-2-酮(化合物61)和0.3g最后洗脱化合物,3,4-顺-4-乙基-3-(3-氯苯基)-1-(3-异丙苯基)吡咯烷-2-酮(化合物E)。
IR ν液体石蜡(cm-1):1702
NMR(CDCl3)δppm:0.91(3H,t,J=7.6Hz),1.24(6H,d,J=6.6Hz),1.21-1.75(2H,m),2.63-2.74(1H,m),2.80-2.95(1H,m),3.69(1H,dd,J=7.4Hz,9.3Hz),4.00(1H,d,J=8.9Hz),4.03(1H,dd,J=7.3Hz,9.3Hz),7.03(1H,d,J=8.0Hz),7.13(1H,d,J=7.3Hz),7.20-7.66(6H,m).
吡咯烷环3-和4-位的空间构象由吡咯烷环3-位的质子(用3-H表示)和吡咯烷环4-位的质子(由4-H表示)的偶合常数确定。也就是说,在4-乙基-3-(3-氯苯基)-1-(3-异丙苯基)-2-吡咯烷-2-酮情况下,3,4-反式异构体由J3H-4H=10.3Hz确定,而3,4-顺式异构体由J3H-4H=8.9Hz确定。
表1列出了有关本发明制备方法的,由式(Ⅰ)代表的化合物(化合物1-57)和本发明由式(Ⅲ)代表的化合物(化合物58-62)的例子。
〔制剂实施例及试验〕
下面,将对本发明的制剂实施例和某些除草剂的除草活性试验进行描述。
制剂实施例1(可湿性粉剂)
将20份重的本发明化合物58,2份重的Neopelex(商标名,Kao公司制造;十二烷基苯磺酸钠),1份重的Neugen EA80(商标名,由Sanyo化学工业有限公司制造;聚氧乙烯壬苯基醚),5份重的白碳和72份重的硅藻土充分磨碎并混合得到可湿性粉剂。
制剂实施例2(可湿性粉剂)
将20份重的本发明化合物59,2份重的烷基苯磺酸钠、1份重的聚氧乙烯烷基苯基醚和77份重的Giecrite充分磨碎并混合得可湿性粉剂。
制剂实施例3(可湿性粉剂)
通过将50份重的本发明的化合物60,5份重的白碳,6份重的聚氧乙烯烷基苯基醚硫酸铵,2份重的木素磺酸钠和37份重的硅藻土用喷射-O-混合器充分磨碎和混合得可湿性粉剂。
制剂实施例4(流动剂)
将91.7份重的水加到5份重的本发明化合物58,2份重的木素磺酸钠,0.3份重的黄原胶和1份重的聚氧乙烯烷芳基醚中,混合,然后用沙磨机磨细混合物得流动剂。
制剂实施例5(流动剂)
将30份重的本发明化合物59和10份重的Sun Ekisu P252(商标名,如前述)于50份重水中的溶液湿磨并混合,然后加入并混合0.2份重的Kelzan S(商标名,Kelco公司制造;黄原胶)于9.6份重的水中的溶液和0.2份重的Deltop(商标名,Takeda化学工业有限公司制造;有机碘杀真菌剂),得流动剂。
制剂实施例6(粉剂)
将1份重的本发明化合物60,0.5份重的Emulgen 910(商标名,Kao公司制造;聚氧乙烯壬苯基醚)和98.5份重的高岭土充分磨细混合得粉剂。
制剂实施例7(粉剂)
将3份重的本发明化合物61,3份重的木素磺酸钠、2份重的聚氧乙烯烷芳基醚和92份重的粘土混合并磨细得粉剂。
制剂实施例8(干流动剂)
将60份重量磨细的本发明化合物60,5份重的烷基苯磺酸钠和35份重的聚丙二醇聚乙二醇醚混合得干流动剂。
制剂实施例9(粒剂)
将0.3份重的本发明化合物58,2份重Neopelex(商标名,如前所述)、2份重的Sun Ekisu P252(商标名,Sanyo-Kokusaku Pulp有限公司制造;木素磺酸钠),72.7份重的膨润土和23份重的滑石充分混合。往生成的混合物中加入适量的水使其湿润,接着将其挤压通过一小喷射模压机成为小球。小球在30-60℃空气中干燥后,然后压碎成为小粒,然后小粒通过筛分机分类收集0.3-2mm的小粒。
制剂实施例10(粒剂)
将0.5份重的本发明化合物61,2份重的GosenolGL-05S(日本合成化学工业有限公司生产的聚乙烯醇),2份重的Sun Ekisu P252(商标名,Sanyo-Kokusaku Pulp有限公司制造;苯磺酸钠)和95.5份粘土充分混合,向混合物中加入适量水使其湿润,接着将其挤压通过小喷射模压机成为小球。小球在60-90℃于空气中干燥后,压碎成为小粒,此小粒通过筛分机分类收集0.3-1mm的小粒。
制剂实施例11(乳剂)
将10份重的本发明化合物60,10份重的Sorpole 800A(商标名,Toho化学工业有限公司制造;非离子/阴离子表面活性剂混合物)和80份重的邻二甲苯相互混合然后溶解得乳剂。
试验1 水下条件下的土壤处理(芽前处理)
将1/5000公亩Wagner罐填满土。将稗草(Echinochloa Crusgalli),藨草属植物(Scirpus juncoides),矮慈菇(Sagittaria Pygmaea),鸭舌草(Monochoria vaginalis),水莎草(Cyperus Serotinus)和母草属(Lindernia pyxidaria)的种子或块茎在水下条件下栽种。将预先培养的两对水稻(Oryza sativa)秧苗(2-3叶期)移植到每个罐中并使其在温室中生长。每对由两株水稻秧苗组成。一天之后(杂草发芽之前),每罐用粒剂处理,该粒剂根据制剂实施例9所述的工艺加工预定量的试验化合物而制备。30天后观察杂草的生长状态和水稻的伤害状态。结果总结在表2和3中。
