CN1036564C - 含具有除草活性的戊二酰亚胺的除草组合物 - Google Patents
含具有除草活性的戊二酰亚胺的除草组合物 Download PDFInfo
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- CN1036564C CN1036564C CN90107393A CN90107393A CN1036564C CN 1036564 C CN1036564 C CN 1036564C CN 90107393 A CN90107393 A CN 90107393A CN 90107393 A CN90107393 A CN 90107393A CN 1036564 C CN1036564 C CN 1036564C
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- Prior art keywords
- alkyl
- group
- carbonyl
- alkoxyl
- methyl
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- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 162
- 239000000203 mixture Substances 0.000 claims abstract description 130
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical class O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000000034 method Methods 0.000 claims abstract description 41
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 37
- 239000000460 chlorine Substances 0.000 claims description 236
- -1 Phenyl Chemical group 0.000 claims description 190
- 125000003545 alkoxy group Chemical group 0.000 claims description 111
- 229910052760 oxygen Inorganic materials 0.000 claims description 101
- 239000001301 oxygen Substances 0.000 claims description 96
- 229910052739 hydrogen Inorganic materials 0.000 claims description 94
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 81
- 229910052731 fluorine Inorganic materials 0.000 claims description 65
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 claims description 61
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 claims description 56
- 239000001257 hydrogen Substances 0.000 claims description 52
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 45
- 229910052801 chlorine Inorganic materials 0.000 claims description 44
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 39
- 125000004414 alkyl thio group Chemical group 0.000 claims description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 35
- 150000003839 salts Chemical class 0.000 claims description 32
- 125000000304 alkynyl group Chemical group 0.000 claims description 31
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 27
- 229910052794 bromium Inorganic materials 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 125000003342 alkenyl group Chemical group 0.000 claims description 24
- 125000000623 heterocyclic group Chemical group 0.000 claims description 24
- 150000002431 hydrogen Chemical class 0.000 claims description 24
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 23
- 241000196324 Embryophyta Species 0.000 claims description 22
- 125000005843 halogen group Chemical group 0.000 claims description 22
- 239000011737 fluorine Substances 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 13
- 239000005864 Sulphur Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 11
- 150000001345 alkine derivatives Chemical class 0.000 claims description 11
- 125000001544 thienyl group Chemical group 0.000 claims description 11
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 9
- 235000007164 Oryza sativa Nutrition 0.000 claims description 9
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 9
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 235000009566 rice Nutrition 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 125000004423 acyloxy group Chemical group 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 229930194542 Keto Natural products 0.000 claims description 6
- 125000004744 butyloxycarbonyl group Chemical group 0.000 claims description 6
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 241000195493 Cryptophyta Species 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 5
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 claims description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 125000004916 (C1-C6) alkylcarbonyl group Chemical group 0.000 claims description 4
- 125000005862 (C1-C6)alkanoyl group Chemical group 0.000 claims description 4
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 claims description 4
- 239000000575 pesticide Substances 0.000 claims description 4
- 230000008635 plant growth Effects 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 108090000723 Insulin-Like Growth Factor I Proteins 0.000 claims description 3
- 102000013275 Somatomedins Human genes 0.000 claims description 3
- 125000005092 alkenyloxycarbonyl group Chemical group 0.000 claims description 3
- 125000005336 allyloxy group Chemical group 0.000 claims description 3
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 claims description 3
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims description 2
- 125000004694 alkoxyaminocarbonyl group Chemical group 0.000 claims description 2
- 125000001887 cyclopentyloxy group Chemical group C1(CCCC1)O* 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 241000209094 Oryza Species 0.000 claims 6
- MJYGPNBYCMSMFL-UHFFFAOYSA-N [O].C1CCOC1 Chemical compound [O].C1CCOC1 MJYGPNBYCMSMFL-UHFFFAOYSA-N 0.000 claims 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims 2
- 230000005791 algae growth Effects 0.000 claims 2
- JWNIBBUFURPRSI-UHFFFAOYSA-N 2-chloro-5-[2,6-dioxo-4-(trifluoromethyl)piperidin-1-yl]-4-fluoro-n-methoxybenzamide Chemical compound C1=C(Cl)C(C(=O)NOC)=CC(N2C(CC(CC2=O)C(F)(F)F)=O)=C1F JWNIBBUFURPRSI-UHFFFAOYSA-N 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 46
- 239000004009 herbicide Substances 0.000 abstract description 28
- 239000003619 algicide Substances 0.000 abstract description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 3
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- WPPOOQHRMXWIDW-UHFFFAOYSA-N thiirane-2,3-dione Chemical compound O=C1SC1=O WPPOOQHRMXWIDW-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 116
- 239000002585 base Substances 0.000 description 108
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 89
- 239000007787 solid Substances 0.000 description 76
- 239000000243 solution Substances 0.000 description 75
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 68
- 238000006243 chemical reaction Methods 0.000 description 54
- 239000000376 reactant Substances 0.000 description 52
- 239000003921 oil Substances 0.000 description 49
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 47
- 235000019439 ethyl acetate Nutrition 0.000 description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 39
- 238000002360 preparation method Methods 0.000 description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 35
- 239000000047 product Substances 0.000 description 33
- 208000035126 Facies Diseases 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 31
- 238000003756 stirring Methods 0.000 description 31
- 239000002904 solvent Substances 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 26
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- 238000005406 washing Methods 0.000 description 25
- 239000011734 sodium Substances 0.000 description 22
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 238000000605 extraction Methods 0.000 description 21
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 20
- 230000000694 effects Effects 0.000 description 19
- PTGCUXZHDCRLEE-UHFFFAOYSA-N 4-(trifluoromethyl)oxane-2,6-dione Chemical compound FC(F)(F)C1CC(=O)OC(=O)C1 PTGCUXZHDCRLEE-UHFFFAOYSA-N 0.000 description 18
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 18
- 241000192043 Echinochloa Species 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 17
- 239000000706 filtrate Substances 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 240000001592 Amaranthus caudatus Species 0.000 description 15
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 13
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
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- 239000012044 organic layer Substances 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 11
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- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 7
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- AFZLCOLNTRPSIF-UHFFFAOYSA-N 5-amino-2-chloro-4-fluorophenol Chemical class NC1=CC(O)=C(Cl)C=C1F AFZLCOLNTRPSIF-UHFFFAOYSA-N 0.000 description 4
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- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- AFLNWZNDCWEJEK-UHFFFAOYSA-N propan-2-yl 2-(5-amino-2-chloro-4-fluorophenyl)sulfanylacetate Chemical compound CC(C)OC(=O)CSC1=CC(N)=C(F)C=C1Cl AFLNWZNDCWEJEK-UHFFFAOYSA-N 0.000 description 1
- LRSQVXIWQFRSST-UHFFFAOYSA-N propan-2-yl 3-amino-4-fluorobenzoate Chemical class CC(C)OC(=O)C1=CC=C(F)C(N)=C1 LRSQVXIWQFRSST-UHFFFAOYSA-N 0.000 description 1
- RYDLWHBYEGZRMI-UHFFFAOYSA-N propan-2-yl 5-amino-2,4-dichlorobenzoate Chemical class CC(C)OC(=O)C1=CC(N)=C(Cl)C=C1Cl RYDLWHBYEGZRMI-UHFFFAOYSA-N 0.000 description 1
- RUSKVPDYYKTEMU-UHFFFAOYSA-N propan-2-yl 5-amino-2,4-difluorobenzoate Chemical class CC(C)OC(=O)C1=CC(N)=C(F)C=C1F RUSKVPDYYKTEMU-UHFFFAOYSA-N 0.000 description 1
- XEHDGJHIPJRFLH-UHFFFAOYSA-N propan-2-yl 5-amino-2-chlorobenzoate Chemical class CC(C)OC(=O)C1=CC(N)=CC=C1Cl XEHDGJHIPJRFLH-UHFFFAOYSA-N 0.000 description 1
- HUSRLTYWWKWYBJ-UHFFFAOYSA-N propan-2-yl 5-amino-4-fluoro-2-(trifluoromethyl)benzoate Chemical class CC(C)OC(=O)C1=CC(N)=C(F)C=C1C(F)(F)F HUSRLTYWWKWYBJ-UHFFFAOYSA-N 0.000 description 1