在表中,每个试验植物的损伤程度和水稻的伤害程度是通过将试验植物和水稻的生长状态与未处理罐中的相应植物和水稻比较而确定的,它们根据如下标准表示。
以干重与未处理组干重相比的
等级 百分数表示的生长率(%)
5 0-5 (死亡)
4 6-10 (严重损伤)
3 11-40 (中等损伤)
2 41-70 (弱损伤)
1 71-90 (轻微损伤)
0 91-100 (无损伤)
比较化合物A、B、C、D和E分别表示如下化合物。
A:1-(3-三氟甲基苯基)-3-氯-4-氯甲基吡咯烷-2-酮。
B:1-甲基-3-苯基-5-(3-三氟甲基苯基)吡啶-4(1H)-酮。
C:4-氯甲基-3-(3-氯苯基)-1-(3-三氟甲苯基)吡咯烷-2-酮。
D:4-乙基-3-(3-氟苯基)-1-(3-三氟甲基苯基)吡咯烷-2-酮。
E:3,4-顺-4-乙基-3-(3-氯苯基)-1-(3-异丙苯基)吡咯烷-2-酮(在参考实施例7中制备)。
在这些试验中,与对比药剂A、C和D相比,本发明的除草组合物尽管以低施用比率,仍对水稻田中的样品杂草显示出较高除草效果,它们还对水稻有优异的安全性。另外,对应于本发明化合物的顺式异构体(对比药剂E)几乎不显示除草作用。
试验2 水下条件下的土壤处理(生长期处理)
将1/5000公亩Wagner罐填满土。在水下条件下播入稗草(Echinochloa crusgalli)、藨草属植物(Scirpus juncoides),鸭舌草(Monochoria vaginalis)和母草属(Lindernia pyxidaria)的种子。将预先培养的两对水稻(Oryza sativa)秧苗(2-3叶期)移栽到每个罐中并使其在温室中生长。每对由两株水稻秧苗组成。当稗草变成二叶时,每罐用粒剂进行处理,该粒剂根据制剂实施例10所述的工艺加工预定量的试验化合物而制备。30天后观察杂草的发芽情况及水稻的伤害情况。结果总结在表4中。表中每种试验植物的损伤程度和水稻的伤害程度用与试验1相同的方法确定。
在这些试验中相似的是,与对比药剂A、C和D相比,本发明的除草组合物尽管以低的施用比率,仍对水稻田中的样品杂草显示较高的除草效果,它们也对水稻显示优异的安全性。另外,对应于本发明化合物的顺式异构体(比较药剂E)几乎不显示除草作用。
Claims (5)
1、一种制备由式(I)代表的4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮的3,4-反式异构体的方法
(I)
(其中R1为氢原子、卤原子或甲基;R2为三氟甲基,具有1至3个碳原子的卤代烷氧基,具有1至3个碳原子的卤代烷硫基,具有1至4个碳原子的低级烷基,具有1至4个碳原子的烷氧基、硝基、氰基、苯氧基、羟基或卤原子;X为氢原子、卤原子、三氟甲基,具有1至3个碳原子的烷基、氰基或硝基;n为1或2并指示由X代表的取代基的数目,当n=2时,基团X可以相同或不同)
该方法包括碱与式(I)代表的4-乙基-1-(取代苯基,-3-(取代苯基)吡咯烷-2-酮的3,4-顺式异构体反应的步骤。
2、根据权利要求1的方法,其中4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮的3,4-顺式异构体包括在4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮的3,4-顺式异构体和3,4-反式异构体混合物中。
3、由式(Ⅲ)代表的4-乙基-1-(取代苯基)-3-(取代苯基)吡咯烷-2-酮的3,4-反式异构体
(Ⅲ)
(其中R2为异丙基,X为在3-位取代的氟原子,氯原子或溴原子,或在3-和4-位或在3-和5-位取代的氟原子)。
5、一种对稻株无伤害防治水稻田中杂草的方法,包括将有效量的权利要求3化合物施用到水稻田中。
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JP2235765A JPH04117359A (ja) | 1990-09-07 | 1990-09-07 | 3,4―トランス―4―エチル―1―(置換フェニル)―3―(置換フェニル)ピロリジン―2―オン類の製造方法 |
JP235765/90 | 1990-09-07 | ||
JP4319791 | 1991-03-08 | ||
JP43197/91 | 1991-03-08 |
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CN1061593A true CN1061593A (zh) | 1992-06-03 |
CN1029766C CN1029766C (zh) | 1995-09-20 |
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US (1) | US5123954A (zh) |
EP (1) | EP0477626A1 (zh) |
KR (1) | KR940005013B1 (zh) |
CN (1) | CN1029766C (zh) |
AU (1) | AU632963B2 (zh) |