- YLZUJFLALUCJQI-UHFFFAOYSA-N propan-2-yl n-(2-chlorophenyl)carbamate Chemical compound CC(C)OC(=O)NC1=CC=CC=C1Cl YLZUJFLALUCJQI-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 238000013207 serial dilution Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004577 thatch Substances 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- NRZWQKGABZFFKE-UHFFFAOYSA-N trimethylsulfonium Chemical class C[S+](C)C NRZWQKGABZFFKE-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000004562 water dispersible granule Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/32—Cyclic imides of polybasic carboxylic acids or thio analogues thereof
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/46—N-acyl derivatives
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- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
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- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
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- A—HUMAN NECESSITIES
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- 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
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- A—HUMAN NECESSITIES
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A—HUMAN NECESSITIES
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings 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 or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings 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 or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
本发明涉及具有除草活性的具有下述结构的戊二酰亚胺(其中R、R2、T、X、Y和Z的定义见说明书)、含这些化合物的除草组合物以及这类化合物作为除草剂和杀藻剂的使用方法。
Description
本发明涉及具有除草和杀藻活性的新的戊二酰亚胺、含有该化合物的组合物及该化合物的使用方法。
在过去的数年中,人们加强了抑制不需要的植物生长的除草剂的研究。美国专利4,400,202公开了N-(间-苯基戊二酰亚氨基)脲和N-(间-苯基琥珀酰亚氨基)脲,以及这些化合物作为除草剂的用途。该专利没有披露任何在苯环上有其它取代基的化合物。
美国专利4,595,408公开了N-(间-酰氨基苯基)琥珀酰亚胺和N-(间-酰氨基苯基)戊二酰亚胺,以及这些化合物作为除草剂的用途。该专利没有披露任何在苯环上有其它取代基的化合物。
人们还需要与现存化合物同样有效或更有效的除草剂。
A为羰基(C=O)、硫代羰基(C=S)或亚甲基(CH2);
A1为羰基(C=O)或亚甲基(CH2);
但当Z为氢(H)时,A和A1不都是CH2
D为CH,但当X为氢时,D为氮(N);
Q为亚甲基[(CH2)n](其中n为0或1),或为氧(O);
R为(C1-C4)烷基、含1-9个卤原子的(C1-C4)卤代烷基或苯基;
R1为氢或(C1-C2)烷基;但当X和Z分别独立地为氢或卤原子且Y为卤原子时,R1为氢;
R2为氢;或者
R、R1和R2一起形成稠合的苯环;
X为氢、氰基(CN)或卤原子;
Y为氢、卤原子、氰基(CN)、(C1-C3)烷硫基、卤代(C1-C3)烷硫基、(C1-C3)烷基、卤代(C1-C3)烷基、硝基、卤代(C1-C3)烷氧基或(C1-C3)烷氧基;
当Y为氢时,R为三氟甲基(CF3),R1和R2为氢且Z不是氢;
T为氢或氟;且
Z为氢、羟基(OH)、卤原子、氰基、硫羟基(SH)、烷基磺酰氧基(-OSO2烷基)、苯基磺酰氧基(-OSO2苯基)、烷基、烷氧基、链烯氧基、链炔氧基、环烷氧基、环烷基烷氧基、苯基烷氧基、烷硫基、链烯硫基、链炔硫基、环烷硫基、环烷基烷硫基、苯基烷硫基、链烷酰氧基、链烷酰硫基、烷氧羰基烷硫基、烷氧羰基烷氧基、烷氧羰基(烷氧基)烷氧基、烷氧基烷氧基、(烷硫基)烷氧基、烷氧基烷硫基、烷硫基烷硫基、(苯硫基)烷氧基、苯氧基烷氧基、苯硫基烷硫基、苯氧基烷硫基、羧基烷硫基、羧基烷氧基、杂环氧基、杂环烷氧基、羧基、甲酰基、烷羰基、烷氧羰基、(烷硫基)羰基、烷氧羰基烷氧羰基、苯氧羰基、烷氧基烷氧羰基、链烯氧基羰基、链炔氧基羰基、环烷氧羰基、环烷基烷氧羰基、(链烯硫基)羰基、(链炔硫基)羰基、(环烷硫基)羰基、(环烷基烷硫基)羰基、杂环羰基、杂环烷氧羰基、杂环氧羰基、三烷基甲硅烷基烷氧羰基、二烷氧基膦酰基羰基[-C(=O)O烷基P(=O)烷氧基)2]、二烷基亚胺基氧羰基[-C(=O)ON=C(烷基)2]、烷基亚胺基氧羰基、烷基(烷氧基)亚胺基氧羰基、烷基(烷硫基)亚胺基氧羰基、苯氨基羰基、氨基羰基、烷氨基羰基、链烯氨基羰基、链炔氨基羰基、烷氧氨基羰基、烷氧基烷基、链烯氧基烷基、链炔氧基烷基、环烷氧基烷基、环烷基烷氧基烷基、烷酰氧基烷基、烷硫基烷基、链烯硫基烷基、链炔硫基烷基、环烷氧基烷基、环烷基烷硫基烷基、(烷酰硫基)烷基、苯氧基烷基、苯硫基烷基、烷氧羰基烷氧基烷基、醛肟基[-CH=NOH]、烷基醛肟基[-CH=NO烷基]、链烯基醛肟基[-CH=NO链烯基]、链炔基醛肟基[-CH=NO链炔基]、烷氧羰基烷基醛肟基[-CH=NO(烷氧羰基)烷基]、烷基(烷氧基)醛肟基[-C(烷氧基)=NO烷基]、链烯基(烷氧基)醛肟基[-C(烷氧基)=NO链烯基]、链炔基(烷氧基)醛肟基[-C(烷基)=NO链炔基]、烷氧羰基烷基(烷氧基)醛肟基[-C(烷氧基)=NO(烷氧羰基)烷基]、烷基(烷基)醛肟基[-C(烷基)=NO烷基]、链烯基(烷基)醛肟基[-C(烷基)=NO链烯基]、链炔基(烷基)醛肟基[-C(烷基)=NO链炔基]、烷氧羰基烷基(烷基)醛肟基[-C(烷基)=NO(烷氧羰基)烷基]、烷基(烷硫基)醛肟基[-C(烷硫基)=NO烷基]、链烯基(烷硫基)醛肟基[-C(烷硫基)=NO链烯基]、链炔基(烷硫基)醛肟基[-(烷硫基)=NO链炔基]、烷氧羰基烷基(烷硫基)醛肟基[-C(烷硫基)=NO(烷氧羰基)烷基]、杂环基、烷氨基、链烯氨基、链炔氨基或烷酰基氨基;
但当X和Y均为溴(Br)或氯(Cl)且D为CH时,Z不是氢;或者
L为氧(O)或硫(S);
R3为氢或烷基;
R4为氢、烷基、链烯基、链炔基、烷氧基烷基、链烯氧基烷基、链炔氧基烷基、氰基烷基、烷氧羰基烷基、环烷基、环烷基烷基、苯基烷基、烷硫基烷基、链烯硫基烷基、链炔硫基烷基、杂环基、杂环基烷基、烷氨基烷基、烷氨基羰基烷基、烷氧羰基或烷酰基;且
R5为氢、(C1-C3)烷基或氟原子。
本发明还包括上述化合物的农药化学可接受的盐。
烷基是指直链或支链烷基,例如(C1-C8)烷基(如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、1-乙基丙基或正辛基)。上述Z取代基中所列的任何一个取代基的烷基部分还可被1-5个卤原子取代,形成如三氟甲基、1,1,1,2,2-五氟乙基或(三氟甲基)甲基等基团;可被苯基取代,形成如苄基或苯乙基等基团;或可被氰基取代,形成如氰基甲基、2-氰基乙基或1-氰基乙基等基团。环烷基为,例如,环丙基、环丁基、环戊基、环己基,并包括可被(C1-C4)烷基取代的环烷基,如2-甲基环丙基,及可被卤原子取代的环烷基,如2,2-二氯环丙基。苯基可被1个或2个取代基如(C1-C3)烷基、卤原子、(C1-C3)烷氧基或三氟甲基所取代。R代表的卤代烷基为,例如,氟甲基、二氟甲基、三氟甲基或五氟乙基。
杂环基指3至6员杂环,其中含1个、2个或3个杂原子如氧、氮或硫,还包括饱和或不饱和环,如四氢呋喃基、呋喃基、环氧基、吡啶基、哌啶基、二氧环戊基、异噁唑烷基、三唑基、噻吩基、噻唑基或哌嗪基,这些基团可被1-3个(C1-C6)烷基取代,如5,5-二甲基噁唑啉基。
卤原子指氟、氯、溴或碘原子。
在取代基Y和Z中,“硫代”指-S-。当不与羰基相连时,“硫代”还包括亚硫酰基(-SO-)和硫酰基。
取代的氨基如烷氨基包括一和二-取代基团,如一烷基氨基和二烷基氨基。
肟可为顺式或反式构型,或两者的混合物。
农药化学可接受的盐包括那些本领域已知形式的盐,如钠、钾、钙和镁等金属盐,铵盐如异丙基铵盐以及三烷基锍盐如三甲基锍盐。
烷氧基为,例如(C1-C6)烷氧基(如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基或仲丁氧基)。链烯氧基为,例如,(C3-C6)链烯氧基(如烯丙氧基、2-氯烯丙氧基或3,3-二氯烯丙氧基)。链炔氧基为,例如,(C3-C6)链炔氧基(如炔丙氧基、1-甲基炔丙氧基、1-(3-丁炔基)氧基或1-(2-丁炔基)氧基。苯基烷氧基为,例如,苯基(C1-C6)烷氧基(如苯基甲氧基)。烷硫基为,例如,(C1-C6)烷硫基(如甲硫基、乙硫基、丙硫基、丁硫基)。链烯硫基为,例如,(C3-C6)链烯硫基。链炔硫基为,例如,(C3-C6)链炔硫基。苯基烷硫基为,例如,苯基(C1-C6)烷硫基。烷酰氧基为,例如,(C1-C6)烷酰氧基。烷酰硫基为,例如,(C1-C6)烷酰硫基(如乙酰硫基)。烷氧羰基烷硫基为,例如,(C1-C6)烷氧羰基(C1-C4)烷硫基(如甲氧羰基甲硫基或异丙氧羰基甲硫基)。烷氧羰基烷氧基为,例如,(C1-C6)烷氧羰基(C1-C4)烷氧基(如甲氧羰基甲氧基)。烷氧羰基(烷氧基)烷氧基为,例如,(C1-C6)烷氧羰基[(C1-C6)烷氧基](C1-C6)烷氧基[如甲氧羰基(甲氧基)甲氧基]。烷氧基烷氧基为,例如,(C1-C6)烷氧基(C1-C6)烷氧基(如甲氧基甲氧基或2-甲氧基乙氧基)。(烷硫基)烷氧基为,例如,[(C1-C6)烷硫基](C1-C6)烷氧基。烷氧基烷硫基为,例如,(C1-C6)烷氧基(C1-C6)烷硫基。烷硫基烷硫基为,例如,(C1-C6)烷硫基(C1-C6)烷硫基。(苯硫基)烷氧基为,例如,(苯硫基)(C1-C6)烷氧基[如(苯硫基)甲氧基]。苯氧基烷氧基为,例如,苯氧基(C1-C6)烷氧基。苯硫基烷硫基为,例如,苯硫基(C1-C6)烷硫基。苯氧基烷硫基为,例如,苯氧基(C1-C6)烷硫基。羧基烷硫基为,例如,羧基(C1-C6)烷硫基。羧基烷氧基为,例如,羧基(C1-C6)烷氧基(如羧基甲氧基)。烷羰基为,例如,(C1-C)烷羰基(如甲羰基,即乙酰基)。烷氧羰基为,例如,(C1-C6)烷氧羰基(如甲氧羰基、乙氧羰基、正丙氧羰基、异丙氧羰基、1-氰基乙氧羰基、异丁氧羰基或仲丁氧羰基)。(烷硫基)羰基为,例如,[(C1-C6)烷硫基]羰基[如(乙硫基)羰基或(异丙硫基)羰基]。烷氧羰基烷氧羰基为,例如,(C1-C6)烷氧基羰基(C1-C6)烷氧羰基[如甲氧羰基(甲基)甲氧羰基或乙氧羰基甲氧羰基]。烷氧基烷氧羰基为,例如(C1-C6)烷氧基(C1-C6)烷氧羰基[如(2-甲氧基)乙氧羰基或(2-甲氧基-1-甲基)乙氧羰基]。链烯氧羰基为,例如,(C3-C6)链烯氧羰基。链炔氧羰基为,例如,(C3-C6)链炔氧羰基(如炔丙氧羰基、3-碘代炔丙氧羰基、1-甲基炔丙氧羰基或3-丁炔氧羰基)。环烷氧羰基为,例如,(C3-C6)环烷氧羰基(如环丁氧羰基、环戊氧羰基或环己氧羰基)。环烷基烷氧羰基为,例如,(C3-C6)环烷基(C1-C6)烷氧羰基。(链烯硫基)羰基为,例如,[(C3-C6)链烯硫基]羰基。(链炔硫基)羰基为,例如,[(C3-C6)链炔硫基]羰基。(环烷硫基)羰基为,例如,[(C3-C6)环烷硫基)羰基。(环烷基烷硫基)羰基为,例如,[(C3-C6]环烷基(C1-C6)烷硫基)羰基。杂环烷氧羰基为杂环(C1-C6)烷氧羰基。杂环氧羰基为,例如,3-四氢呋喃氧羰基。三烷基甲基硅烷氧基羰基为,例如,三(C1-C6)烷基甲硅烷基(C1-C6)烷氧羰基(如三甲基甲硅烷基甲氧羰基)。二烷氧基膦酰基烷氧羰基为,例如,二(C1-C6)烷氧基膦酰基(C1-C6)烷氧羰基(如二乙氧基膦酰基甲氧羰基)。二烷基亚氨基氧羰基为,例如,二(C1-C6)烷基亚氨基氧羰基(如二甲基亚氨基氧羰基)。烷基亚氨基氧羰基为,例如,(C1-C6)烷基亚氨基氧羰基。烷基(烷氧基)亚氨基氧羰基为,例如,(C1-C6)烷基[(C1-C6)烷氧基]亚氨基氧羰基。烷基(烷硫基)亚氨基氧羰基为,例如,(C1-C6)烷基[(C1-C6)烷硫基]亚氨基氧羰基。烷基氨基羰基为,例如,-(C1-C6)烷基氨基羰基(如异丙基氨基羰基)或二(C1-C6)烷基氨基羰基。链烯氨基羰基为,例如,-(C3-C6)链烯氨基羰基。链炔氨基羰基为,例如,-(C3-C6)链炔氨基羰基(如炔丙氨基羰基)。烷氧基氨基羰基为,例如,-(C1-C6)烷氧基氨基羰基(如甲氧基氨基羰基)。烷氧基烷基为,例如,(C1-C6)烷氧基(C1-C6)烷基(如甲氧甲基、乙氧甲基或异丙基氧甲基)。链烯氧烷基为,例如,(C3-C6)链烯氧(C1-C6)烷基。链炔氧烷基为,例如,(C3-C6)链炔氧(C1-C6)烷基(如炔丙氧甲基或1-甲基炔丙氧甲基)。环烷氧烷基为,例如,(C3-C6)环烷氧(C1-C6)烷基。环烷基烷氧基烷基为,例如,(C3-C6)环烷基(C1-C6)烷氧基(C1-C6)烷基。烷酰氧烷基为,例如,(C1-C6)烷酰氧(C1-C6)烷基(如乙酰氧甲基)。烷硫基烷基为,例如,(C1-C6)烷硫基(C1-C6)烷基(如甲基硫基甲基、异丙硫基甲基或乙硫基甲基)。链烯硫烷基为,例如,(C3-C6)链烯硫(C1-C6)烷基。链炔硫烷基为,例如,(C3-C6)链炔硫(C1-C6)烷基。环烷基硫烷基为,例如,(C3-C6)环烷基硫(C1-C6)烷基。环烷基烷基硫烷基为,例如,(C3-C6)环烷基(C1-C6)烷硫(C1-C6)烷基。(烷酰硫)烷基为,例如,[(C1-C6)烷酰硫](C1-C6)烷基。苯氧烷基为,例如,苯氧(C1-C6)烷基(如苯氧甲基)。苯基硫烷基为,例如,苯基硫(C1-C6)烷基(如苯基硫甲基)。烷氧羰基烷氧烷基为,例如,(C1-C6)烷氧羰基(C1-C6)烷氧基(C1-C6)烷基[如乙氧羰基(甲基)甲氧甲基]。烷氨基烷基为,例如,二(C1-C6)烷基氨基(C1-C6)烷基(如二甲基氨基乙基)。链烯基为,例如,(C3-C6)链烯基(如烯丙基)。链炔基为,例如(C3-C6)链炔基(如炔丙基或1-甲基炔丙基)。烷基醛肟基为,例如,(C1-C6)烷基醛肟基(如甲基醛肟基、异丙基醛肟基或叔丁基醛肟基)。链烯基醛肟基为,例如,(C3-C6)链烯基醛肟基(如烯丙基醛肟基)。链炔基醛肟基为,例如,(C3-C6)链炔基醛肟基(如炔丙基醛肟基)。烷氧羰基烷基醛肟基为,例如,(C1-C6)烷氧羰基(C1-C6)烷基醛肟基。苯基烷基醛肟基为,例如,苯基(C1-C6)烷基醛肟基(如苯甲基醛肟基)。烷基(烷基)醛肟基为,例如,(C1-C6)烷基[(C1-C6)烷基]醛肟基。链烯基(烷基)醛肟基为,例如,(C3-C6)链烯基[(C1-C6)烷基]醛肟基。链炔基(烷基)醛肟基为,例如,(C3-C6)链炔基[(C1-C6)烷基]醛肟基。烷氧羰基烷基(烷基)醛肟基为,例如(C1-C6)烷氧羰基(C1-C6)烷基[(C1-C6)烷基]醛肟基。烷基(烷氧基)醛肟基为,例如,(C1-C6)烷基[(C1-C6)烷基]醛肟基。链烯基(烷氧基)醛肟基为,例如,(C3-C6)链烯基[(C1-C6)烷氧基]醛肟基。链炔基(烷氧基)醛肟基为,例如,(C3-C6)链炔基[(C1-C6)烷氧基]醛肟基。烷氧基羰基烷基(烷氧基)醛肟基为,例如,(C1-C6)烷氧基羰基(C1-C6)烷基[(C1-C6)烷氧基]醛肟基。烷基(烷硫基)醛肟基为,例如,(C1-C6)烷基[(C1-C6)烷硫基]醛肟基。链烯基(烷硫基)醛肟基为,例如,(C3-C6)链烯基[(C1-C6)烷硫基]醛肟基。链炔基(烷硫基)醛肟基为,例如,(C3-C6)链炔基[(C1-C6)烷硫基]醛肟基。烷氧羰基烷基(烷硫基)醛肟基为,例如,(C1-C6)烷氧羰基(C1-C6)烷基[(C1-C6)烷硫基1醛肟基。烷基氨基为,例如,-(C1-C6)烷基氨基或二(C1-C6)烷基氨基。链烯氨基为,例如,-(C3-C6)链烯氨基或二(C3-C6)链烯氨基。链炔氨基为,例如,-(C3-C6)链炔氨基。烷酰氨基为,例如,-(C1-C6)烷酰氨基(如乙酰氨基)。烷氧羰基烷基为,例如,(C1-C6)烷氧羰基(C1-C6)烷基(如异丙氧羰基甲基)。氰基烷基为,例如,氰基(C1-C6)烷基(如氰基甲基或1-氰基乙基)。苯基烷基为,例如,苯基(C1-C6)烷基(如苄基)。杂环烷基为,例如,杂环(C1-C6)烷基(如环氧甲基或2-四氢呋喃甲基)。杂环羰基为,例如,异丁噁唑烷羰基。杂环烷氧基为,例如,杂环(C1-C6)烷氧基(如环氧甲氧基、2-吡啶甲氧基或2-四氢呋喃甲氧基)。杂环氧基为,例如,3-四氢呋喃氧基。
A为C=O、C=S或CH2;
A1为C=O、或CH2;
但当Z为氢时,A和A不都是CH;
D为CH,当X为H时,D为N;
Q为(CH2)n(其中n为0或1)或为氧;
R为(C1-C4)烷基、(C1-C4)卤代烷基或苯基;
R1为H或(C1-C2)烷基,但当X和Z相互独立地为氢或卤原子且Y为卤原子时,R1为H;
R2为H,或与R和R1-起形成稠合苯环;
X为H、Cl、Br、CN或F;
Y为H、Cl、Br、F、I、CH3、SCH3、硝基或OCH3;
但当Y为氢时,R为三氟甲基,R1和R2为氢且Z不是氢;
T为H或F;
Z为H、OH、卤原子、CN、SH、(C1-C6)烷基、(C1-C6)卤代烷基、-OSO2(C1-C6)烷基、-OSO2苯基、羧基、甲酰基、苯氧羰基、(C1-C6)烷氧基、(C3-C6)链烯氧基、(C3-C6)链炔氧基、氰基(C1-C6)烷氧基、苯基(C1-C6)烷氧基、(C1-C6)烷硫基、(C1-C6)烷酰氧基、(C1-C6)烷酰硫基、(C1-C6)烷氧羰基(C1-C4)烷硫基、(C1-C6)烷氧羰基(C1-C4)烷氧基、(C1-C6)烷氧羰基[(C1-C6)烷氧基](C1-C6)烷氧基、(C1-C6)烷氧基(C1-C6)烷氧基、(苯硫基)(C1-C6)烷氧基、羧基(C1-C6)烷氧基、杂环氧基、杂环(C1-C6)烷氧基、(C1-C6)烷基羰基、(C1-C6)烷氧羰基、[(C1-C6)烷硫基]羰基、(C1-C6)烷氧羰基(C1-C6)烷氧羰基、(C1-C6)烷氧基(C1-C6)烷氧羰基、氰基(C1-C6)烷氧羰基、(C3-C6)链烯氧基羰基、(C3-C6)链炔氧基羰基、卤代(C3-C6)链炔氧羰基、(C3-C6)环烷氧羰基、杂环羰基、杂环氧羰基、三(C1-C6)烷基甲硅烷基(C1-C6)烷氧基羰基、二(C1-C6)烷氧膦酰(C1-C6)烷氧羰基、二(C1-C6)烷基亚氨基氧羰基、-(C1-C6)烷基氨基羰基、-(C3-C6)链炔氨基羰基、苯基氨基羰基、-(C1-C6)烷氧基氨基羰基、(C1-C6)烷氧基(C1-C6)烷基、(C3-C6)链烯氧基(C1-C6)烷基、(C3-C6)链炔氧基(C1-C6)烷基、(C1-C6)烷酰氧基(C1-C6)烷基、(C1-C6)烷硫基(C1-C6)烷基、苯氧基(C1-C6)烷基、苯硫基(C1-C6)烷基、(C1-C6)烷氧羰基(C1-C6)烷氧基(C1-C6)烷基、(C1-C6)烷基醛肟基、(C3-C6)链烯醛肟基、(C3-C6)链炔醛肟基、苯基(C1-C6)烷基醛肟基、杂环基,-(C1-C6)烷酰氨基;或者
L为氧或硫;
R3为氢或(C1-C3)烷基;且
R4为氢、(C1-C8)烷基、(C3-C6)链烯基、(C3-C6)链炔基、(C1-C6)烷氧基(C1-C6)烷基、(C3-C6)环烷基、(C3-C6)环烷基(C1-C6)烷基、(C1-C6)烷硫基(C1-C6)烷基、苯基(C1-C6)烷基、氰基(C1-C6)烷基、(C1-C6)烷氧羰基(C1-C6)烷基、(C1-C6)烷氧羰基、杂环基、杂环基(C1-C6)烷基、二(C1-C6)烷氨基(C1-C6)烷基、二(C1-C6)烷氨基羰基(C1-C6)烷基或(C1-C6)烷酰基。
本发明的一类优选化合物是具有式(I)的醚戊二酰亚胺和硫醚戊二酰亚胺,式(I)中:
A为C=O或CH2;
A1为C=O或CH2;
D为CH,当X为H时,D为N;
Q为(CH2)n(其中n为0或1);