BR (1) | BR9103881A (zh) |
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CN108137512A (zh) * | 2015-07-31 | 2018-06-08 | 杜邦公司 | 用作除草剂的环状n-酰胺化合物 |
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DE4213931A1 (de) * | 1992-04-28 | 1993-11-04 | Thomae Gmbh Dr K | Cyclische iminoderivate, diese verbindungen enthaltende arzneimittel und verfahren zu ihrer herstellung |
US5302726A (en) * | 1992-12-21 | 1994-04-12 | Imperial Chemical Industries Plc | N-benzyl-4-alkyl-pyrrolidinone herbicides |
US5908934A (en) * | 1996-09-26 | 1999-06-01 | Bristol-Myers Squibb Company | Process for the preparation of chiral ketone intermediates useful for the preparation of flavopiridol and analogs |
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US4069038A (en) * | 1975-03-28 | 1978-01-17 | Stauffer Chemical Company | Acyclic and alicyclic N-substituted halo-2-pyrrolidinones and their utility as herbicides |
EP0055215B1 (de) * | 1980-12-19 | 1985-01-30 | Ciba-Geigy Ag | Neue Fluorpyrrolidinone, Verfahren zu deren Herstellung, sie enthaltende herbizide Mittel und deren Verwendung |
US4960457A (en) * | 1988-12-27 | 1990-10-02 | Ici Americas Inc. | Substituted 1,3-diphenyl pyrrolidones and their use as herbicides |
JP2833817B2 (ja) * | 1989-03-15 | 1998-12-09 | 三井化学株式会社 | 4―エチル―3―(置換フェニル)―1―(3―トリフルオロメチルフェニル)―2―ピロリジノン誘導体、その製造法およびこれらを有効成分とする除草剤 |
-
1991
- 1991-09-02 AU AU83545/91A patent/AU632963B2/en not_active Ceased
- 1991-09-06 EP EP91115087A patent/EP0477626A1/en not_active Ceased
- 1991-09-06 US US07/755,366 patent/US5123954A/en not_active Expired - Fee Related
- 1991-09-07 KR KR1019910015638A patent/KR940005013B1/ko not_active IP Right Cessation
- 1991-09-07 CN CN91109570A patent/CN1029766C/zh not_active Expired - Fee Related
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CN108137512A (zh) * | 2015-07-31 | 2018-06-08 | 杜邦公司 | 用作除草剂的环状n-酰胺化合物 |
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BR9103881A (pt) | 1992-05-26 |
AU632963B2 (en) | 1993-01-14 |
EP0477626A1 (en) | 1992-04-01 |
CN1029766C (zh) | 1995-09-20 |
KR920006312A (ko) | 1992-04-27 |
AU8354591A (en) | 1992-03-12 |
KR940005013B1 (ko) | 1994-06-09 |
US5123954A (en) | 1992-06-23 |
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