R为(C1-C4)烷基、(C1-C4)卤代烷基或苯基;
R1为H或(C1-C2)烷基;
R2为H,或与R和R1一起形成稠合苯环;
X为H、Cl、Br或F;
Y为H、Cl、Br、或CH3;
T为H或F;且
Z为(C1-C6)烷氧基、(C3-C6)链烯氧基、(C3-C6)链炔氧基、苯基(C1-C6)烷氧基、(C1-C6)烷硫基、(C1-C6)烷酰氧基、(C1-C6)烷酰硫基、(C1-C6)烷氧羰基(C1-C6)烷硫基、(C1-C6)烷氧羰基(C1-C4)烷氧基、氰基(C1-C6)烷氧基、(C1-C6)烷氧基(C1-C6)烷氧基、(苯硫基)(C1-C6)烷氧基、羧基(C1-C6)烷氧基、杂环氧基、杂环(C1-C6)烷氧基、(C3-C6)环烷氧基、(C3-C6)环烷基(C1-C6)烷氧基或(C1-C6)烷氧羰基((C1-C6)烷氧基](C1-C6)烷氧基。
这些醚戊二酰亚胺和硫醚戊二酰亚胺中,优选的是具有式(I)且其中A和A1为C=O、D为CH、Q为(CH2)n(n为0)、R为CH3、CHF2或CF3、R1为H、R2为H、X为Cl或F、Y为Br、F或Cl、T为H且Z为(C1-C6)烷氧基、(C3-C6)链烯氧基、(C3-C6)链炔氧基、(C3-C6)环烷氧基、(C3-C6)环烷基(C1-C6)烷氧基或(C1-C6)烷氧基(C1-C6)烷氧基的那些化合物。
更优选的是,当R为CF3、R1和R2为氢、X为氟且Y为氯时,Z为烯丙氧基、异丙氧基、仲丁氧基、炔丙氧基、1-甲基炔丙氧基、环戊氧基、环丙甲氧基、3-四氢呋喃氧基或甲氧基甲氧基。
更优选的是,当R为CHF2、R1和R2为氢、X为氟且Y为氯时,Z为炔丙氧基。
更优选的是,当R为CF3、R1和R2为氢、X为氟且Y为溴时,Z为炔丙氧基。
本发明的第二类优选化合物是具有式(I)的酯戊二酰亚胺,式(I)中:
A为C=O或CH2;
A1为C=O或CH2;
D为CH,当X为H时,D为N;
Q为(CH2)n(其中n为0或1);
R为(C1-C4)烷基、(C1-C4)卤代烷基或苯基;
R1为H或(C1-C2)烷基;
R2为H,或与R和R1一起形成稠合苯环;
X为H、Cl、Br或F;
Y为H、Cl、Br、F或CH3;
T为H或F;
Z为羧基、甲酰基、(C1-C6)烷氧羰基、(C1-C6)烷氧羰基(C1-C6)烷氧羰基、氰基(C1-C6)烷氧羰基、(C1-C6)烷氧基(C1-C6)烷氧羰基、[(C1-C6)烷硫基]羰基、(C1-C6)烷羰基、(C3-C6)链烯氧羰基、卤代(C3-C6)链炔氧羰基、(C3-C6)链炔氧羰基、(C3-C6)环烷氧羰基、杂环氧羰基、三(C1-C6)烷基甲硅烷基(C1-C6)烷氧羰基、二(C1-C6)烷氧基膦酰基(C1-C6)烷氧羰基、二(C1-C6)烷基亚氨基氧羰基、-烷基氨基羰基、-(C1-C6)烷氧氨基羰基、-(C3-C6)链炔氨基羰基或苯基氨基羰基。
这些酯戊二酰亚胺中,优选的是具有式(I)且其中A和A1为C=O、D为CH、Q为(CH2)n(n为0)、R为CH3、CHF2
或CF3、R1为H、R2为H、X为Cl或F、Y为Br、F或Cl、T为H且Z为CO2H、(C1-C6)烷氧羰基、(C3-C6)环烷氧羰基、(C3-C6)链烯氧羰基或(C3-C6)链炔氧羰基的那些化合物。
更优选的是,当R为CF3、R1和R2为氢、X为氟且Y为氯时,Z为羰基、甲氧羰基、正丙氧羰基、异丙氧羰基、仲丁氧羰基、环丁氧羰基或乙氧羰基。
更优选的是,当R为CF3、R1和R2为氢、X为氟且Y为溴时,Z为异丙氧羰基。
更优选的是,当R为CHF2、R1和R2为氢、X为氟且Y为氯时,Z为异丙氧羰基。
更优选的是,当R为CH3、R1和R2为氢、X为氟且Y为为氯时,Z为异丙氧羰基。
本发明的第三类优选化合物是具有式(I)的烷基戊二酰亚胺和醛肟基戊二酰亚胺,式(I)中:
A为C=O或CH2;
A1为C=O或CH2;
D为CH,当X为H时,D为N;
Q为(CH2)n(其中n为0或1);
R为(C1-C4)烷基、(C1-C4)卤代烷基或苯基;
R1为H或(C1-C2)烷基;
R2为H,或与R和R1一起形成稠合苯环;
X为H、Cl、Br或F;
Y为H、Cl、Br、F或CH3;
T为H或F;
Z为(C1-C6)烷基、(C1-C6)烷氧基(C1-C6)烷基、(C3-C6)链烯氧基(C1-C6)烷基、(C3-C6)链炔氧基(C1-C6)烷基、(C1-C6)烷酰氧基(C1-C6)烷基、[(C1-C6)烷硫基](C1-C6)烷基、苯氧基(C1-C6)烷基、苯硫基(C1-C6)烷基、(C1-C6)烷氧羰基(C1-C6)烷氧基(C1-C6)烷基、(C1-C6)烷基醛肟基、(C3-C6)链烯醛肟基、(C3-C6)链炔醛肟基或苯基(C1-C6)烷基醛肟基。
这些烷基戊二酰亚胺和醛肟基戊二酰亚胺中,优选的是具有式(I)且其中A和A1为C=O、D为CH、Q为(CH2)n(n为0)、R为CH3、CHF2或CF3、R1为H、R2为H、X为Cl或F、Y为Br、F或Cl、T为H且Z为(C1-C6)烷基、(C1-C6)烷氧甲基、(C3-C6)链烯氧甲基、(C3-C6)链炔氧甲基、(C1-C6)烷基醛肟基或(C3-C6)链炔醛肟基的那些化合物。
更优选的是,R为CF3,R1和R2为氢,X为氟,Y为氯且Z为异丙氧甲基、1-甲基炔丙氧甲基、甲基醛肟基、异丙基醛肟基、炔丙基醛肟基或叔丁基醛肟基。
A和A1为C=O ;
D为CH;
Q为(CH2)n(其中n为0);
L为O或S;
X为H或F;
R为(C1-C4)烷基、(C1-C4)卤代烷基或苯基;
R1为H或(C1-C2)烷基;
R2为H,或与R和R1一起形成稠合苯环;
R3为H或(C1-C3)烷基;且
R4为氢、(C1-C8)烷基、(C3-C6)链烯基、(C3-C6)链炔基、(C1-C6)烷氧基(C1-C6)烷基、(C1-C6)烷硫基(C1-C6)烷基、(C3-C6)环烷基、(C3-C6)环烷基(C1-C6)烷基、苯基(C1-C6)烷基、氰基(C1-C6)烷基、(C1-C6)烷氧羰基(C1-C6)烷基、杂环基、杂环(C1-C6)烷基、二(C1-C6)烷氨基(C1-C6)烷基、二(C1-C6)烷氨基羰基(C1-C6)烷基、(C1-C6)烷氧羰基或(C1-C6)烷酰基。
L为O或S;
X为H或F;
R为CH3、CHF2或CF3;
R3为H或(C1-C3)烷基;且
R4为氢、(C1-C6)烷基、(C3-C6)链烯基、卤代(C3-C6)链烯基、(C3-C6)链炔基、(C3-C6)环烷基、(C3-C6)环烷基(C1-C6)烷基、(C1-C6)烷氧甲基、(C1-C6)烷硫甲基、氰基(C1-C6)烷基、杂环基、杂环(C1-C6)烷基、二(C1-C6)烷氨基(C1-C6)烷基或二(C1-C6)烷基氨基羰基(C1-C6)烷基。
更优选的是,X为H或F,R为CH3、CHF2或CF3,R3为H、CH3或CH2CH3,R4为炔丙基、烯丙基、乙氧甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、1-乙基丙基、2-甲氧乙基、甲氧甲基、甲硫甲基、1-氰基乙基、1-甲基炔丙基、2-甲基烯丙基、氰基甲基、环丙甲基、环戊基、二甲氨基羰甲基、2-四氢呋喃甲基、3-四氢呋喃基、2-氯烯丙基或3,3-二氯烯丙基。
最优选的是,当R为CH3、R3为H、L为氧且R4为炔丙基时,X为F。
最优选的是,当R为CF3、R3为CH3L为氧且R4为炔丙基时,X为H或F。
最优选的是,当R为CF3、R3和X为H且L为氧时,R4为炔丙基、正丙基、1-甲基炔丙基、烯丙基、仲丁基、甲氧甲基或2-甲氧乙基。
最优选的是,当R为CF3、R3为H、L为氧且X为F时,R4为炔丙基、氰基甲基、烯丙基、甲氧甲基、乙氧甲基、正丙基、异丙基、正丁基、异丁基、仲丁基、1-氰乙基、2-甲基烯丙基、甲基硫甲基、2-乙基丙基、环丙甲基、环戊基、二甲氨基羰甲基、2-四氢呋喃甲基、3-四氢呋喃基、2-氯烯丙基、3,3-二氯烯丙基或乙基。
最优选的是,当R为CHF2、R3为H、L为氧且X为F时,R4为烯丙基。
最优选的是,当R为CF3、R3为CH2CH3、L为氧且X为F时,R4为炔丙基。
最优选的是,当R为CF3、R3为H、L为硫且X为F时,R4为炔丙基。
R为CF3或CH3,X为H或F,R4为(C1-C6)烷基。
最优选的是,R为CF3,X为F,R4为正丙基。
该反应的适宜溶剂包括醚,如乙醚、四氢呋喃(THF)和甘醇二甲醚;烃,如甲苯;乙腈;N,N-二烷基酰胺,如二甲基酰胺;以及卤代烃,如二氯甲烷和氯仿。为取得均化效果,还可使用溶剂混合物。该反应一般在大气压左右的压力下,于约-10℃至约100℃的温度下进行。优选的温度范围为约0℃至约70℃。
然后,在乙酐和乙酸钠或乙酰氯或乙酸乙酯的存在下,用亚硫酰氯和N,N-二甲基甲酰胺将式(IV)化合物环化,得到所需的本发明的N-取代戊二酰亚胺(式V)。该反应一般在约-10℃至约250℃温度下进行。更优选的是,该反应在约30℃至约150℃的温度下进行。
举例来说,可通过采用硫羰基转化剂如Lawesson试剂[2,4-双(4-甲氧苯基)-1,3-二硫-2,4-二磷丁环-2,4-二硫化物]或五硫化二磷,在六甲基磷酰胺或二甲苯的存在下,将具有式(V)的N-取代戊二酰亚胺:(其中Q不是氧)转化为本发明的硫代戊二酰亚胺(式VI):
该反应一般在约-10℃至约250℃的温度下进行,优选温度是约50℃至约150℃。
该反应一般在非质子传递溶剂如乙醚或四氢呋喃中进行。该反应一般在约-20℃至约100℃的温度下进行。优选的温度为约0℃至约65℃。
先将式(IV)戊酰胺酸还原为相似的5-羟基戊酰胺。例如,使用于溶剂(如四氢呋喃或乙醚)中的还原剂(如甲硼烷-二甲硫配合物)。温度范围为约-20℃至约150℃,优选约0℃至约100℃
例如,通过与亚硫酰氯于非质子传递溶剂如二氯甲烷中,在约-20℃~约150℃(最好在约0℃~约100℃)温度范围内反应,使5-羟基戊酰胺转化成相应的5-氯戊酰胺。
然后,例如,通过用碱如氢氧化钠,在非质子传递溶剂如四氢呋喃中,在约-20℃~约150℃(最好在约0℃~100℃)温度范围处理,使5-氯戊酰胺环化成式(VIII)哌啶酮。
在Z是取代的羰基的情况下,式(V)羧酸(Z=CO2H,其中Q不是氧)可通过与氯化试剂如亚硫酰氯,在惰性溶剂(最好是烃如甲苯或氯仿)中,在-20℃~200℃(最好在约50℃~约100℃)温度范围内反应,转化成相应的酰氯(Z=C(O)Cl)。然后将酰卤与适当的亲核试剂(例如醇、硫醇和胺)在适当的碱(最好是三乙胺或吡啶)存在下反应,生成相应的式(I)化合物。反应在惰性有机溶剂(最好是在THF或二氯甲烷)中进行。
在Y和Z共同形成杂环的情况下,用本领域已知方法制备氨基取代的杂环,然后与上述戊二酸酐(III)反应。此外,若杂环含有可被烷基化的部位,则可以在与戊二酸酐反应之后,进行烷基化反应,随后进行环化反应。
在Z是取代的烷氧基情况下,式(V)酚(Z=OH,其中Q不是氧)用非亲核碱如氢化钠处理,并与适当的烷基化试剂反应,生成相应的戊二酰亚胺。反应在惰性有机溶剂(如四氢呋喃或乙醚)中,在约-20℃~约150℃(最好约0℃~约100℃)温度范围内进行。
在Z是醛肟基的情况下,式(V)苯甲醛(Z=CHO,Q不是氧)与适当的烷氧基胺或烷氧基胺盐在极性有机溶剂如乙醇中,在约-20℃~约150℃(最好在约0℃~约100℃)温度范围内反应。若采用盐,则可向反应混合物中加入碱,如吡啶。
原料戊二酸酐按照本领域已知方法制备,例如见J.GOOtjes和W.Th.Nanto,Rec.Trav.Chem.,80,1183(1965)。此外,将4,4,4-三氟巴豆酸乙酯和钠代丙二酸二乙酯在催化量的催化剂如溴化四丁铵存在下反应,生成2-(三氟甲基)丙三酸乙酯,后者与强碱如氢氧化钾,最好在约50℃~约150℃温度范围内反应,然后酸化并脱去羧基,生成3-(三氟甲基)戊二酸。
原料苯胺基和氨基化合物可按已知方法制备,例如见US4,439,229;4,484,940;4,484,941;4,594,099;和4,640,707以及PCT/EP87/00279和PCT/us87/00056,上述文献在此列作参考。
以下实施例将进-步说明本发明,但绝非用以限制本发明。表I至IV列举了制得的N-取代的戊二酰亚胺的例子及其熔点。表V给出了未提供熔点的化合物的H-NMR数据。在表V之后叙述了化合物的具体制备例。
表INo. R.R1 X Y Z m.p.(℃)1. CF3,H F Cl OCH3 55-702. CF3,H F Cl OCH2CH3 72-753. CF3,H F Cl OCH2CH2CH3 106-1104. CF3,H F Cl OCH2CH2CH2CH3 112-1145. CF3,H F Cl OCH(CH3)2 88-906. CF3,H F Cl OCH(CH3)CH2CH3 油7. CF3,H F Cl OCH2CH(CH3)2 124-1278. CF3,H F Cl OCOCH3 71-769. CF3,H F Cl OCH2CH=CH2 80-8310. CF3,H F Cl OCH2C=CH 88-9111. CF3,H F Cl OCH2CN 123.5-12712. CF3,H F Cl OCH2OCH3 油13. CF3,H F Cl OSO2C6H5 214-21517. CF3,H F Br H 140-143
表I(续)No. R.R1 X Y Z m.p.(C)18. CF3,H F F H 108-11319. CF3,H F Cl OH 112-11420. CF3,H H Cl Cl 44-4621. CF3,H H Br CF3 99-10222. CF3,H H Br H 163-6423. CF3,H H CH3 H 179-18224. CF3,H H Cl OCH2C=CH 155-15625. CF3,H Cl Cl OCH2C=CH 油29. CH3,H F Cl OCH2C=CH 130-13330. CH3,H F Cl OCH(CH3)2 104-10731. CH3,H Cl Cl OCH2C=CH 170-17532. CH3,H H Cl OCH2C=CH 171-17433. CF3,H F H CO2CH(CH3)2 146-14834. CH3,H F Br H 99-10138. CH3,CH3 F Cl OCH2C=CH 101-102.539. CF3,H CN Cl H 135-13840. CF3,H H SCH3 H 144-145.541. CF3,H F Cl SCH(CH3)2 油42. CH3,H F Cl OCOCH3 135-14143. CH2CH3,H F Cl OCH2C=CH 102-10744. CH2CH3,H F Cl OCH(CH3)2 81-8445. CF2CF3,H F Cl OCH2C=CH 131-13246. CF2CF3,H F Cl OCH(CH3)2 66-67.547. CH(CH3)2,H F Cl OCH2C=CH 103-10648. CH(CH3)2,H F Cl OCH(CH3)2 油49. C6H5,H F Cl OCH2C=CH 188-19050. CF3,H F Cl SCH2CO2CH(CH3)2 油51. CF3,H F Cl CO2CH(CH3)2 96-9852. CF3,H F Cl OCH2SC6H5 108-109.5
表I(续)No. R.R1 X Y Z m.p.(℃)53. CF3,H F Cl OCH(CH3)CN 175-177(分解)54. CF3,H F Cl OCH2CO2CH3 90-9155. CF3,H F Cl OCH(OCH3)CO2CH3 40.5-4356. CF3,H F Cl SCH2CO2CH3 油57. CF3,H F Cl SCH2CO2H 137-13958. CF3,H F SH 68-7259. CF3,H F Cl SCOCH3 油60. CF3,H F Cl3 SCH3 114-11661. CF3,H F Cl CO2CH3 172-17462. CF3,H F Cl CO2H 220-22563. CH2CH3,H H Br H 140-14566. CH3,H H F H 125-12767. CH3,H H Cl H 163-16468. CH3,H H I H 174-17769. CH3,H H OCH3 H 112-11370. CH3,H H Cl Cl 156-15971. CF3,H F Cl CO2CH2CH3 104-10572. CF3,H F Cl CO2(CH2)2CH3 79-8073. CF3,H F Cl OCH2C6H5 121-122.574. CF3,H F Cl CO2CH(CH3)CO2CH3 94-9675. CF3,H F Cl CO2CH2CH(CH3)2 82-8576. CF3,H F Cl OCH2C=CCH3 95-9777. CF3,H F Cl CONHC6H5 55-6078. CF3,H F Cl CONHCH(CH3)2 95-11279. CF3,H F Cl CH2OCOCH3 115-116.580. CF3,H Cl Cl CO2CH(CH3)2 油81. CF3,H F Cl CH2OCH3 86-8882. CF3,H F Cl CH2OCH(CH3)2 77-7983. CF3,H F Cl CH2OCH2C=CH 油
表I(续)No. R.R1 X Y Z m.p.(℃)92. CF3,H F Cl CH3 119-12093. CF3,H F Cl CH=NOCH3 150.5-152.594. CF3,H F Cl CHO 146-148.595. CF3,H F Cl COCH3 127-12999. CF3,H H H OCH2C=CH 70.5-72100. CF3,H F Cl CO2N=C(CH3)2 144-145101. CF3,H F Cl CO2CH2PO(OC2H5)2 油102. CF3,H F Cl COSC2H5 102-104103. CF3,H F Cl CO2CH2CO2C2H5 139-140104. CF3,H F Cl COSCH(CH3)2 102-105106. CF3,H F Cl CH2SCH(CH3)2 107-109107. CF3,H F Cl CH2SC2H5 oil108. CF3,H F Cl CH2OC6H5 120-122109. CF3,H F Cl CH2SC6H5 oil110. CF3,H F Cl CO2CH2C=CH 120-123111. CF3,H F Cl CO2CH(CH3)C=CH 45-50112. CF3,H F Cl CO2CH2CH2C=CH 油113. CF3,H F Cl CO2CH(CH3)CN 油114. CF3,H F Cl CONHOCH3 158-162115. CF3,H F Cl CH2OCH(CH3)CO2C2H5 油116. CF3,H F Cl CO2CH2CH2OCH3 油117. CF3,H F Cl CO2CH(CH3)CH2OCH3 油118. CF3,H F Cl CO2CH(CH3)CH2CH3 油127. CF3,H F Cl
77-78130. CF3,H F Cl
52-55133. CF3,H F Cl CONHC(CH3)2C=CH 166-170
表I(续)No. R.R1 X Y Z m.p.(C)135. CF3,H F Cl
油140. CF3,H F Cl OCH2CH2C=CH 89-91141. CF3,H F Cl OCH(CH3)C=CH 102-104144. CF3,H F Cl CH2OCH(CH3)C=CH 油148. CF3,H F OCH3 NHCOCH3 155-157150. CF3,H F Cl CH=NOCH2CH=CH2 油152. CF3,H F CN H 154-155156. CF3,H F Cl CH=NOCH2C6H5 187-188158. CF3,H F Cl CH=NOC2H5 111.5-113.5159. CF3,H F Cl CH=NOH 75-80(升华)160. CF3,H F Cl OCH2CH2OCH3 95-97161. CF3,H F Cl CO2C6H5 206-208162. CF3,H F Cl CO2CH2Si(CH3)3 95-98163. CF3,H F Cl
53-55164. CF3,H F Cl CONHCH2C=CH 63-65168. CF3,H F Cl CH=NOC(CH3)3 140-141.5169. CF3,H F Cl CN 210-212172. CF3,H F Cl C(CH3)=NOCH3 130-135173. CF3,H F Cl C(CH3)=NOH 178-179.5174. CF3,H F Cl C(CH3)=NOCH2CH3 106-109175. CF3,H F Cl C(CH3)=NOC(CH3)3 132-134176. CF3,H F Cl C(CH3)=NOCH2CH=CH2 95.5-98177. CF3,H F Cl CO2-NH3CH(CH3)2+ 168-173(分解)178. CF3,H F Cl C(CH3)=NOCH2C6H5 92-97180. CF3,H H OCF3 H 113-116183. CF3,H H Cl N(CH3)C(=O)CH3 203-204
表I(续)No. R.R1 X Y Z m.p.(℃)185. CF3,H H NO2 H 133-134186. CF3,H F Cl CH=NOCH(CH3)2 140-415187. CF3,H F Cl CH=NOCH2C=CH 57-61190. CF3,H F Cl OSO2CH2CH3 41-44191. CF3,H H CF3 H 143-144192. CF3,H F Cl
63-65.5193. CF3,H F Cl
157-159194. CF3,H F Cl CO2CH2C6H5 50-55195. CF3,H F Cl CO2CH2CH=CH2 107-108196. CF3,H F Cl
91-92197. CF3,H F Cl
188-90199. CF3,H F Cl CO2CH2C=Cl 55-60201. CH3,H F Cl CO2CH(CH3)2 101-103202. CF3,H F Cl SO2CH2CH(CH3)2 48-51203. CF3,H F Cl SCH2CH(CH3)2 71-74206. CF3,H F Cl
137.5-140206. CF3,H F Br CO2CH(CH3)2 98-99207. CF3,H H Cl CO2CH(CH3)2 113-115209. CF3,H F F F 97-99212. CF3,H F F OCH2C=CH 67-68213. CF3,H F Cl CO2-K+ 133-143214. CF3,H H CH3 Cl 148-149.5
表I(续)No. R.R1 X Y Z m.p.(℃)215. CF3,H F Cl
175-178216. CF3,H F Cl
125-128218. CF3,H F Cl CO2N=CHCH(CH3)2 110-117219. CF3,H F Cl
105-107220. CF3,H F Cl
油221. CF3,H F Cl CO2N=C(CH3)OCH2CH3油222. CF3,H F Cl NO2 164-167223. CF3,H F F CO2CH(CH3)2 127-129224. CF3,H F Br OCH2C=CH 105-107.5225. CF3,H F Cl N(COCH3)2 164-169227. CF3,H F Cl
165-173228. CF3,H F CF3 CO2CH(CH3)2 89-92229. CF3,H F OCH3 OCH3 55-60231. CF3,H F Cl
152-153232. CF3,H F Cl
84-86
表I(续)No. R.R1 X Y Z m.p.(℃)234. CF3,H F Cl
144-147236. CF3,H F Cl OSO2CH3 96-99237. CHF2,H F Cl CO2CH(CH3)2 油240. CF3,H F Cl OCH(CH3)CH=CH2 油241. CF3,H F Cl OCH2C(Cl)=CH2 103-106242. CF3,H F Cl CO2CH(CH3)CH=CH2 79-81243. CF2H,H F Cl OCH2C=CH 110-111.5244. CF3,H F Cl OCH2CH=C(Cl)2 106-108245. CF3,H F Cl
121-123.3246. CF3,H F Cl S(O)CH2CH(CH3)2 133-134247. CH2F,H F Cl CO2CH(CH3)2248. CH2F,H F Cl OCH2C=CH264. CF3,H F Cl NCH2CH2CH3265. CF3,H F OCH3 NCH2CH2CH3266. CF3,H F Cl NCH2C=CH267. CF3,H F Cl NCH2CH=CH2268. CF3,H F Cl
269. CF3,H F Cl C(OCH3)=NOCH3271. CF3,H F OCH3 CO2CH(CH3)2272. CF3,H F OCHF2 CO2CH(CH3)2273. CF3,H F OCF3 CO2CH(CH3)2
表IINo. R.R1 X Y Z A Al O T D m.p.(℃)14. CF3,H F Cl OCH(CH3)2 CH2 C=O - H CH 98-10215. CF3,H F Cl OCH2C=CH CH2 CH2 - H CH 油16. CF3,H F F H C=O C=O - F CH 94-9726. CF3,H H Cl H C=O C=O - H N 119-12127. CF3,H F Cl H C=O C=O CH2 H CH 113-11528. CF3,H H Cl H C=O C=O CH2 H CH 114-11935. CH3,H H Cl H C=O C=O - H N 15436. CH3,H H F H C=S C=O - H CH 84.5-87.537. CH3,H H F CN C=O C=O - F CH 92-9464. CF3,H H Cl H C=O C=O O H CH 148-15265. CF3,H H NO2 CO2CH3 C=O C=O O H CH 152-155132. CF3,H F Cl H C=O C=O - F CH 134-135
表IIINo. X L M R R3 R4 m.p.(℃)84. H O C=O CF3 CH3 CH2C=CH 100-10285. H O C=O CF3 H CH2C=CH 203-204.588 F O C=O CF3 CH3 CH2C=CH 147-14889. F O C=O CF3 H CH2C=CH 182-18396. F O C=O CF3 H CH2CN 126-12897. F O C=O CF3 H CH2CH=CH2 126-12898. F O C=O CF3 H CH2OCH2CH3 151-152105. H O C=O CF3 H CH2CH2CH3 170-171121. F O C=O CF3 H CH2SCH3 油122. F O C=O CF3 H CH2CH2CH3 油124. H S C=O CF3 H CH2C=CH 165-168126. F O C=O CF3 H CH2C6H5 212-216128. F O C=O CF3 H CH2CH(CH3)2 180-181129. F O C=O CF3 H CH(CH3)CH2CH3 108-109131. F O C=O CF3 H CH3 170-173134. F O C=O CF3 H CH2(CH2)6CH3 91-94136. H O CH2 CF3 H CH2CH2CH3 68-71137. F O C=O CF3 H CH2CO2CH(CH3)2164-166138. F O C=O CF3 H H 油139. F O C=O CF3 H COCH3 油142. F O C=O CF3 H CO2CH3 油
表III(续)No. X L M R R3 R4 m.p.(℃)143. F O C=O CF3 H CH(CH3)2 油145. F O C=O CH3 H CH2C=CH 192-194146. F O C=O CF3 H CH(CH2CH3)2 油147. H O C=O CF3 H CH(CH3)C=CH 68-70149. F O C=O CF3 H CH(CH3)CN 油151. H O C=O CF3 H CH2OCH3 138-140154. H O C=O CF3 H CH2CH=CH2 144-146155. F O C=O CF3 H CH2C(CH3)=CH2 200-202157. H O C=O CF3 H CH(CH3)CH2CH3 115-118165. F O C=O CF3 H CH2CH3 148-150166. F O C=O CF3 H CH2CH2CH2CH3 165-167167. H O C=O CF3 H CH2CH2OCH3 143-146171. H O C=O CH3 H CH2C=CH 200-204179. F O C=O CF3 H CH2CH2CH2Cl 138-140182. F O C=O CF3 H
146-148184. F S C=O CF3 H CH2CH=CH2 148-150188. F O C=O CF3 H CH2OCH3 175-176189. F O C=O CF3 H
油200. F O C=O CF3 H CH2CON(CH3)2 >200204. F O C=O CF3 H
180-181208. F O C=O CF3 H
发泡210. F O C=O CF3 H
″211. H O C=O CF3 H CH(CH3)2 153-155
表III(续)No. X L M R R3 R4 m.p(℃)217. H O C=O CF3 H CH2CH2Cl 109-110226. F O C=O CF3 H CH2CH2N(CH3)2122-124230. F O C=O CF3 H CH2C(Cl)=CH2 178-180233. F O C=O CF3 H CH2CH=CCl2 173-175235. F O C=O CF3 CH2CH3CH2C=CH 发泡238. F O C=O CF2H H CH2C=CH >200239. F O C=O CF3 H
发泡249. F O C=O CFH2 H CH2C=CH250. H O C=O CFH2 H CH2C=CH251. H O C=O CF2H H CH2C=CH252. F O C=O CF2H H CH2CH=CH2253. F O C=O CF2H H CH(CH3)2254. F O C=O CF2H H CH2CH(CH3)2255. F O C=O CF2H H CH2OCH3256. F O C=O CFH2 H CH2OCH3257. F O C=O CFH2 H CH(CH3)2258. F O C=O CFH2 H CH2CH(CH3)2259. F O C=O CFH2 H CH2CH=CH2260. F O C=O CF3 H CH2C(=O)CH3261. F O C=O CF3 H CH2CH(OH)CH3
表V NMR数据实施 (200MHZ,δ位移以ppm例号 溶剂 表示,以四甲基-甲硅烷
(TMS)作内标)6. CDCl3 1.0(t,3H),1.3(d,H),1.6-1.9(m,2H),
2.8-3.2(m,5H),4.1-4.3(m,1H),
6.7(dd,1H),7.3(dd,1H)12. CDCl3 3.0(m,4H),3.5(s,3H),3.5(m,1H),
5.2(s,2H),7.0(d,1H),7.3(d,1H)15. CDCl3 1.8(m,4H),2.2(m,1H),2.6(m,1H),
2.7(t,2H),3.5(d,2H),4.7(s,2H),
6.7(d,1H),7.1(d,1H)25. CDCl3 2.6(t,1H),2.9-3.3(m,5H),4.9(d,2H),
6.9(m,1H),7.6(m,1H)41. d6-丙酮 1.3(d,6H),3.1(m,4H),3.4(m,1H),
4.0(m,1H),7.4(t,1H),7.5(d,1H)48. " 1.0(d,6H),1.4(d,6H),1.7(m,1H),
2.5-3.0(m,4H),4.1(m,1H),4.6(m,1H),
7.1(m,1H),7.4(m,1H)
表V(续)实施 溶剂 (200MHz,δ位移以例号 ppm表示,以四甲基甲硅
烷(TMS)作内标)50. d6-丙酮 1.2(d,6H),3.1(m,4H),3.5(m,1H),
3.8(d,2H),4.9(m,1H),7.4(dd,1H),
7.5(d,1H)56. " 3.2(m,4H),3.7(s,3H),3.6(m,1H),
3.8(d,2H),7.5(dd,1H),7.6(d,1H)59. " 2.5(s,H),3.2(m,4H),3.6(m,1H),
7.5(t,1H),7.6(d,1H)80. CDCl3 1.33(d,6H),2.80-3.23(m,5H),
5.25(heptet,1H),7.65(m,2H)83. CDCl3 2.5(s,1H),2.8-3.2(m,5H),4.25(d,2H),
4.65(s,2H),7.2-7.4(m,2H)101. d6-DMSO 1.3(t,6H), 2.9-3.2(m,4H),3.6(m,1H),4.1
(quintet,4H),4.7(d,2H),7.8-8.0(m,2H)107. CDCl3 1.2-1.3(t,3H),2.5(q,2H),2.9-3.3(m,5H),
3.8(s,2H),7.25(d,1H), 7.30(d,1H)109. CDCl3 2.8-3.2(m,5H),4.1(s,2H),6.9-7.1(q,1H),
7.2-7.4(m,6H)112. CDCl3 2.02(s,1H),2.64(td,2H),2.82-3.28(m5,H),
4.39(t,2H),7.36(d,1H),7.80(dd,1H)113. d6-DMSO 1.70(d,3H),2.96-3.19(m,5H),5.78(m,1H),
7.86-8.08(m,2H)115. CDCl3 1.3(t,3H),1.4-1.5(d,3H),2.8-3.2(m,5H),
4.1-4.2(q,1H),4.2-4.3(q,2H),4.55(d,1H),
4.75(d,1H),7.2-73(d,1H),7.3-7.4(d,1H)
表V(续)实施例号 溶剂 (200MHz,δ位移以
ppm表示,以四甲基甲硅
烷(TMS)作内标)116. CDCl3 2.8-3.2(m,5H),337(s,3H),3.72(m,2H),
4.45(t,2H),7.35(d,1H),7.78(d,1H)117. CDCl3 1.35(d,3H),2.86-3.22(m,5H),3.38(s,3H),
3.55(m,2H),535(m,1H),7.35(d,1H),
7.73(d,1H)118. CDCl3 0.92(t,3H),1.35(d,3H),1.70(heptet,2H),
2.85-3.25(m,5H),5.10(sextet,1H),
7.35(d,1H),7.7(dd,1H)121. d6-丙酮 2.2(s,3H),3.1(m,4H),3.5(m,1H),
4.8(s,2H),5.1(d,2H),6.9(d,1H),7.1(t,1H)122. " 0.9(t,3H),1.7(m,2H),3.1(m,4H),
3.5(m,1H)3.9(m,2H),4.7(s,2H),
7.0(d,1H),7.1(d,1H)135. CDCl3 1.65-2.00(m,2H),2.20(m,2H),
2.45(m,2H),2.85-3.25(m,5H),
5.20(quintet,1H),7.30(d,1H),7.75(d,1H)138. d6-丙酮 3.1(m,4H),3.5(m,1H),4.7(s,2H),
6.8(d,1H),6.9(d,1H),9.8(bs*,1H)139. " 2.6(s,3H),3.2(bm**,4H),3.6(m,1H),
4.9(s,2H),7.1(d,1H),7.7(d,1H)142. " 3.1(bm,4H),3.6(m,1H),4.0(s,H),
4.8(s,2H),7.0(d,1H),7.4(d,1H)143. " 1.5(d,6H),3.1(m,4H),3.5(m,1H),
4.6(s,2H),4.7(m,1H),6.9(d,1H),
7.2(d,1H)
表V(续)实施 溶剂 (200MHz,δ位移以例号 ppm表示,以四甲基甲硅
烷(TMS)作内标)144. CDCl3 1.55(d,3H),2.5(d,1H),2.8-3.3(m,5H),
4.3(m,1H),4.55(d,1H),4.80(d,1H),
7.2(d,1H),7.35(d,1H)146. d6-丙酮 0.9(d,6H),1.8(m,4H),3.0(m,4H),
3.5(m,1H),4.5(bm,1H),4.7(s,2H),
6.9(d,1H),7.2(d,1H)149. d6-DMSO 0.9(d,3H),3.2(m,4H),3.6(m,1H),
4.8(s,2H),6.0(quintet,1H),7.1(d,1H),
7.3(d,1H)150. CDCl3 2.75-3.25(m,5H),4.6(d,2H),5.3(t,2H),
6.0-6.1(m,1H),7.2(t,1H),7.7(dd,1H),
8.4(s,1H)189. d6-丙酮 2.1(m,4H),2.3(m,4H),3.2(m,4H),
3.5(m,1H),4.6(s,2H),4.7(m,1H),
7.0(d,1H),7.4(d,1H)208. " 1.8(m,1H),1.9(m,3H),3.1(m,4H),
3.5(m,1H),3.8(m,2H),4.2(m,3H),
4.7(s,2H),6.9(d,1H),7.2(d,1H)210. " 2.2(m,2H),3.1(m,4H),3.5(m,1H),
3.8(m,2H),3.9(m,2H),4.6(s,2H),
5.5(m,1H),7.0(d,1H),7.3(dd,1H)220. " 3.0-3.4(m,4H),3.55(m,1H),5.45(s,2H),
7.35(dd,1H),7.53(d,1H),7.62(d,1H),
7.85(td,1H),7.98(dd,1H),8.59(d,1H)221. " 1.34(t,3H),2.13(s,H),3.0-3.3(m,4H),
3.55(m,1H),4.22(q,2H),7.65(d,1H),
7.90(dd,1H)
表V(续)实施 溶剂 (200MHz,δ位移以例号 ppm表示,以四甲基甲硅
烷(TMS)作内标)235. d6-丙酮 1.1(t,3H),1.9(m,2H),2.8(d,1H),
3.1(m,4H),3.5(m,1H),4.7(m,3H),
7.0(m,2H)237. " 1.5(d,6H),2.9-3.2(m,5H),5.2(heptet,1H),
6.2(tdd,1H),7.5(dd,1H),7.8(dd,1H)239. " 2.6(m,1H),2.7(m,1H),3.1(m,4H),
3.5(m,b,2H),3.8(dt,1H),4.3(dt,1H),
4.8(s,2H),6.9(d,1H),7.2(t,1H)240. CDCl3 1.5(d,3H),3.0(m,H),4.65(t,1H),
5.15(d,1H),5.25(d,1H),5.85(m,1H),
6.65(dd,1H),7.25(d,1H)*bs=宽的单峰**bm=宽的多重峰实例A:1-氯-2-氟-5-炔丙氧基苯胺的制备
向-漏斗、半器、度计式漏.00ml三颈圆底烧瓶中圆底烧瓶中加入氧基-2-氯-2-氯氟苯氟苯酸1.0g,0.103l)和二甲基亚砜(DMSO)(100Ml)。混合物在室温下搅拌并用10分钟滴加氢氧化钾(KOH)水溶液(7.0gKOH,88%w/w,1.01当量,溶于10ml水中)。加料过程中,观察到反应放热(25℃至40℃)。溶液搅拌1小时,然后滴加炔丙基溴溶液(80%,在甲苯中,12.7ml,1.10当量)。加料过程中,观察到反应放热(自25℃至40℃)。混合物在室温下搅拌过夜。
早晨,由薄层色谱法(TLC)(硅胶,1∶1V/V已烷/乙酸乙酯(EtoAc))证明反应已完全。将混合物倾入冰水(600ml)中,过滤,水洗并于50℃通宵真空干燥,得到所需的炔丙氧基-N-乙酰苯胺,为褐色粉末(24.0g,96%,熔点142-5℃)。
向配有高架搅拌器、温度计和冷凝器的250ml三颈圆底烧瓶中加入炔丙氧基-N-乙酰苯胺(9.64g,40mmol)、乙醇(无水,43ml)、水(56ml)和浓盐酸(Hl)(35%,W/W,37.5ml)。在搅拌下,用加热夹套将混合物加热至回流。回流(92℃)1小时后,对碱化的试样进行薄层色谱分析(硅胶,3∶1已烷/EtoAc,V/V),表明反应已完全。将混合物倾入冰水(200ml)中,并用50%氢氧化钠(NaOH)水溶液(25ml)将PH值调节至10,其间析出棕色固体。混合物用乙醚(3×100ml)萃取,合并的有机层用水洗(2×50ml水,1×50ml盐水)。并于无水硫酸镁(MgSO4)中干燥。过滤混合物,真空蒸发溶剂并于25℃干燥过夜,得到所需的苯胺,为棕色油状物。实例B:3-(三氟甲基)戊二酸酐
向于5ml THF中的115mg(5mmol)金属钠(切割成细条并用已烷洗涤)中加入于10ml THF中的丙二酸二乙酯(800mg,5mmol)溶液。混合物在室温下搅拌,直至金属钠全部耗尽(2~3小时)。加入催化量的溴化四丁铵,随后加4,4,4-三氟巴豆酸乙酯(0.84g,5mmol)的THF溶液(10ml)。加热该混合物至40℃并搅拌17小时。冷至10℃后,加入冰醋酸(300mg,5mmol),并且真空除去THF。所得残余物用在10ml水中的87.3%KOH(1.28g,20mmol)处理并回流4.5小时。冷至10℃后,通过移液管滴加2.5ml(26mmol)浓HCl,并将混合物再加热至回流,直至停止释放CO2(约1小时)。将溶液冷至15℃并用Et2O(3×10ml)萃取。合并的有机相在Na2SO4中干燥,过滤并真空浓缩,得到3-(三氟甲基)戊二酸,为白色固体,产率95%(熔点100-100.5℃)。
向配有机械搅拌器和回流冷凝器的2升三颈烧瓶中加入320g(1.6mol)3-(三氟甲基)戊二酸和775ml乙酐。溶液回流2.5小时,然后冷却至室温。真空(80℃)除去大部分乙酐,得到的棕色固体溶于位于蒸汽浴之上的800ml CHCl3中。随着加入200ml已烷,白色固体开始析出。在冷藏室中存放进一步诱发结晶。滤出白色絮凝物并在烘箱中干燥(50℃,30mmHg),得到261g(产率89%)所需产物,熔点88-91℃。实例1N-(4′-氯-2′-氟-5′-炔丙氧基苯基)-3-(三氟甲基)戊酰胺酸
向配有高架搅拌器、滴液漏斗、温度计和氮气(N2)导管的1升三颈圆底烧瓶内加入3-(三氟甲基)戊二酸酐(18.2g,0.100mol)和二氯甲烷(CH2Cl2)(250ml)。混合物搅拌至均匀,然后滴加4-氯-2-氟-5-炔丙氧基苯胺(19.9g,0.100mol)在CH2Cl2(50ml)中的溶液,历时10分钟。得到澄清的溶液。混合物在室温下搅拌过夜,其间形成白色沉淀。
早晨,真空过滤反应混合物并用CH2Cl2略微洗涤,得到36.6g戊酰胺酸白色固体,(产率96%),熔点140-2℃。实例2:N-(4′-氯-2′-氟-5′-炔丙氧基苯基)-3-(三氟甲基)戊二酰亚胺(化合物10)
向配有磁力搅拌棒、冷凝器、温度计和氮气导入接管的500ml三颈圆底烧瓶加入N-(4′-氯-2′-氟-5′-炔丙氧基苯基)-3-(三氟甲基)戊酰胺酸(13.1g,0.034mol)、乙酐(150ml)和乙酸钠(0.45g)。通宵搅拌混合物并加热至95℃。在最高温度不超过50℃(1-5mmHg)下,采用短路蒸馏除去易挥发成分。将残余物溶于EtOAC(150ml),并且洗涤(1×100ml饱和碳酸氢钠(NaHCO3)水溶液,1×100ml水和1×100ml盐水),干燥(MgSO4)和真空蒸发,得到棕色油状物,于50℃真空干燥,得到浅棕色固体(9.8g,产率79%,熔点80-82℃)。甲醇/水中重结晶,得到褐色戊二酰亚胺固体,熔点88-91℃。
采用实施例1和2所述的相同方法,制备表I、II和IV所述化合物1-9,11,16-18,20,21,23-28,33,39-41,50,51,56,57,59-62,64,65,71,72,79-83,86,92,94,95,99,106-109,115,119,120,125,132,144,152,160,180,185,191,192,203,206,207,209,212,214,223,224,228,229,241和275,不同的是苯胺基或氨基化合物(式II)为:4-氯-2-氟-5-甲氧基苯胺,4-氯-2-氟-5-乙氧基苯胺,4-氯-2-氟-5-正丙氧基苯胺,4-氯-2-氟-5-正丁氧基苯胺,4-氯-2-氟-5-异丙氧基苯胺,4-氯-2-氟-5-仲丁氧基苯胺,4-氯-2-氟-5-异丁氧基苯胺,4-氯-2-氟-5-羟基苯胺,4-氯-2-氟-5-烯丙氧基苯胺,4-氯-2-氟-5-氰基甲氧基苯胺,2,4,6-三氟苯胺,4-溴-2-氟苯胺,2,4-二氟苯胺,3,4-二氯苯胺,4-溴-3-(三氟甲基)苯胺,对甲苯胺,4-氯-3-炔丙氧基苯胺,2,4-二氯-5-炔丙氧基苯胺,5-氨基-2-氯吡啶,4-氯-2-氟苄基胺,4-氯苄基胺,2-氨基-5-氯苄睛,4-(甲硫基)苯胺,4-氯-2-氟-5-(异丙硫基)苯胺,4-氯-2-氟-5-〔(异丙氧基羰基)甲硫基〕苯胺,5-氨基-2-氯-4-氟苯甲酸异丙基酯,4-氯-2-氟-5-〔(甲氧羰基)甲硫基〕苯胺,4-氯-2-氟-5-〔(羧基)甲硫基〕苯胺,5-氨基-2-氯-4-氟苯硫酚,4-氯-2-氟-5-(甲硫基)苯胺,5-氨基-2-氯-4-氟苯甲酸甲酯,5-氨基-2-氯-4-氟苯甲酸,4-氯苯氧基胺,3-甲氧基羰基-4-硝基苯氧基胺,5-氨基-2-氯-4-氟苯甲酸乙酯,5-氨基-2-氯-4-氟苯甲酸正丙基酯,4-氯-2-氟-5-(羟甲基)苯胺,5-氨基-2,4-二氯苯甲酸异丙基酯,4-氯-2-氟-5-(甲氧基甲基)苯胺,4-氯-2-氟-5-(异丙氧基)苯胺,4-氯-2-氟-5-(炔丙氧基甲基)苯胺,6-氨基吲唑,5-氨基-2-氯-4-氟甲苯,5-氨基-2-氯-4-氟苯甲醛,3-炔丙氧基苯胺,3,4-(亚甲二氧基)苯胺,1,4-苯并二噁唑-6-胺,5-氨基-2-甲基苯并噻唑,4-氯-2-氟-5-(异丙硫基甲基)苯胺,4-氨-2-氟-5-(乙硫基甲基)苯胺,4-氯-2-氟-5-(苯氧基甲基)苯胺,4-氯-2-氟-5-(苯硫基甲基)苯胺,4-氯-2-氟-5-〔(1-乙氧基羰基)乙氧基甲基〕苯胺,4-氯-2-氟-5-〔(3-丁炔-2-氧基)甲基〕苯胺,4-氯-2-氟-5-(甲氧基乙氧基)苯胺,3-氨基-4-氟-苯甲酸异丙基酯,4-氯-2,6-二氟苯胺,4-氰基-2-氟苯胺,5-氨基-2-氯-4-氟乙酰酮,6-氨基-3,4-苯并香豆素,4-(三氯甲氧基)苯胺,4-硝基苯胺,4-(三氟甲基)苯胺,4-氯-5-环戊氧基-2-氟苯胺,4-氯-2-氟-5-(异丁硫基)苯胺,5-氨基-2-溴-4-氟苯甲酸异丙基酯,5-氨基-2-氯苯甲酸异丙基酯,2,4,5-三氟苯胺,2,4-二氟-5-炔丙氧基苯胺,3-氯-4-甲基苯胺,5-氨基-2,4-二氟苯甲酸异丙基酯,4-溴-2-氟-5-炔丙氧基苯胺,5-氨基-4-氟-2-(三氟甲基)苯甲酸异丙基酯,2-氟-4,5-二甲氧基苯胺或4-氯-5-(2-氯烯丙氧基)-2-氟苯胺。
此外,采用实施例1和2的方法制备表I、II和III所述化合物30,35,38,43-49,91,201和237,不同的是合适的式(III)戊二酸酐(即:3-甲基戊二酸酐,3-乙基戊二酸酐,3,3-二甲基戊二酸酐,3-(氟甲基)戊二酸酐,3-(二氟甲基)戊二酸酐,3-(五氟乙基)戊二酸酐,3-异丙基戊二酸酐,3-苯基戊二酸酐或高邻苯二酸)与如下的氨基化合物(式II)反应:4-氯-2-氟-5-异丙氧基苯胺,4-氯-2-氟-5-炔丙氧基苯胺,4-溴-2-氟苯胺,5-氨基-2-氯-4-氟苯甲酸异丙基酯或5-氨基-2-氯吡啶。实例3:N-(4′-氯-2′-氟-5′-(甲氧基甲氧基)苯基)-3-(三氟甲基)戊二酰亚胺(化合物12)a.4-氯-2-氟-5-(甲氧基甲氧基)硝基苯
向1.12g(5.9mmol)2-氯-4-氟-5-硝基苯酚在100ml CH2Cl2中的溶液中加入2ml二甲氧基甲烷,随后加7.48g(53mmol)五氧化二磷。反应物在室温下搅拌3小时,随后另加100ml CH2Cl2。将反应混合物倾在200ml冰上,并分离形成的液层。水相用CH2Cl2萃取-次(1×100ml),而合并的有机相用水洗涤(2×100ml),在MgSO4中干燥并浓缩,得到1.16g(产率95%)浅黄色固体4-氯-2-氟-5-(甲氧基甲氧基)硝基苯。
按实例13C所述,采用铁和乙酸将硝基苯中间体转化成相应的苯胺。按实例1和2所述方法将苯胺转化成表I中的化合物12。实例4:N-(4′-氯-2′-氟-5′-苯磺酰氧基)苯基)-3-(三氟甲基)戊二酰亚胺(化合物13)
用注射器向N-(4′-氯-2′-氟-5′-羟基苯基)-3-(三氟甲基)戊二酰亚胺(1.64g,5.05mmol,化合物19)在约20ml二氯甲烷中的溶液中加入约2.5当量自CaH2中新蒸馏过的吡啶(1ml),然后在冰浴冷却下,向反应混合物中缓慢滴加苯磺酰氯(0.64ml,5.0mmol)在4.5ml二氯甲烷中的溶液。将反应混合物加热至室温并搅拌12小时。随后另加入0.17g戊二酰亚胺并且使反应混合物在室温下另搅拌12小时。将反应混合物倾入50ml水中,分离液层。真空蒸发有机层,残余物在真空烘箱中干燥(20-50乇,50℃)。用约5ml二氯甲烷漂洗所得棕色固体并且抽吸过滤,得到1.9g(产率82%)所需产物,为灰白色粉末,熔点214-215℃。
按照与本实例所述相同的方法,用乙磺酰氯代替苯磺酰氯,制备化合物190。实例5:N-(4′-氯-2′-氟-5′-异丙氧基苯基)-4-(三氟甲基)-2-哌啶酮(化合物14)a.N-(4′-氯-2′-氟-5′-异丙氧基苯基)-5-羟基-3-(三氟甲基)戊酰胺
用注射器向N-(4′-氯-2′-氟-5′-异丙氧基苯基)-3-(三氟甲基)戊酰胺酸(4.32g,11.4mmol)在20ml四氢呋喃(自钠/二苯甲酮新蒸过)的溶液缓慢加入10M甲硼烷-二甲硫配合物(1.18ml)。利用冰浴将温度维持在10-20℃,出现明显的剧烈鼓泡。将混合物缓慢加热至室温并在氮气下搅拌150小时,于55℃加热6小时,然后冷却至室温并静置16小时。将烧瓶在冰/水浴中冷却,然后通过漏斗缓慢加入7ml甲醇(MeOH)。反应混合物变得非常粘稠难以继续搅拌。使温度缓慢升至室温,使搅拌棒能够继续搅拌混合物。真空(20-50乇)除去MeOH和THF,残余物借助快速色谱分离(2"×7"柱,3∶1己烷/乙酸乙酯,75ml馏分)。合并馏分18-45并真空除去溶剂。残余物于50℃真空干燥,得到1.66g(产率39%)戊酰胺,为近无色油状物。b.N-(4′-氯-2′-氟-5′-异丙氧基苯基)-5-氯-3-(三氟甲基)戊酰胺
用移液管向N-(4′-氯-2′-氟-5′-异丙氧基苯基)-5-羟基-3-(三氟甲基)戊酰胺(1.2g,3.2mmol)在100ml二氯甲烷中的溶液,一次加入亚硫酰二氯(0.24ml)。溶液变为棕色。将其于40-50℃加热约7小时,室温下静置64小时,于40℃加热3小时,然后在室温下搅拌18小时。然后另加入亚硫酰二氯(0.1ml),加热至40℃并保持约4小时。将反应混合物冷却至室温并且真空除去溶剂。真空干燥残余物(50℃),所得金黄棕色半固体混合物借助快速色谱法(20ml馏分,2"×7"柱,1∶9乙酸乙酯/己烷)提纯,得到棕色固体,熔点57-63℃。c。N-(4′-氯-2′-氟-5′-异丙氧基苯基)-4-(三氟甲基)-2-哌啶酮
向1.4g(3.6mmol)N-(4′-氯-2′-氟-5′-异丙氧基苯基)-5-氯-3-(三氟甲基)戊酰胺的四氢呋喃(16ml)溶液中加入16ml水和2ml50%NaOH水溶液)。将混合物加热至50℃并剧烈搅拌。6小时后使反应混合物冷却至室温,停止搅拌并除去水层。有机层在真空中蒸发,然后将残余物置于乙醚(50ml),用水(2×50ml)随后用盐水洗涤。最初的水层用50ml乙醚萃取,合并的有机层用盐水(50ml)洗涤并干燥(MgSO4)。真空除去溶剂,得到1.3g棕色固体,自己烷中重结晶得到0.81g(产率64%)棕色固体,熔点98-102℃。实例6:N-(4′-氯-2′-氟-5′-炔丙氧基苯基)-4-(三氟甲基)哌啶(化合物15)
向三颈圆底烧瓶中加入0.56g(15mmol)氢化锂铝和60ml四氢呋喃。将含有3.60g(10.0mmol)N-(4′-氯-2′-氟-5′-炔丙氧基苯基)-3-(三氟甲基)戊二酰亚胺的套管装入索格利特萃取器并连接在反应容器上。将油浴加热至85℃并加入11ml THF和25ml乙醚。6小时后,大部分的戊二酰亚胺被萃取到反应混合物中,在反应烧瓶中生成灰色固体妨碍了搅拌。将反应混合物冷却至室温。缓慢加入水(0.56ml),随后加15%NaOH(0.5ml)。然后另加水(1.68ml)以使锂盐沉淀。吸滤混合物,固体用乙醚漂洗。真空蒸发滤液,得到3.4克棕色油状物。借助色谱法(硅胶,3∶1己烷/二氯甲烷)提纯油状物,得到100mg(产率3%)所需产物,为油状物。
实例7:N-(4′-氯-2′-氟-5′-羟基苯基)-3-(三氟甲基)戊二酰亚胺(化合物19)a.N-(4′-氯-2′-氟-5′-羟基苯基)-3-(三氟甲基)戊酰胺酸
向配有磁力搅拌棒、温度计、滴液漏斗、冷凝器和N2导管的1升三颈圆底烧瓶中加入4-氯-2-氟-5-羟基苯胺(25.7g,0.159mol)、水(24ml)、乙酸(8.4ml)和四氢呋喃(THF)(48ml)。将混合物搅拌至均匀后,加热至40℃并通过加料漏斗滴加3-(三氟甲基)戊二酸酐(34.8g,0.191mol)在THF(60ml)中的溶液,观察到反应放热3-4℃。将反应混合物于50℃加热3小时,然后冷却至室温。
将反应混合物倾在600ml冰上。待冰融化后,固体通过粗烧结玻璃板漏斗吸滤分离。固体用水彻底洗涤,并于50℃真空干燥,得到灰色的戊酰胺酸固体(51,91g,产率95%,熔点171-174℃)。b.N-(4′-氯-2′-氟-5′-羟基苯基)-3-(三氟甲基)戊二酰亚胺
向配有搅拌棒、N2导管和橡胶隔片的250ml三颈圆底烧瓶中加入N-(4′-氯-2′-氟-5′-羟基苯基)-3-(三氟甲基)戊酰胺酸(9.51g,24mmol)和EtOAc(75ml)。将混合物搅拌至均匀并经注射器加入亚硫酰二氯(99+%,3.87ml,2当量),随后加入0.25当量无水N,N-二甲基甲酰胺。将反应物加热至80℃并保持6小时,然后在室温下静置过夜。
将反应混合物倾入125ml水中并用总共100mlEtOAc萃取两次。合并有机层,然后用100ml水洗两次并用50ml盐水洗一次。分离有机层,用MgSO4干燥,减压下蒸发并真空干燥(20-50乇,50℃)。静置,残余物固化,得到8.6g(产率99%)深棕色戊二酰亚胺固体,熔点112-114℃
按照与该例的相同方法,采用苯胺基化合物(式II)5-氨基-2-氯-4-氟苯硫酚,制备上表I所述的化合物58。实例8:N-(4′-溴苯基)-3-(三氟甲基)戊二酰亚胺(化合物22)
向装有搅拌棒的50ml单口圆底烧瓶中,加入2.50g(7.96mmol)N-(4′-溴苯基)-3-(三氟甲基)戊酰胺酸(如实施例1所述,自适当的苯胺和戊二酸酐制备)和乙酰氯(15ml)。加热混合物至回流并保持6小时,产生澄清、亮灰色溶液。利用一个短路蒸馏头通过常压蒸馏除去乙酰氯。所得亮灰色结晶固体用已烷研制,过滤并用己烷洗涤,得到灰白色结晶固体,于50℃真空干燥,得到2.10g(产率89%)产物,熔点163-4℃。
按照该例所述相同方法,制备表I和II中所述的化合物29,34,37,42,63,66,68,69和70。实例9:N-(4′-氟苯基)-3-甲硫基戊二酰亚胺(化合物
36)
将盛于50ml圆底烧瓶中的由1.02g(4.68mmol)N-(4′-氟苯基)-3-甲基戊二酰亚胺(化合物66)、0.88g(2.2mmol)2,4-双(4-甲氧基苯基)-1,3-二硫-2,4-二磷丁环-2,4-二硫化物(称作劳伦森试剂)和6ml六甲基磷酰胺组成的混合物加热至95-100℃并保持21小时。另加入1.05g(2.5mmol)劳伦森试剂并加热至100℃并另保持30小时。混合物冷却至室温并加入水(50ml)。混合物用乙醚萃取(4×50ml)。合并有机相,在MgSO4中干燥并真空除去溶剂。所得2g橙色油借助快速色谱法(硅胶,1∶1己烷/二氯甲烷)纯化,得到300mg(产率28%)黄色油,固化成固体,熔点84.5-87.5℃。实例10:N-(4′-氯-2′-氟-5′-((苯硫基)甲氧基〕-苯基〕-3-(三氟甲基)戊二酰亚胺(化合物52)
在N2下,0.15g(3.7mmol,60%油悬浮液)氢化钠用戊烷洗涤(2×0.5ml),然后悬浮于2ml无水THF(自钠/二苯甲酮中新蒸过)中。向在冰浴中冷却的悬浮液中加入溶解于3.5ml无水THF(自钠/二苯甲酮新蒸过)中的1.1g(3.4mmol)N-(4′-氯-2′-氟-5′-羟基苯基)-3-(三氟甲基)戊二酰亚胺(化合物19)并用两份1ml无水THF冲洗。然后使反应物温热至室温并搅拌15分钟。将烧瓶于冰浴中再次冷却,同时滴加氯甲基苯基硫醚(0.46ml,0.54g,3.4mmol)在3ml无水THF中的溶液。将反应混合物缓慢加热至室温并搅拌约24小时,然后加热至50℃并保持54小时。真空(2-10乇)蒸发THF并将反应混合物溶于12ml无水二甲基甲酰胺中。将反应加热至100℃并保持8小时,然后冷却至室温。反应混合物通过天然二氧化铝薄滤板吸滤并用30ml EtoAc洗涤。滤液在真空中蒸发,残余物在真空烘箱中干燥12小时(20-50乇,50℃)。真空蒸馏所得残余物(2-10乇,70℃)。残余物借助色谱法(硅胶,1∶1己烷/二氯甲烷)纯化,得到所需产品,为白色固体,熔点108-109.5℃。
按照该例所用的方法,采用适当的取代的烷基卤化物(例如,制备化合物73时采用苄基氯)代替氯甲基苯基硫醚,制备表I中所述的化合物53,54,55,73和76。实例11:N-(4′-氯苯基)-3-甲基戊二酰亚胺(化合物67)
在装有搅拌棒的500ml单口圆底烧瓶中,将3-甲基戊二酸酐(6.41g,0.05mol)、对氯苯胺(6.39g,0.05mol)和四氢呋喃(50ml)混合。将混合物搅拌至均匀,反应有延迟(5分钟)的温和放热。将浅黄色溶液放置过夜。
真空蒸发混合物,然后真空(约2-10乇)加热干燥,得到褐色固体。固体在真空烘箱中干燥过夜,得到褐色的N-(4′-氯苯基)-3-甲基-戊酰胺酸固体(12.72g,99.4%),熔点116-118。
按实例8所述方法处理戊酰胺酸,得到N-(4′-氯苯基)-3-甲基戊二酰亚胺(产率96%),熔点163-164℃。
按该例所用方法,还制备了表I所述的化合物31和32。实例12:N-(5′-(2-甲基丙氧基羰基)-4′-氯-2′-氟苯基〕-3-(三氟甲基)戊二酰亚胺(化合物75)
a.N-(5′-氯羰基-4′-氯-2′-氯苯基)-3-(三氟甲基)戊二酰亚胺
向N-(5′-羧基-4′-氯-2′-氟苯基)-3-(三氟甲基)戊二酰亚胺(化合物62)(3.0g,8.5mmol)和35ml甲苯的混合物加入亚硫酰二氯(0.80ml,1.3g,1.1mmol),随后滴加两滴N,N-二甲基甲酰胺,加热悬浮液至90℃并保持2小时。将所得澄清、橙色溶液冷却至室温并真空除去溶剂(1mmHg)。所得N-(5′-氯羰基-4′-氯-2′-氟苯基)-3-(三氟甲基)戊二酰亚胺黑色半固体不必进一步提纯便可使用。b.N-(5′(2-甲基丙氧基羰基)-4′-氯-2′-氟苯基〕-3-(三氟甲基)戊二酰亚胺
将由N-(5′-氯羰基-4′-氯-2′-氟苯基)-3-(三氟甲基)戊二酰亚胺(3.1g,8.3mmol)和20mlTHF组成的混合物冷却至0+10℃并加入2-甲基丙醇(0.80ml,0.64g,8.6mmol),随后加三乙胺(1.2ml,0.86g,8.5mmol)。在反应混合物加热至室温时,开始生成白色沉淀。悬浮液在室温搅拌过夜,生成粘稠的白色浆液。反应混合物在水(50ml)和乙酸乙酯(50ml)中分配,并分离液层。水相用乙酸乙酯(3×25ml)萃取,洗涤合并的有机层(1×25ml饱和的NaHCO3,1×25ml盐水)并在MgSO4中干燥。浓缩得到的3.1g橙棕色固体,通过硅胶柱(100g)并用50%乙酸乙酯/己烷洗脱。自甲醇/水中重结晶,得到2.8g(产率82%,自羧酸)所需产物,为褐色固体,熔点82-85℃
按照与该例所用相同的方法,分别采用适当取代的醇、硫醇、肟、肟盐、胺或胺盐酸盐(例如制备化合物78时用异丙胺)代替2-甲基丙醇,制备表I所述的化合物74,77,78,100-104110-114,116-118,127,130,133,135,161-164,194,195,197,199,215,218-221和242。实例13:4-炔丙基-6-(N-(3-(三氟甲基)戊二酰亚胺基))-2H-1,4-苯并噁嗪-3(4H)-酮(化合物85)a.6-硝基-2H-1,4-苯并噁嗪-3(4H)-酮
向10.6g(182mmol)氟化钾和55ml无水二甲基甲酰胺的混合物中加入7.76ml(72mmol)溴代乙酸乙酯,反应混合物在室温下搅拌15分钟。然后加入10.79g(70.0mmol)2-氨基-4-硝基苯酚,并将反应混合物加热至55℃并保持6小时。将反应混合物缓慢地冷却至室温,搅拌12小时,然后倾入300ml冰中。滤出生成的固体,水洗并干燥(20-50乇,50℃,16小时)。将生成的橙色固体溶于100ml EtOAc和100ml H2O中。用EtOAc(2×100ml)萃取水层。然后合并有机层并用水(3×150ml)和10%HCl洗涤并干燥(MgSO4)。真空除去溶剂,生成的固体自二氯乙烷中重结晶,得到3.6g(产率27%)6-硝基-2H-1,4-苯并噁嗪-3(4H)-酮橙色固体。熔点221-223℃。b.6-硝基-4-炔丙基-2H-1,4-苯并噁嗪-3(4H)-酮
在N2下,0.81g(20mmol)氢化钠(60%油悬浮液)用3ml戊烷洗涤并悬浮于20ml无水二甲基甲酰胺中。在用冰/盐水浴冷却的同时,通过干燥的填料斗加入3.59g(18.5mmol)6-硝基-2H-1,4-苯并噁嗪-3(4H)酮(放热约5℃)。另加入10ml DMF,混合物在0℃下搅拌30分钟。然后加入2.06ml(18.5mmol)炔丙基溴在甲苯中的80%溶液,反应混合物在室温下搅拌12小时。将反应混合物倾入50ml水中并用EtOAC(2×50ml)萃取。合并有机相,水洗(2×50ml)并干燥(MgSO4)。真空除去溶剂,得到4g6-硝基-4-炔丙基-2H-1,4-苯并噁嗪-3(4H)-酮黄色固体(产率93%)。c.6-氨基-4-炔丙基-2H-1,4-苯并噁嗪-3(4H)-酮
向5.1g(91mmol)铁粉在42.5ml 5%乙酸水溶液中的淤浆中,滴加4g(17mmol)溶解于42.5ml冰醋酸和42.5ml EtOAc中的6-硝基-4-炔丙基-2H-1,4-苯并噁嗪-3(4H)-酮。加热反应混合物至温和回流1小时,然后冷却至室温。通过吸滤除去铁粉。将EtOAc(50ml)加入到滤液中并分离液层。水相用EtOAc(2×50ml)萃取并合并有机层,用饱和碳酸氢钠水溶液洗涤(100ml),并且干燥(MgSO4)。真空除去溶剂,将得到的浅棕色的油状物溶于50ml水中并用EtOAc(3×50ml)再次萃取,然后干燥(MgSO4)。真空除溶剂,得到2.55g(产率75%)深棕色6-氨基-4-炔丙基-2H-1,4-苯并噁嗪-3(4H)-酮固体,熔点136-140℃。
按实例1和2所述的方法,使6-氨基-4-炔丙基-2H-1,4-苯并噁嗪-3(4H)-酮与3-(三氟甲基)戊二酸酐反应,得到所需产物,熔点203-204.5℃。
按照与该例所用相同的方法,制备表III和IV所述的化合物84,90和171,不同的是,制备化合物84时,用2-氯丙酸甲酯代替溴代乙酸乙酯;制备化合物90时,用在乙酸乙酯中的光气与2-氨基-4-硝基苯酚反应;制备化合物171时,用3-甲基戊二酸酐代替3-(三氟甲基)戊二酸酐。
采用与本实例b和c部分相同的步骤,由6-硝基吲哚、6-硝基二氢吲哚和6-硝基吲唑,制备化合物87、123、153和170。实例14
7-氟-2-甲基-4-炔丙基-6-(N-(3-(三氟甲基)戊二酰胺基))-2H-1,4-苯并噁嗪-3(4H)-酮(化合物88)
a.2-(3′-氟苯氧基)丙酸
向用油浴加热至45℃的间氟苯酚(24.2g,0.22mol)的79.2ml 25%氢氧化钠水溶液中加入29.5ml(0.26mol)2-氯丙酸甲酯。将反应混合物加热至80℃,17小时后使之冷却。温度降至40℃时,加入浓HCl(25ml)然后冷却至室温。用100ml乙醚萃取反应混合物两次,合并有机层,用200ml 1.5M碳酸钠水溶液洗涤。分离出水相,加入浓HCl酸化至PH为1(用PH试纸试出)。用200ml乙醚萃取酸化的水相,分出有机层。经MgSO4干燥后过滤。真空除去溶剂,得到17g(产率41%)2-(3′-氟苯氧基)丙酸,为黄色固体(m·P.72.5-74℃)。
b.2-(2′,4′-二硝基-5′-氟苯基)丙酸
向5g(25mmol)2-(3′-氟苯氧基)丙酸的11.55ml浓硫酸(H2SO4)溶液中经加料漏斗缓慢加入3.59ml70%硝酸(2.1当量)和3.2ml浓H2SO4,加料过程在冰浴冷却下进行。然后使反应混合物缓慢升至室温,并搅拌3小时。将反应混合物倾入200ml冰水中,过滤收集生成的固体,干燥(20-50乇,50℃)12小时,得到3.6g(产率50%)2-(2′,4′-二硝基-5′-氟苯基)丙酸,m。P.141-142℃。
c.6-氨基-7-氟-2-甲基-2H-1,4-苯并噁嗪-3(4H)-酮
向5.05g(90mmol)铁粉于26.5ml 5%乙酸水溶液的悬浮液中滴加3.6g(12.5mmol)2-(2′,4′-二硝基-5′-氟苯基)丙酸于26.5ml EtOAc和26.5ml冰醋酸中的溶液。将反应混合物加热至轻度回流并保持1小时,然后冷却至室温。用抽滤法经Celite膜滤板脱除铁粉,过滤板用50ml EtOAc冲洗。将滤液移至分液漏斗分开各相。水相用EtOAc萃取(3×50ml),合并的有机相用碳酸氢钠洗涤(2×50ml),经MgSO4干燥后过滤。真空下从滤液中脱除溶剂,得到1.5g(产率61%)6-氨基-7-氟-2-甲基-2H-1,4-苯并噁嗪-3(4H)-酮,为褐色固体,m.P.208-211℃。
d.6-氨基-7-氟-2-甲基-4-炔丙基-2H-1,4-苯并噁嗪-3(4H)-酮
氮气下用1ml戊烷洗涤0.30g(7.4mmol)氢化钠(60%分散于油中),然后将其悬浮于2ml无水二甲基甲酰胺。冰冷却下将1.36g(6.9mmol)6-氨基-7-氟-2-甲基-2H-1,4-苯并噁嗪-3(4H)-酮的10ml二甲基甲酰胺溶液用注射器缓慢加到上述氢化钠浆液中,室温下搅拌混合物0.5小时。然后在冰冷却下用注射器加入0.77ml(8.6mmol)炔丙基溴。使反应混合物升至室温,搅拌84小时,然后倾入50ml水中。所得混合物用EtOAc萃取(2×50ml),合并有机相,用水洗涤(3×50ml),经MgSO4干燥后过滤。真空脱除溶剂,得到金色固体,由氯仿重结晶,得到0.66g6-氨基-7-氟-2-甲基-4-炔丙基-2H-1,4-苯并噁嗪-3(4H)-酮,为褐色固体,m.P.142-145℃。
6-氨基-7-氟-2-甲基-4-炔丙基-2H-1,4-苯并噁嗪-3(4H)-酮按实例1和2所述与3-(三氟甲基)戊二酸酐反应,得到目的化合物,m.P.147-148℃。
采用与本实例相同的步骤,不同之处是用实例17a代替a部分,用适当取代的烷基卤或甲磺酰酯(如化合物97用烯丙基溴),制备表III所述化合物89、97、137-139、155、182、208、210、226、230和233。
采用与本实例相同的步骤,不同的是用实例17a代替a部分,用2-溴丁酸乙酯代替溴乙酸甲酯,制备化合物235。
还采用本实例步骤制备化合物145,不同之处是用3-甲基戊二酸酐代替3-(三氟甲基)戊二酸酐。
实例15
N-〔4′-氯-2′-氟-5′-(0-甲基肟基)苯基〕-3-(三氟甲基)戊二酰亚胺(化合物93)
用移液管向甲氧基胺盐酸盐(0.55g,6.6mmol)于无水乙醇(10ml)的悬浮液中加入吡啶(0.52g,6.6ml)。室温下搅拌反应物1小时,然后加入N-(4′-氯-2′-氟-5′-甲酰苯基)-3-(三氟甲基)戊二酰亚胺(2.03g,6.0mmol)(化合物94)固体。再加乙醇(31ml),得到的琥珀色溶液在氮气下搅拌过夜。真空脱除溶剂,剩余物在乙酸乙酯和水间分配。有机相用2.5%HCl(1×25ml)和盐水(1×25ml)洗涤,然后用MgSO4干燥。浓缩后得到棕色固体,经MeOH/H2O重结晶,得到目的化合物戊二酰亚胺,为棕色晶体(1.33g,产率60%,m.p.150.5-152.5℃)。
采用与本实例相同的步骤,使用适当取代的烷氧基胺或烷氧基胺盐代替甲氧基胺盐酸盐,制备表I所述化合物150、156、158、159、168、186、187和205。
采用与本实例相同的步骤,不同的是用N-(4′-氯-2′-氟-5′-乙酰苯基)-3-(三氟申基)戊二酰亚胺(化合物95)代替化合物94与适当取代的烷氧基胺或烷氧基胺盐反应,制备化合物172-176和178。
实例16
4-炔丙基-6-(N-(3-(三氟甲基)戊二酰亚胺基))-2H-1,4-苯并噻嗪-3(4H)-酮(化合物124)
a.S-(2,4-二硝基苯基)巯基乙酸乙酯
向100ml圆底烧瓶中装入14.8g(10ml,79.6mmol)2,4-二硝基氟代苯、THF(20ml,自二苯酮/钠新鲜蒸馏)和三乙胺(11.1ml,79,6mmol)。反应物于冰浴中冷却,同时滴加9.55g(8.73ml,79.6mmol)2-巯基乙酸乙酯的THF(10ml)溶液。将得到的近黑色溶液缓慢升至室温,搅拌18小时。将反应混合物倾在150ml冰水中,分离各层。水相用EtOAc萃取(2×125ml)。合并有机相,用水洗涤(100ml),经MgSO4干燥后真空浓缩至干,得到16.9红褐色固体(产率74.1%)。
b.6-氨基-2H-1,4-苯并噻嗪-3(4H)-酮
向铁粉(15g,0.27mol)在21.7ml 5%乙酸水溶液的悬浮液中经加料漏斗滴加S-(2,4-二硝基苯基)巯基乙酸乙酯(5.91g,20.6mmol)的20.6ml冰醋酸和21mlEtOAc溶液。将反应混合物加热至80℃,2小时后冷却至室温。抽滤出铁粉,滤液用EtOAc萃取(3×75ml)。合并的有机相用100ml水洗涤1次,100ml饱和碳酸氢钠水溶液洗涤两次,干燥(MgSO4)并真空浓缩至干,得到2.3g暗褐色固体。
6-氨基-2H-1,4-苯并噻嗪-3(4H)-酮按实例13b用炔丙基溴烷基化,然后按实例1和2的步骤转化为化合物124。
采用上述步骤,但用2,4-二硝基-1,5-二氟苯代替2,-二硝基氟代苯,制备化合物184。
实例17
7-氟-4-异丁基-6-N-(3-(三氟甲基)戊二酰胺基))-2H-1,4-苯并噁嗪-3(4H)-酮(化合物128)
a。5-氟-2-硝基苯氧基乙酸甲酯
向10g(63.7mmol)5-氟-2-硝基苯酚的100ml甲乙酮溶液中加入10.5g(76.4mmol)研碎的碳酸钾,然后加10.7g(70.1mmol)溴代乙酸甲酯。将所得悬浮液回流6小时。室温下搅拌过夜。在这期间,反应混合物由深红色变为浅黄色。将混合物倾入1升水中,分离各层,水相用EtOAc萃取(2×100ml)。合并有机相,干燥(Na2SO4),过滤并真空蒸发至干,得到13.3g(产率91%)5-氟-2-硝基苯氧基乙酸甲酯,为淡黄色固体(m.P.85-87℃)。
b.7-氟-2H-1,4-苯并噁嗪-3(4H)-酮
将500mg 5%Pd/C装入帕尔烧瓶,加入100mlEtOH,然后加入5.0g(21.8mmol)5-氟-2-硝基苯氧基乙酸甲酯。将烧瓶置于帕尔仪上,抽真空后充入氢气。然后震摇悬浮液2小时。再将烧瓶抽真空,充入氮气,经Celite真空过滤除去固体。由于-些产物尚未析出,滤饼反复用EtOAc(200ml)冲洗。滤液回流4小时,然后真空蒸发至干,得到定量产率的目的产物7-氟-2H-1,4-苯并噁嗪-3(4H)-酮,为白色固体(m.P.201-202℃)。
c.7-氟-4-异丁基-2H-1,4-苯并噁嗪-3(4H)-酮
向3.96g(99mmol)经已烷洗涤过的60%氢化钠的150ml N,N-二甲基甲酰胺溶液中分批加入15g(90mmol)7-氟-2H-1,4-苯并噁嗪-3(4H)-酮固体。加完后,室温下搅拌反应物10分钟,然后加入19.8g异丁基碘。反应混合物搅拌过夜,然后倾入200ml水中。水相用EtOAc萃取(2×150ml),合并的有机相经Na2SO4干燥,过滤和真空蒸发,得到目的烷基化产物,为黄色油体(13g,产率65%)。
d。7-氟-4-异丁基-6-硝基-1,4-苯并噁嗪-3(4H)-酮
向2.50g(11.2mmol)7-氟-4-异丁基-2H-1,4-苯并噁嗪-3(4H)酮的25ml乙酐溶液中用10分钟滴加2.5g(26.9mmol)70%硝酸的5ml冰醋酸溶液。加完后,室温下搅拌反应物1小时,然后倾入50ml冰/水中。真空过滤收集形成的白色沉淀,在真空箱中于60℃干燥过夜,得到2.71g(产率90%)目的硝酸化产物,m.P.108-110℃。
e.6-氨基-7-氟-4-异丁基-1,4-苯并噁嗪-3(4H)-酮
向2.82g(50.5mmol)铁粉在30ml 5%冰醋酸的悬浮液中用0.5小时滴加2.71g(10.1mmol)7-氟-4-异丁基-6-硝基-1,4-苯并噁嗪-3(4H)-酮的60ml EtOAc/冰醋酸(1∶1)溶液。加完后,回流反应物2小时,真空过滤除去固体。滤液用EtOAc萃取(2×100ml),合并的有机相用NaHCO3饱和水溶液洗涤(2×150ml),经Na2SO4干燥后过滤并浓缩(真空),得到2.32g(产率96%)目的苯胺,6-氨基-7-氟-4-异丁基-1,4-苯并噁嗪-3(4H)-酮,为红色半固体。
6-氨基-7-氟-4-异丁基-1,4-苯并噁嗪-3(4H)-酮按实例1和2所述与3-(三氟甲基)戊二酸酐反应,得到目的产物,m.P.180-181℃。
照使适当的烷基化剂代替步骤C中的异丁基碘,采用上述方法制备化合物96、98、122、126、129、131、134、143、146、149、165、166、089和204。基本采用与上述相同的步骤,但在C中使用实例3a的反应条件,制备化合物188。
采用上述步骤,但使用炔丙基溴代替异丁基碘,并使所得6-氨基-7-氟-4-炔丙基-1,4-苯并噁嗪-3(4H)-酮按实例1和2所述与3-(二氟甲基)戊二酸酐反应,制备化合物238。
实例18
4-(正丙基)-6-(N-(3-(三氟甲基)戊二酰亚胺基))-1,4-苯并噁唑啉(化合物136)
向氢化铝锂(1.2g,31.6mmol)的100mlTHF(自钠/二苯酮新鲜蒸馏过)浆液中,用加料漏斗滴加6-氨基-4-正丙基-2H-1,4-苯并噁嗪-3(4H)-酮(1.89g,9.16mmol,用实例13所述的方法制备)的60ml THF溶液。缓慢加料产生轻度回流。加完后,回流反应72小时,然后冷却至室温。加水(1.2ml)后加入3.6ml15%NaOH水溶液,然后再加水(1.2ml)。轻度温升消失后,抽滤反应混合物,固体用100ml THF洗涤。真空浓缩滤液至干,得到1.43g(产率74%)6-氨基-4-正丙基-1,4-苯并噁唑啉,为褐色油体。
使苯胺按实例1和2所述进行反应,得到目的戊二酰亚胺。
实例19
N-〔5′-(3-丁炔氧基)-4′-氯-2′-氟苯基〕-3-(三氟甲基)戊二酰亚胺(化合物140)
将碳酸钾(7.8g,56mmol)加到5-氨基-2-氯-4-氟苯酚(3.23g,19.9mmol)的50ml甲乙酮溶液中,室温下搅拌反应混合物1小时。然后加入4.2g(19.9mmol)4-苯磺酰氧基-1-丁炔(按已知方法由苯磺酰氯和3-丁炔-1-醇制备),回流反应混合物24小时。将反应混合物倾入50ml水中,分开各相。水相用EtoAc萃取(1×50ml),合并的有机相用水洗涤(3×50ml),MgSo4干燥并浓缩。将剩余物溶于110ml CH2Cl2,经硅胶薄填料层过滤,填料层反复用CH2Cl2冲洗(4×100ml)。真空浓缩合并的有机相,得到0.95g(产率22%)目的产物,为褐色油体。将苯胺按实例1和2所述与3-(三氟甲基)戊二酸酐反应,得到目的产物,m.P.89-91℃。
采用与本例相同的步骤,不同的是使用适当的烷基化剂(由甲磺酰氯和醇按已知方法制备)代替4-苯磺酰氧基-1-丁炔,制备化合物141、196、216、231-234和236。
实例20
7-氟-4-甲氧羰基-6-(M-(3-(三氟甲基)戊二酰亚胺基))-2H-1,4-苯并噁嗪-3(4H)-酮(化合物142)
向0.165g(4.13mmol)氢化钠(己烷洗涤)的10ml DMF溶液中加入1.3g(3.75mmol)7-氟-6-(N-(3-(三氟甲基)-戊二酰亚胺基))-2H-1,4-苯并噁嗪-3(4H)-酮(化合物138)的20ml DMF溶液。室温下搅拌反应物10分钟,然后加入0.425g(450mmol)氯甲酸甲酯。搅拌混合物1小时,然后倾入50ml冰/水中,用EtOAc萃取(2×50ml)。合并有机相,经无水Na2SO4干燥后真空浓缩至干。剩余物经色谱层析(硅胶,己烷/EtOAc=1∶1),得到0.58g(产率38%)目的化合物,为黄色油体。
采用相同的步骤,但采用适当的烷基化剂代替氯甲酸甲酯,制备化合物121、179和200。
实例21
N-(3-乙酰氨基-4-甲氧苯基)-3-(三氟甲基)戊二酰亚胺(化合物148)
购得2-甲氧基-5-硝基苯胺,按已知方法使用HOAc/Ac2O的H2O/THF溶液使其乙酰化,制备出2-甲氧基-5-硝基乙酰苯胺。采用催化氢化法(PtO2,H2,EtOH)使之还原,得到3-乙酰氨基-4-甲氧基苯胺,再按实例1和2所述进行反应,得到目的戊二酰亚胺。
实例22
4-甲氧基甲基-6-(N-(3-(三氟甲基)戊二酰胺基))-2H-1,4-苯并噁嗪-3(4H)-酮(化合物151)
a。6-硝基-2H-1,4-苯并噁嗪-3(4H)-酮
向2-氨基-4-硝基苯酚(10.7g,69.4mmol)的150ml CH2Cl2浆液中加入19.37ml(139mmol)三乙胺,搅拌混合物至均相。然后将反应烧瓶冷却至0℃,同时滴加氯乙酰氯(11.06ml,139mmol)的CH2Cl2(50ml)溶液。使反应物升至室温,搅拌16小时,然后将其倾倒在250ml冰上。真空过滤收集形成的白色沉淀,用CH2Cl2(25ml)洗涤,真空烘箱50℃干燥,得到20.56g(产率90%)目的中间产物。
向7。82g(25.6mmol)N,O-双-(氯甲基羰基)-2-氨基-4-硝基苯酚的25ml THF溶液中加入2.67ml(51.2mmOl)50%NaOH和10ml水。室温下搅拌两相反应混合物16小时,然后真空脱除溶剂。将剩余物分布于Et2O(100ml)和水(100ml)并分开各相。水相用Et2O(2×100ml)和EtOAc(2×100ml)相继萃取,合并的有机相经MgSO4干燥并真空浓缩,得到1.3g(产率26%)目的产物(m.P.223-228℃),为黄色固统
b.4-甲氧基甲基-6-硝基-2H-1,4-苯并噁嗪-3(4H)-酮
向0.976g(5.02mmol) 6-硝基-2H-1,4-苯并噁嗪-3(4H)-酮的100ml氯仿溶液中加2ml二甲氧基甲烷。加五氧化二磷(5g,35mmol),室温下搅拌反应混合物16小时。TLC分析表明仍有初始物存在,因此再加二甲氧基甲烷(2ml)和几份五氧化二磷(2×1.2g和2.0g)以及氯仿(50ml)。再搅拌反就物16小时,然后加水(50ml)中止反应。用50ml 1NNaOH缓慢中和反应混合物,在此期间出现升温。反应混合物冷至室温后,分开各相,水相用氯仿萃取(2×50ml)。合并的有机相用水洗涤(2×50ml),经MgSO4干燥和浓缩,得到中间产物(0.5g,产率42%),为浅黄色固体。
采用实例13c的步骤还原该硝基化合物,得到6-氨基-4-甲氧基甲基-2H-1,4-苯并噁嗪-3-酮,再使之按实例1和2所述与3-(三氟甲基)戊二酸酐反应,得到目的产物,m.P.138-140℃。
采用与本例相同的步骤,不同之处是用实例13b代替b部分,使用适当的烷基化剂,制备化合物105、147、154、157、167、211和217。
实例23
N-(4′-氯-5′-氰基-2′-氟苯基)-3-(三氟甲基)戊二酰亚胺(化合物169)
向1.07g(3.03mmol)N-〔4′-氯-2′-氟-5′-(N′-醛肟基苯基)〕-3-(三氟甲基)戊二酰亚胺(化合物159)的CH2Cl2(30ml,含有2.0g无水MgSO4)溶液中加0.40g(0.25ml,3.36mmol)亚硫酰氯。室温下强烈搅拌反应混合物3天,TLC分析表明仍有初始物存在。再加亚硫酰氯(0.1ml),回流反应3小时。TLC表明此时初始物已完全反应。滤出MgSO4,真空脱除溶剂,得到浅黄色固体(0.90g,产率89%),NMR表明其为目的氰基化合物,m.P.210-212℃。
实例24
N-〔5′-(异丙基羧酸铵)-4′-氯-2′-氟苯基〕-3-(三氟甲基)戊二酰亚胺(化合物177)
向N-(5′-羧基-4′-氯-2′-氟苯基)-3-(三氟甲基)戊二酰亚胺(化合物62,1.3g,3.6mmol)的10ml EtOAc溶液中加0.31ml(0.21g,3.6mmol)异丙基胺。室温下搅拌15分钟后形成白色沉淀。滤出该粉未并真空干燥,得到0.95g(产率75%)目的产物盐,m.P.168-173℃(分解)。
实例25
N-〔5′-(羧酸钾)-4′-氯-2′-氟苯基〕-3-(三氟甲基)戊二酰亚胺(化合物213)
向KH(0.6g,以35%(重量)分散于矿物油,用2×5ml己烷洗涤过)的5ml THF溶液中滴加N-(5′-羧基-4′-氯-2′-氟苯基)-3-(三氟甲基)戊二酰亚胺(化合物62,1.8g,5.1mmol)的20ml THF溶液中。氢逸出消失后,搅拌清澈的溶液10分钟,过滤脱除残存的颗粒物。浓缩滤液得到1.8g(产率90%)目的产物钾盐,为白色固体,m.P.133-143℃。
实例26
N-〔3′-(N-甲基乙酰氨基)-4′-氯苯基〕-3-(三氟甲基)戊二酰亚胺(化合物183)
a.N-甲基-2-氯-5-硝基乙酰苯胺
氮气下用戊烷(2×2.5ml)洗涤3.12g氢化钠(78mmol,60%分散于油中),然后将其悬浮于150ml无水DMF。向该悬浮液中加14.0g(65.1mmol)2-氯-5-硝基乙酰苯胺,接着加50ml DMF冲洗。室温下搅拌15分钟,然后加甲基碘(20ml,45g,32mmol),加热至45℃,3小时后再于室温下搅拌85小时。将反应混合物倾入500ml水中,用500ml EtOAc萃取。有机相用水(3×200ml)和盐水(1×200ml)洗涤,干燥(MgSO4)并真空浓缩,得到13.3g(产率89%)N-甲基-2-氯-5-硝基乙酰苯胺,为黄色固体。
b.N-甲基-4-氨基-2-氯乙酰苯胺
在帕尔烧瓶中装入300ml无水乙醇,向其中加12。55g(54.9mmol)N-甲基-2-氯-5-硝基乙酰苯胺。向溶液中鼓入氮气15分钟后,加入300mg氧化铂(IV)。将烧瓶置于帕尔仪器上氢气氛下振摇20分钟。经Celite滤除催化剂,真空浓缩滤液得到10.25g(产率94%)目的苯胺,为黄色固体。
使N-甲基-4-氨基-2-氯乙酰苯胺按实例1和2所述与3-(三氟甲基)戊二酸酐反应,得到目的产物,m.P.203-204℃。
实例27
N-〔4′-氯-2′-氟-5′-(1,3-二氧杂环己基)苯基〕-3-(三氟甲基)戊二酰亚胺(化合物193)
向3.4 g(10mmol)N-(4′-氯-2′-氟-5′-甲酰苯基)-3-(三氟甲基)戊二酰亚胺(化合物94)的110ml甲苯溶液中加0.94g(15mmol)1.2-亚乙基二醇和催化量对甲苯磺酸-水合物(0.48g,2mmol)。混合物回流72小时,同时用迪安-斯达克汽水阀脱除水。真空脱除溶剂.剩余物分布于EtOAc和水。有机相用水和盐水洗涤,经MgSO4干燥后过滤并浓缩,得到4.1g(产率105%)油状乳脂,NMR分析表明其主要含有产物。由Et2O重结晶,得到1.0g1.3-二噁烷,为浅黄色固体,m.P.158-161℃。
实例28
N-(5′-异丁基磺酰基-4′-氯-2′-氟苯基)-3-(三氟甲基)戊二酰亚胺(化合物202)
a.4-氟-2-氟-5-(异丁硫基)乙酰苯胺
将碳酸钾(26g,188mmol)加到5-乙酰氨基-2-氯-4-氟硫代苯酚(11.35g,52.4mmol)的50ml无水DMF溶液中,室温下搅拌反应混合物10分钟。然后加6.63ml(57.0mmol)1-碘-2-甲基丙烷,加热反应混合物至50℃,保持18小时。将反应混合物倾入200ml水中,然后抽滤分离出近白色固体,真空干燥后得到13.31g(产率93%)烷基化产物,为灰白色固体。
b.4-氯-2-氟-5-(异丁基磺酰基)乙酰苯胺
将间-氯过氧苯甲酸(7.7g,36.6mmol)加到4-氯-2-氟-5-(异丁硫基)乙酰苯胺(4.9g,17.8mmol)的50ml CH2Cl2溶液中。在室温下搅拌反应物2.5小时后,再加间一氯过氧苯甲酸(4.6g,21.9mmol),搅拌30分钟后将反应混合物倾入50ml水中。分离有机相,用碳酸氢钠饱和水溶液(2×50ml)、水(1×50ml)和碳酸氢钠饱和水溶液(2×50ml)相继洗涤。真空脱除溶剂,将剩余物溶于100ml CH2Cl2,用10%亚硫酸钠水溶液(1×100ml)和碳酸氢钠水溶液(1×10ml)洗涤。有机相真空浓缩至干,得到5.5g黄色固体,NMR鉴定主要含目的产物。这一相产物用于下一反应。
C,4-氯-2-氟-5-(异丁基磺酰基)苯胺将浓盐酸(16.65ml,200mmol)加到4-氯-2-氟-5-(异丁基磺酰基)乙酰苯胺(5.46g,17.7mmol)的水(24.85ml)和乙醇(19.08)浆液中。反应混合物回流2小时,倾在200ml冰上,通过加50%NaOH使其呈强碱性。水相用Et2O萃取(2×100ml),合并的有机相用水(1×100ml)和盐水(1×100ml)洗涤,干燥(Na2SO4)和真空浓缩。得到的褐色固体(3.8g,产率81%)经NMR证实主要含有目的苯胺。
上述4-氯-2-氟-5-(异丁基磺酰基)苯胺按实例1和2所述与3-(三氟甲基)戊二酸酐反应,制备化合物202,m.P。48-51℃。
实例29
N-(5′-双-乙酰氨基-4′-氯-2′-氟苯基)-3-(三氟甲基)戊二酰亚胺(化合物225)
将100ml无水乙醇装入帕尔烧瓶,向其中加3.21g(8.61mmol)N-(4′-氯-2′-氟-5′-硝基苯基)-3-(三氟甲基)戊酰胺酸(采用实例1的方法由4-氯-2-氟-5-硝基苯胺和3-(三氟甲基)戊二酸酐制备)。向溶液中鼓入氮气15分钟后,加100mg氧化铂(IV)。将烧瓶置于帕尔仪器上于氢气氛下振摇1小时。经Celite过滤脱除固体物,滤液浓缩至干,得到3.1g(产率100%)含有N-(5′-氨基-4′-氯-2′-氟苯基)-3-(三氟甲基)戊酰胺酸的灰白色固体。
采用实例2所述的步骤,将N-(5′-氨基-4′-氯-2′-氟苯基)-3-(三氟甲基)戊酰胺酸转化为化合物225,m.P.164-160℃。
实例30
N-〔4′-氯-2′-氟-5′-(4″,4″-二甲基-2-噁唑啉-2-基)苯基〕-3-(三氟甲基)戊二酰亚胺(化合物227)
a.2-氟-4-氟-5-硝基苯甲酰氯
向2-氟-4-氟-5-硝基苯甲酸(4.0g,18mmol)的65ml甲苯溶液中加2滴DMF,接着加1.8ml(25mmol)亚硫酰氯。混合物加热至回流18小时,冷却至室温,真空脱除溶剂,得到4.0g(产率93%)白色固体,IR和NMR鉴定为目的产物苯甲酰氯,这一粗产物直接用于下一步骤。
b.N-(1,1-二甲基-2-羟乙基)-2-氯-4-氟-5-硝基苯甲酰胺
向冷却的(0℃)2-氨基-2-甲基-1-丙醇(2.4ml,2.2g,25mmol)的CH2Cl2(10ml)溶液中用加料漏斗滴加3.0g(12mmol)2-氯-4-氟-5-硝基苯甲酰氯的20ml CH2Cl2溶液。加完后使反应混合物升至室温,形成白色沉淀。1.5小时后,加入10ml水,过滤,得到2.1g浅黄色固体,NMR鉴定为目的产物。滤液用EtOAc萃取(3×75ml),合并的有机相用盐水、饱和碳酸钠和再次用盐水洗涤。然后用MgSO4干燥。浓缩后得到1.0g产物(3.1g,总产率86%)。
c.2-(2′-氯-4′-氟-5′-硝基苯基)-4,4-二甲基-2-噁唑啉
向N-(1,1-二甲基-2-羟乙基)-2-氯-4-氟-5-硝基苯甲酰胺(2.0g,6.9mmol)的30ml EtOAc溶液中滴加1.6ml(2.6g,22mmol)亚硫酰氯。得到的清澈黄色溶液在室温下搅拌25分钟,在此期间形成白色沉淀。用30ml 10%NaOH处理反应混合物,由于固体溶解而导致轻微放热。水相用EtOAc萃取(3×25ml),合并的有机相用盐水洗涤,干燥(MgSO4),浓缩,得到1.85g(产率98%)产物,为黄色固体。
如实例13c所述将2-(2′-氯-4′-氟-5′-硝基苯基)-4,4-二甲基-2-噁唑啉还原为相应的苯胺,再采用实例1和2的步骤将其转化为戊二酰亚胺(化合物227)。
实例31
6-氟-3-正丙基-5-N-(3-(三氟甲基)戊二酰亚胺基))-1,3-苯并噁唑啉-2(3H)-酮(化合物181)
a.2-氨基-5-氟苯酚
将500mg 10%钯/碳催化剂装入含有50ml无水乙醇的帕尔烧瓶中,向其中加入10g(64mmol)5-氟-2-硝基苯酚的150ml乙醇溶液。将烧瓶抽真空,充入氢气,在帕尔仪器上振摇1小时。经Celite滤除催化剂,真空蒸发滤液至干,得到7.54g(产率93%)黑色固体。
b.6-氟-1,3-苯并噁唑啉-2(3H)-酮
向置于0℃下的5.0g(39.3mmol)2-氨基-5-氟苯酚的150ml CH2Cl2溶液中加13.4g(98mmol)碳酸钾和23g(47mmol)碳酰氯的20%(重)甲苯溶液。升至室温后,搅拌反应1小时,然后倾入200ml冰/水中。分离各相,用EtOAc萃取(1×100ml),然后合并有机相并用Na2SO4干燥。真空脱除溶剂,得到5.76g(产率96%)目的产物,由1H-NMR测定。
c.6-氟-3-正丙基-1,3-苯并噁唑啉-2(3H)-酮
向670mg(16.74mmol)氢化钠(用己烷洗涤过)的20ml DMF溶液中加2.33g(15.22mmol)6-氟-1,3-苯并噁唑啉-2(3H)-酮的40ml DMF溶液。搅拌反应10分钟,加入3.11g(18.3mmol)1-碘代丙烷,然后在室温下搅拌3小时。将其倾入50ml冰/水后,水相用EtOAc萃取(2×100ml)。合并的有机相用水洗涤(1×100ml),Na2SO4干燥并真空蒸发至干,得到2.2g(产率75%)烷基化产物,为褐色固体。
d。6-氟-5-硝基-3-正丙基-1,3 -苯并噁唑啉-2(3H)-酮
向2.0g(10.3mmol)6-氟-3-正丙基-1,3-苯并噁唑啉-2(3H)-酮的25ml乙酐溶液中滴加2.3g(24.7mmol)70%硝酸的2ml冰醋酸溶液。加完后,室温下搅拌反应2小时,然后将其倾入50ml冰/水中。水相用EtOAc萃取(2×70ml),合并的有机相经Na2SO4干燥并真空蒸发至干,得到1.66g(产率67%)硝酸化产物,为黄色油体。
按实例17e的步骤将上述制备的6-氟-5-硝基-3-正丙基-1,3-苯并噁唑啉-2(3H)-酮还原为相应的苯胺,再按实例1和2的步骤使其与3-(三氟甲基)戊二酸酐反应,得到目的产物,m.P.198-152℃。
实例32
N-(6-氟-1-正丙基-4H-3,1-苯并噁嗪-2(H)-酮-7-基)-3-(三氟甲基)戊二酰亚胺(化合物198)
a.3,1,4-苯并噁嗪-2(1H)-酮
向置于0℃的4.0g(32.5mmol)2-氨基苄醇的200ml CH2Cl2溶液中加11.12g(81.2mmol)碳酸钾,接着加19.3g(39.0mmol)碳酰氯的20%(重)甲苯溶液。将反应混合物缓慢升至室温,然后搅拌5小时。将反应混合物倾入200ml饱和NaHCO,分离各相,有机相用Na2SO4干燥,浓缩后得到4.55g(产率84%)产物,为白色固体。
按实例17c-e和实例1和2所述,但使用1-碘代丙烷代替异丁基碘,将上述3,1,4-苯并噁嗪-2(1H)-酮转化为目的产物戊二酰亚胺(m.P。158-160℃)。
实例33
7-氟-4-环氧丙基-6-N-(3-三氟甲基)戊二酰亚胺基))-2H-1,4-苯并噁嗪-3(4H)-酮(化合物239)
向1.0g(2.6mmol)4-烯丙基-7-氟-6-N-(3-三氟甲基)戊二酰亚胺基))-2H-1,4-苯并噁嗪-3(4H)-酮(化合物97)的50ml CH2Cl2溶液中加2.45g(7.8mmol)间-氯过氧苯甲酸。室温下搅拌混合物过夜,然后将其倾入50ml饱和NaHCO3中。分离各相,有机相用Na2SO4干燥并真空浓缩至干。粗产物用制备薄层色谱提纯(60/40正烷:EtOAc),得到400mg(产率38%)目的环氧化物,为清澈的油。
采用上述步骤,不同的是初始物为N-(5′-烯丙基氧基-4′-氯-2′-氟苯基)-3-(三氟甲基)戊二酰亚胺(化合物9)以及反应在CHCl3中回流过夜,制备化合物245。
实例34
N-〔4′-氯-5′-(3,3-二氯烯丙氧基)-2′-氟苯基〕-3-(三氟甲基)戊二酰亚胺(化合物244)
将溶于5ml水的氢氧化钾(1.95g,34.8mmol)加到5-氨基-2-氯-4-氟苯酚(5.65g,34.8mmol)的40ml二甲亚砜溶液中。室温下搅拌所得混合物18小时,然后将其倾入100ml水,用Et2O萃取(2×100ml)。合并的有机相用水洗涤(2×100ml),Na2SO4干燥并经中性二氧化铝薄填料层过滤(伴随Et2O冲洗,3×50ml)。真空浓缩滤液,得到7.56g(产率74%)主要含产物(1H-NMR鉴定)的褐色油。
使上述粗产物苯胺按实例1和2所述与3-(三氟甲基)戊二酸酐反应,得到目的产物,m.P.106-108℃。
采用与本例相同的步骤,但使用的烷基化剂是2-氯-1-丁烯,制备化合物240。采用这一步骤也制备了化合物243,只是用炔丙基溴作为烷基化剂并使所得苯胺与3-(二氟甲基)戊二酸酐反应,而不是与3-(三氟甲基)戊二酸酐反应。
实例35
N-(4′-氯-2′-氟-5′-硝基苯基)-3-(三氟甲基)戊二酰亚胺(化合物222)
a.4-氯-2-氟-5-硝基乙酰苯胺
向装有机械搅拌器的500ml三颈圆底烧瓶中装入4-氯-2-氟代乙酰苯胺(56.3g,0.3mmol)和浓H2SO4(100ml)。将其冷却至0℃,用30分钟加入发烟硝酸(21g,0.33mol),然后将反应混合物倾在2升冰上。待冰融化后,过滤收集固体物,水洗并在减压下干燥,得到44g(产率63%)硝酸化物,为褐色固体。
b。4-氟-2-氟-5-硝基苯胺
将4-氯-2-氟-5-硝基乙酰苯胺(10.88g,46.8mmol)、50.4ml乙醇、65.7ml水和43.8ml(526mmol)浓盐酸的混合物回流1小时,然后倾在300ml冰上。加入50%氢氧化钠水溶液使水相呈强碱性,用2×200ml Et2O萃取。合并的有机相用水(200ml)和盐水(200ml)洗涤,Na2SO4干燥并真空浓缩至干,得到8g(产率90%)目的产物苯胺,为黄色固体。
按实例1和2所述,将该苯胺与3-(三氟甲基)戊二酐反应,得到所需的戊二酰亚胺,熔点为164-167℃。
实例36
N-(5′-异丁基亚砜-4′-氯-2′-氟苯基)-3-(三氟甲基)戊二酰亚胺(化合物246)
向已冷却至0℃的4-氯-2-氟-5-(异丁硫基)N-乙酰苯胺(见实例28a)(1.04g,3.8mmol)于30ml乙醇的溶液中加入高碘酸钠(1.29g,6.0mmol)于30ml水的溶液。使反应温热至室温并搅拌18小时。抽滤除去固体,将滤液溶于75ml二氯甲烷,然后用水(50ml)洗涤。用Na2SO4干燥有机层,浓缩至干,得到1g(产率90%)白色固状的所需亚砜。
采用实例28C的步骤制备相应的苯胺,按实例1和2所述,将苯胺与3-(三氟甲基)戊二酐反应,得到所需的戊二酰亚胺,熔点为133-134℃。
本发明的化合物是广谱除草剂,可用于选择性地防治农艺和园艺作物、森林、果园、草场、葡萄园中的单子叶和/或双子叶杂草或用于杂草的全面防治。
本发明的化合物具有选择性或非选择性,这取决于施用量、所施用的植物的组合情况以及芽前或芽后施用。这些变化对本专业领域的熟练技术人员来说是可理解的。当剂量较高时,它们往往是非选择性的,而当剂量较低时,它们往往是选择性的。例如,上述醚和硫醚戊二酰亚胺化合物均具有芽前和芽后活性并可芽后防治小麦中的双子叶杂草;酯戊二酰亚胺可芽前和芽后防治单子叶和双子叶杂草,防治双子叶杂草的所需剂量通常比防治单子叶杂草的低;杂环戊二酰亚胺在作物如小麦、玉米、稻谷、大豆、向日葵、花生和棉花中具有芽前和/或芽后防治选择性。
本发明的戊二酰亚胺可按能控制不需要的植物生长所需的任何剂量施用。本发明的除草剂的用量通常约为0.0001至12,较好为约0.001至5磅戊二酰亚胺化合物/英亩,最好为约0.002至2磅戊二酰亚胺化合物/英亩(分别为1.12×10-5-1.344克/米2,11.2×10-5-0.56克/米2,22.4×10-5-0.224克/米2)。
本发明的化合物可用作芽前和芽后除草剂,芽前除草剂可施用在土壤表面或掺入土壤中。芽后除草剂可在植物出芽后和生长期间施用。本发明的戊二酰亚胺可在植物出芽前施用在土壤表面或在种植前掺入土壤或其它生长介质中。可采用任何常规方法进行掺和,包括与土壤简单混合;将戊二酰亚胺施用在土壤表面,然后翻入或耙入土壤中至所需深度;或用液态载体进行必要的渗透和浸透。
本发明的戊二酰亚胺可单独或通常作为其中还含有农用载体的除草组合物或制剂的一个组分在芽后施用于生长介质或要处理的植物。除草组合物中的戊二酰亚胺的浓度可在约1至98%范围内变化。
所谓农用载体是指任何能用于溶解、分散或扩散组合物中的除草化合物而不减弱除草化合物的作用且其本身对土壤、农机、作物或农业环境无有害作用的物质。本发明的戊二酰亚胺的混合物也可用于任何除草制剂。本发明的除草组合物可以是固体或液态制剂或溶液。可将戊二酰亚胺制成本领域熟练技术人员已知的剂型,例如可湿性粉剂、溶液、浓乳液、粉剂、颗粒剂、喷雾剂、水分散性颗粒剂或可流动浓缩液。在这些制剂中,化合物与液态或固态载体混匀,如果需要,可加入合适的表面活性剂或乳化剂。可用于本发明的溶剂的例子有水、醇类、酮类、芳族烃、卤代烃、二甲基甲酰胺、二噁烷、二甲亚砜等。也可使用这些溶剂的混合物。
根据农用实际情况,特别是在芽后应用下,通常需要使除草剂合有助剂,如湿润剂、扩展剂、分散剂、附着剂、粘合剂等。本领域常用的助剂的例子可在John W.McCutcheon,Inc、Publication″Detergents and Emulsifiers Annual″中找到。
本发明的戊二酰亚胺在施用前可与肥料或具有肥料作用的物料混合。在一类可使用戊二酰亚胺的固态肥料组合物中,可用一种或多种戊二酰亚胺涂覆肥料或肥料组分如硫酸铵、硝酸铵或磷酸铵的颗粒。固态戊二酰亚胺和固态肥料也可在掺合或混合装置中混合,或将它们与肥料一起合并在颗粒制剂中。可采用任何适合于作物生长和杂草处理的成二酰亚胺与肥料的相对比例。
本发明的戊二酰亚胺可作为除草喷洒剂用常规方法如加仑液压喷洒、低加仑液压喷洒、空气喷洒、气雾喷洒或粉尘喷洒的方法施用。对于某些应用,可使用本发明的二种或多种戊二酰亚胺,以提供附加的优势和作用。当使用本发明的戊二酰亚胺的混合物时,所用的各个化合物的相对比例取决于混合物中化合物对要处理的植物的相对效应。
对于某些应用而言,可往本发明的戊二酰亚胺中加入一种或多种其它除草剂,从而提供附加的优势和作用。当使用除草剂的混合物时,所用的相对比例取决于混合物中化合物对要处理的植物的相对效应。可与本发明的戊二酰亚胺组合的其它除草剂的例子包括:
羧酸和衍生物
2,3,6-三氯苯甲酸和其盐;
2,3,5,6-四氯苯甲酸和其盐;
2-甲氧基-3,5,6-三氯苯甲酸和其盐;
2-甲氧基-3,6-二氯苯甲酸和其盐;
2-甲基-3,6-二氯苯甲酸和其盐;
2,3-二氯-6-甲基苯甲酸和其盐;
2,4-二氯苯氧乙酸和其盐和酯;
2,4,5-三氯苯氧乙酸和其盐和酯;
2-甲基-4-氯苯氧乙酸和其盐和酯;
2-(2,4,5-三氯苯氧基)丙酸和其盐和酯;
4-(2,4-二氯苯氧基)丁酸和其盐和酯;
4-(2-甲基-4-氯苯氧基)丁酸和其盐和酯;
2,3,6-三氯苯基乙酸和其盐;
3,6-环氧六氢化邻苯二甲酸和其盐;
2,3,5,6-四氯对苯二甲酸二甲酯;
三氯乙酸和其盐;
2,2-二氯丙酸和其盐;
2,3-二氯异丁酸和其盐;
2-(4-异丙基-4-甲基-5-氧-2-咪唑啉-2-基)烟酸异丁铵;
2,〔4,5-二氢-4-甲基-4-(1-甲基乙基)-5-氧-1H-咪唑-2-基〕-3-喹啉羧酸;
6-(4-异丙基-4-甲基-5-氧-2-咪唑啉-2-基)-间甲苯甲酸甲酯和6-(4-异丙基-4-甲基-5-氧-2-咪唑啉-2-基)对甲苯甲酸甲酯;
N-(磷酰基甲基)甘氨酸异丙铵盐;
〔3,5,6-三氯-(2-吡啶-)氧基〕乙酸;
3,7-二氯-8-喹啉羧酸;
dl-同型丙氨-4-酰基(甲基)次膦酸铵;
氨基甲酸衍生物
N,N-二正丙基硫羟氨基甲酸乙酯;
N,N-二正丙基硫羟氨基甲酸正丙酯;
N-乙基-N-(正丁基)硫羟氨基甲酸乙酯;
N-乙基-N-(正丁基)硫羟氨基甲酸正丙酯;
N,N-二乙基二硫代氨基甲酸2-氯烯丙酯;
N-甲基二硫代氨基甲酸盐;
1-六亚甲基亚胺硫代羧酸乙酯;
N-苯基氨基甲酸异丙酯;
N-(间氯苯基)氨基甲酸异丙酯;
4-氯-2-丁炔基-N-(间氯苯基)氨基甲酸酯;
N-(3,4-二氯苯基)氨基甲酸甲酯;
二硝基-邻-(仲丁基)苯酚和其盐;
五氯苯酚和其盐;
S-(4-氯苄基)-N,N-二乙基硫羟氨基甲酸酯;
取代的脲
2-氯-N-〔(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基羰基〕-苯磺酰胺;
3-(3,4-二氯苯基)-1,1-二甲基脲;
3-苯基-1,1-二甲基脲;
3-(3,4-二氯苯基)-3-甲氧基-1,1-二甲基脲;
3-(4-氯苯基)-3-甲氧基-1,1-二甲基脲;
3-(3,4-二氯苯基)-1-正丁基-1-甲基脲;
3-(3,4-二氯苯基)-1-甲氧基-1-甲基脲;
3-(4-氯苯基)-1-甲氧基-1-甲基脲;
3-(3,4-二氯苯基)-1,1,3-三甲基脲;
3-(3,4-二氯苯基)二乙基脲;
二氯脲;
2-〔〔〔〔(4,6-二甲基-2-嘧啶基)氨基〕羰基〕氨基〕磺酰基〕苯甲酸甲酯;
N-((6-甲氧基-4-甲基-1,3,5-三嗪-2-基)氨基羰基)-2-(2-氯乙氧基)苯磺酰胺;
2-〔〔〔(4-氯-6-甲氧基嘧啶-2-基)氨基羰基〕氨基〕-磺酰基〕苯甲酸乙酯;
2-〔〔〔〔(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基〕羰基〕氨基〕磺酰基〕苯甲酸甲酯;
3-〔〔〔〔(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基〕羰基〕氨基〕磺酰基〕-2-噻吩羧酸甲酯;
2-〔〔〔〔(4,6-二甲氧基嘧啶-2-基)氨基〕羰基〕氨基〕磺酰基〕甲基〕苯甲酸甲酯;
2-〔〔〔〔(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)甲基氨基〕羰基〕氨基〕磺酰基〕苯甲酸甲酯;
取代的三嗪
2-氯-4,6-二(乙基氨基)-仲三嗪;
2-氯-4-乙基氨基-6-异丙基氨基-仲三嗪;
2-氯-4,6-二(甲氧基-正丙基氨基-仲三嗪;
2-甲氧基-4,6-二(异丙基氨基)-仲三嗪;
2-氯-4-乙基氨基-6-(3-甲氧基-正丙基氨基)-仲三嗪;
2-甲基巯基-4,6-二(异丙基氨基)-仲三嗪;
2-甲基巯基-4,6-二(乙基氨基)-仲三嗪;
2-甲基巯基-4-乙基氨基-6-异丙基氨基-仲三嗪;
2-氯-4,6-二(异丙基氨基)-仲三嗪;
2-甲氧基-4,6-二(乙基氨基)-仲三嗪;
2-甲氧基-4-乙基氨基-6-异丙基氨基-仲三嗪;
2-甲基巯基-4-(2-甲氧基乙基氨基)-6-异丙基氨基-仲三嗪;
4-氨基-6-(叔丁基)-3-(甲巯基)-1,2,4-三嗪-5(4H)酮;
二苯醚衍生物
2,4-二氯-4 ′-硝基二苯醚;
2,4,6-三氯-4′-硝基二苯醚;
2,4-二氯-6-氟-4′-硝基二苯醚;
3-甲基-4′-硝基二苯醚;
3,5-二甲基-4′-硝基二苯醚;
2,4-二硝基-4-(三氟甲基)二苯醚;
2,4-二氯-3′-甲氧基-4′-硝基二苯醚;
5-(2-氯-4-(三氟甲基)苯氧基)-2-硝基苯甲酸钠;
2-氯-1-(3-乙氧基-4-硝基苯氧基)-4-(三氟甲基)苯;
5-〔2-氯-4-(三氟甲基)苯氧基〕-2-硝基苯甲酸-1-(乙酯基)乙酯;
5-〔2-氯-4-(三氟甲基)苯氧基〕-N-(甲基磺酰基)-2-硝基苯甲酰胺;
N-酰苯胺
2-氯-N-(2-乙基-6-甲基苯基)-N-(2-甲氧基-1-甲基乙基)乙酰胺;
2-氯-2′,6′-二乙基-N-(2-丙氧基乙基)乙酰苯胺;
N-(3,4-二氯苯基)丙酰胺;
N-(3,4-二氯苯基)甲基丙烯酰胺;
N-(3-氯-4-甲基苯基)-2-甲基戊酰胺;
N-(3,4-二氯苯基)三甲基乙酰胺;
N-(3,4-二氯苯基)-α,α-二甲基正戊酰胺;
N-异丙基-N-苯基氯乙酰胺;
N-正丁氧基甲基-N-(2,6-二乙基苯基)氯乙酰胺;
N-甲氧基甲基-N-(2,6-二乙基苯基)氯乙酰胺;
氧苯氧基除草剂
丙酸2-(4-(2,4-二氯苯氧基)苯氧基)甲酯;
2-(4-(3-氯-5-(三氟甲基)-2-吡啶基氧基)苯氧基)丙酸甲酯;
(R)-L-〔4-〔5-(三氟甲基)-2-吡啶基氧基)苯氧基〕丙酸丁酯;
2-〔4-〔(6-氯-2-苯并噁唑基)氧基〕苯氧基〕丙酸乙酯;
2-〔4-〔〔5-(三氟甲基)-2-吡啶基〕氧基〕苯氧基〕丙酸丁酯;
2-〔4-〔(6-氯-2-喹喔啉基)氧基〕苯氧基〕丙酸乙酯;
尿嘧啶
5-溴-3-仲丁基-6-甲基尿嘧啶;
5-溴-3-环己基-1,6-二甲基尿嘧啶;
3-环己基-5,6-亚丙基尿嘧啶;
5-溴-3-异丙基-6-甲基尿嘧啶;
3-叔丁基-5-氯-6-甲基尿嘧啶;
腈
2,6-二氯苄腈;二苯乙腈;3,5-二溴-4-羟基苄腈;3,5-二碘-4-羟基苄腈;
其它有机除草剂
2-氯-N,N-二烯丙基乙酰胺;
N-(1,1-二甲基-2-丙炔基)-3,5-二氯苯甲酰胺;
马来酰肼;
3-氨基-1,2,4-三唑;
甲胂酸-钠;
甲胂酸二钠;
N,N-二甲基-α,α-二苯基乙酰胺;
N,N-二正丙基-2,6-二硝基-4-(三氟甲基)苯胺;
N,N-二正丙基-2,6-二硝基-4-甲基苯胺;
N,N-二正丙基-2,6-二硝基-4-甲基磺酰基苯胺;
异丙基氨基硫基磷酸0-(2,4-二氯苯基)-0-甲酯;
4-氨基-3,5,6-三氯吡啶甲酸;
2,3-二氯-1,4-萘醌;
二(甲氧基硫基羰基)二硫化物;
3-(1-甲基乙基)-1H-2,1,3-苯并噻二嗪-(4)3H-酮-2,2-二氧化物;
6,7-二氢联吡啶醇〔1,2-a:2′,1′-C〕吡嗪二盐;
1,1′-二甲基-4,4′-联吡啶盐;
3,4,5,6-四氢-3,5-二甲基-2-硫基-2H-1,3,5-噻二嗪;
2-〔1-乙氧基亚氨基)丁基〕-5-〔2-(乙基硫基)丙基〕-3-羟基-2-环己-1-酮;
2-(2-氯苯基)甲基-4,4-二甲基-3-异噁唑烷酮;
N-(1-乙基丙基)-3,4-二甲基)-2,6-二硝基苯甲酰胺;
4-氯-5-(甲基氨基)-2-(α,α,α-三氟-1-甲苯甲酰)-3-(2H)-哒嗪酮;
2-(3,5-二氯苯基)-2-(2,2,2-三氯甲基)环氧乙烷。
采用温室测试方法评估本发明的戊二酰亚胺对几种常规杂草的除草活性采用下述步骤评估本发明的戊二酰亚胺对下述杂草的防治效果:
单子叶
稗子(BYG) Echinochloa crug-galli
马唐(CRB) Digitaria sanguinilis
狗尾草(FOX) Setaria viridis
石茅高粱(JON) Sorghum halepense
草原看麦娘(MF) Alopecurus pratensis
油莎草(NUT) Cyperus esculentus
野燕麦(WO) Avena fatua
双子叶
鬼针草(BID) Bidens pilosa
苍耳(CKL) Xanthium strumarium
朝颜草(MG) Ipomoea lacunosa
龙癸(NS) Solanum nigrum
藜 (PIG) Amaranthus retroflexus
大马蓼(SMT) Polygonum lapathifolium
绒毛页(VEL) Abutilon theophrasti
采用下列试验步骤,将选择植物的种子种植在平地或盆内。对于芽前试验,在种植后立即将试验化合物直接喷洒到土壤表面。然后用顶部灌溉法往平地或盆内浇水。对于芽后试验,让种子发芽并生长10至21天。从生长的均匀性、大小和叶龄的角度出发选择各组试验植物,然后用试验化合物处理试验植物。芽后试验植物仅用地下灌溉的方法浇水。
将要评估的化合物溶于一种合适的溶剂(通常为丙酮)中,使用体积等于25或50加仑/英亩的载体,以表中所定的施用量磅/英亩)喷洒在平地或盆内。施用试验化合物约10至21天后,观察植物的生长情况。以0-100的等级评估各组植物,其中0等于无效,100等于全部控制,下列各表(表VI和VII)给出了在所述用量下试验化合物所获得的结果。表中,PRE表示芽前,POST表示芽后。
表 VI
除草活性
应用化合物 比例编号 (Ib/A)类型 CKL MG PIG VEL SMT BYG FOX ION NUT WO1. 2 PRE 100 100 100 100 100 100 100 100 100 100
2 POST 100 100 100 100 100 100 99 98 1002. 2 PRE 100 100 100 100 100 100 100 100 100 100
2 POST 100 100 100 100 - 100 100 99 5 1003. 2 PRE 100 100 100 100 - 100 100 100 80 99
2 POST 100 100 100 100 100 100 100 99 80 904. 2 PRE 0 100 100 100 100 100 100 85 10 90
2 POST 99 100 100 100 100 100 100 65 10 705. 1 PRE 71 100 100 100 100 100 100 100 65 100
1 POST 100 100 100 100 100 99 100 90 90 1006. 1 PRE 100 100 100 100 100 100 100 98 100 100
1 POST 100 100 100 100 100 100 100 100 0 607. 1 PRE 100 100 100 100 100 99 100 100 0 100
1 POST 100 99 100 100 100 100 100 100 0 358. 1 PRE 0 90 0 100 15 41 98 0 0 0
1 POST 45 15 100 100 100 6 75 15 0 359. 2 PRE 75 100 100 100 - 100 100 90 80 90
2 POST 100 100 100 100 100 100 100 70 65 10010. 1 PRE 100 100 100 100 100 100 100 100 30 100
1 POST 71 100 100 100 100 100 100 100 100 10011. 1 PRE 0 0 0 100 0 0 21 15 0 0
1 POST 70 60 95 100 100 15 25 5 0 012. 1 PRE 0 100 100 100 100 99 100 95 80 98
1 POST 100 100 100 100 100 95 100 98 10 10013. 4 PRE - 0 0 0 0 0 0 0 0 0
4 POST 15 45 100 45 15 10 30 10 0 1014. 4 PRE 80 100 100 100 100 100 100 100 100 100
4 POST 0 100 100 100 0 100 100 98 45 9815. 4 PRE 0 0 100 100 100 10 100 20 0 0
4 POST 5 35 20 60 10 15 90 10 0 516. 4 PRE 0 95 100 100 0 0 95 0 0 27
4 POST 0 80 100 100 10 20 100 10 0 1017. 4 PRE 100 100 100 100 100 100 100 98 100 75
4 POST 100 100 100 100 100 100 99 25 65 65
应用 表VI(续)化合物 比例 类型编号 (Ib/A) CKL MG PlG VEL SMT BYG FOX ION NLT WO18. 4 PRE 0 100 100 100 50 100 100 70 98 65
4 POST 35 100 100 100 98 85 100 10 80 1019. 4 PRE 0 90 100 100 0 45 100 0 20 25
4 POST 100 90 98 100 20 100 100 25 10 8520. 4 PRE 0 0 100 100 50 0 0 0 0 0
4 POST 100 20 100 100 100 90 100 20 10 1521. 4 PRE 31 64 100 100 100 0 100 0 0 0
4 POST 15 10 100 95 100 0 0 0 0 022. 4 PRE 98 100 100 100 100 100 100 80 75 51
4 POST 55 55 100 100 85 20 100 5 45 523. 4 PRE 0 0 100 100 0 90 100 15 0 0
4 POST 0 0 25 0 0 0 0 0 0 024. 1 PRE 0 100 100 100 100 70 100 85 70 10
1 POST 100 99 100 100 100 40 100 20 10 2025. 1 PRE 0 100 100 100 100 99 100 85 85 90
1 POST 40 100 100 100 100 100 100 30 10 2526. 4 PRE 0 0 100 15 0 15 100 20 0 0
4 POST 15 15 90 100 35 0 15 5 0 027. 4 PRE 0 0 100 20 - 75 100 51 0 20
4 POST 0 70 100 35 100 70 45 15 0 1528. 4 PRE 0 90 100 100 100 98 100 95 25 85
4 POST 0 5 100 100 100 5 5 0 0 029. 2 PRE 100 100 100 100 100 100 100 100 100 100
2 POST 100 100 100 100 100 100 100 85 95 9930. 1 PRE 0 100 100 100 100 100 100 80 85 80
1 POST 45 100 100 100 100 95 95 40 0 4531. 4 PRE 0 0 100 100 - 50 100 85 - 0
4 POST 0 0 5 0 - 0 0 0 0 032. 4 PRE 0 15 100 100 80 75 100 0 60 21
4 POST 0 5 10 5 10 0 0 0 0 034. 4 PRE 0 5 100 100 0 75 100 5 5 0
4 POST 5 45 90 100 98 20 15 5 0 5
表VI(续)
应用化合物 比例 类型编号 (Ib/A) CKL MG PIG VEL SMT BYG FOX ION NUT WO35. 4 PRE 0 0 - 100 0 0 21 0 0 0
4 POST 0 10 0 0 0 0 0 0 0 036. 4 PRE 0 0 0 0 0 0 0 0 0 0
4 POST 0 20 15 25 0 10 5 0 0 037. 4 PRE 0 0 0 21 51 21 51 51 51 61
4 POST 0 0 0 0 0 0 0 0 0 038. 1 PRE 0 0 100 100 100 60 100 25 0 15
1 POST 5 10 15 10 10 0 0 0 0 039. 4 PRE 0 0 - 45 0 0 0 0 0 0
4 POST 0 0 0 0 0 0 0 0 0 040. 4 PRE 0 0 0 0 0 0 0 0 0 0
4 POST 0 0 0 0 10 0 0 0 0 041. 1 PRE 0 100 - 100 100 98 100 100 0 98
1 POST 100 70 100 100 100 80 75 15 10 6542. 4 PRE 0 15 0 100 70 0 85 0 10 0
4 POST 15 25 10 5 10 10 25 0 0 543. 2 PRE 100 100 100 100 100 100 100 90 100 100
2 POST 100 100 100 100 100 100 100 90 100 10044. 1 PRE 0 50 100 100 100 100 100 15 100 75
1 POST 100 100 100 100 100 80 100 70 0 3045. 1 PRE 100 100 100 100 100 100 100 99 55 100
1 POST 100 100 100 100 100 99 85 70 20 8546. 1 PRE 15 70 100 100 100 100 100 90 100 80
1 POST 100 80 100 100 100 80 60 45 10 2547. 1 PRE 10 100 100 100 100 97 100 45 11 90
1 POST 90 90 100 100 100 20 5 5 5 1548. 1 PRE 0 90 100 100 100 85 100 15 0 60
1 POST 95 90 100 100 100 25 10 10 0 1049. 4 PRE 0 0 - 90 20 0 15 0 0 0
4 POST 0 10 0 0 - 0 0 0 0 050. 1 PRE 0 100 100 100 100 95 100 80 0 10
1 POST 100 100 70 100 100 80 40 30 0 20
表VI(续)
应用化合物 比例 类型编号 (Ib./A) CKL MG PIG VEL SMT BYG FOX ION NUT WO51. 1 PRE 100 100 100 100 100 100 100 80 65 100
1 POST 100 100 100 100 100 100 100 100 45 10053. 1 PRE 61 100 100 100 100 25 100 75 20 15
1 POST 100 20 96 100 95 10 35 0 0 1054. 1 PRE 0 0 0 0 0 0 0 0 0 0
1 POST 0 100 100 100 100 95 15 0 0 1055. 4 PRE 0 85 100 20 90 0 15 0 0 0
4 POST 80 100 100 100 100 45 40 5 0 556. 1 PRE 0 0 - 0 - 0 0 0 0 0
1 POST 80 100 100 100 100 100 35 90 10 6057. 1 PRE 0 100 0 100 100 0 0 - 0 0
1 POST 100 100 100 100 90 20 25 0 0 058. 1 PRE 0 20 100 100 25 0 0 - 0 0
1 POST 5 80 65 70 100 0 0 25 0 059. 1 PRE 0 0 100 100 0 0 0 0 0 0
1 POST 100 100 100 75 100 15 70 10 0 060. 1 PRE 51 100 100 100 100 70 100 90 0 0
1 POST 100 100 100 100 100 100 100 100 20 2561. 1 PRE 0 0 0 50 0 0 85 0 0 0
1 POST 100 100 100 100 100 100 100 100 30 4562. 1 PRE 0 0 0 0 0 0 0 0 0 0
1 POST 98 70 100 100 85 90 100 35 0 063. 4 PRE 0 0 0 100 100 0 75 0 0 10
4 POST 5 0 0 0 0 0 0 0 0 064. 2 PRE 0 0 0 0 0 0 0 0 0 0
2 POST - 0 85 15 100 15 0 0 0 065. 2 PRE - 0 100 0 0 0 0 0 0 0
2 POST 30 30 100 90 100 0 10 10 0 066. 4 PRE 0 0 0 25 0 0 5 0 0 0
4 POST 0 0 10 35 0 0 0 0 0 067. 4 PRE - 0 100 0 100 - 0 90 0 0
4 POST 0 5 5 10 0 0 0 0 0 5
表VI(续)
应用化合物 比例编号 (Ib./A)类型 CKL MG PIG VEL SMT BYG FOX ION NUT WO68. 4 PRE 0 0 - 100 25 0 5 0 0 0
4 POST 0 0 0 0 0 0 0 0 0 069. 4 PRE 0 0 0 100 0 90 0 0 0 0
4 POST 0 15 5 0 5 0 0 0 0 070. 4 PRE 0 0 - 100 0 0 11 0 0 0
4 POST 0 5 0 0 0 0 0 0 0 071. 1 PRE 36 100 100 100 - 80 100 25 0 0
1 POST 100 100 100 100 100 100 100 100 60 7572. 1 PRE 0 100 - 100 - 90 100 0 0 60
1 POST 100 100 100 100 100 95 100 85 5 6573. 1 PRE 0 95 - 0 - 75 100 0 0 20
1 POST 60 20 80 100 100 15 80 5 15 574. 1 PRE 0 0 0 100 0 0 15 5 0 0
1 POST 100 100 100 100 100 100 100 95 10 2575. 1 PRE 15 100 100 100 100 70 100 60 0 70
1 POST 100 100 100 100 100 95 100 75 0 1076. 1 PRE 0 100 100 100 100 100 100 90 35 90
1 POST 55 100 100 100 25 80 95 80 10 4077. 4 PRE 30 100 100 100 100 99 100 80 0 55
4 POST 45 70 100 95 100 15 40 0 0 078. 4 PRE 90 100 100 100 100 100 100 99 45 75
4 POST 25 20 20 100 100 0 25 0 0 079. 4 PRE 0 100 100 100 100 99 95 95 0 15
4 POST 35 50 55 95 100 0 0 10 10 1080. 4 PRE 90 100 100 100 100 100 100 100 15 99
4 POST 60 85 100 100 100 100 100 85 30 4581. 1 PRE 80 100 100 100 100 100 100 100 75 90
1 POST 55 100 100 100 98 30 60 15 20 3082. 1 PRE 0 100 100 100 100 100 100 98 25 85
1 POST 100 100 100 100 100 100 100 95 35 8083. 1 PRE 25 100 100 100 100 100 100 95 25 50
1 POST 100 100 100 100 100 95 100 70 20 0
表VI(续)
应用化合物 比例编号 (Ib./A) 类型 CKL MG PIG CKL SMT BYG FOX ION NUT WO84. 4 PRE 100 100 100 100 100 100 100 100 70 98
4 POST 30 100 100 100 100 15 70 100 100 7085. 1 PRE 100 100 100 100 100 100 100 100 100 100
1 POST 60 100 100 100 100 0 100 100 0 086. 4 PRE 0 0 - 0 0 0 20 0 0 0
4 POST 0 0 100 99 0 80 100 70 0 1087. 4 PRE 30 100 100 100 100 100 100 100 98 90
4 POST 45 10 100 100 100 50 65 55 35 1588. 1 PRE 80 100 100 100 100 100 100 100 15 95
1 POST 70 100 90 100 100 25 50 50 0 089. 0.3 PRE 100 100 100 100 100 100 100 100 80 100
0.3 POST 100 100 100 100 100 100 100 100 85 10090. 0.3 PRE 60 100 100 100 100 55 100 60 0 0
0.3 POST 100 100 100 100 100 20 35 25 15 2591. 4 PRE 0 0 100 60 100 0 100 15 0 20
4 POST 5 0 20 0 0 0 0 0 0 092. 1 PRE 95 15 100 100 100 100 100 100 100 80
1 POST 100 75 100 100 100 100 100 95 100 4096. 1 PRE 100 100 - 100 100 100 100 100 100 100
1 POST 75 100 100 100 100 95 90 35 100 097. 1 PRE 100 100 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100 100 7598 1 PRE 100 100 - 100 100 100 100 100 100 100
1 POST 98 100 100 100 100 100 100 100 100 9599. 4 PRE 0 0 0 20 - 0 45 0 0 0
4 POST 0 25 45 70 0 5 10 0 0 0100. 1 PRE 0 20 100 100 65 0 30 10 0 0
1 POST 35 90 100 100 65 25 15 15 10 15101. 1 PRE 0 0 100 50 100 0 0 0 0 0
1 POST 20 25 10 65 100 25 0 0 0 0102. 1 PRE 100 100 100 100 100 90 100 85 0 15
1 POST 100 100 100 100 100 100 100 30 10 0
表VI(续)
应用化合物 比例 类型编号 (Ib./A) CKL MG PIG VEL SMT EYG FOY ION NUT WO103. 1 PRE 0 0 100 90 99 0 25 0 0 0
1 POST 100 98 100 100 100 50 98 20 0 0104. 1 PRE 100 100 100 100 100 95 100 95 0 50
1 POST 100 100 100 100 100 40 95 10 0 0105. 1 PRE 100 100 100 100 100 100 100 100 65 100
1 POST 85 100 100 100 100 55 85 85 35 -106. 1 PRE 0 50 100 100 100 85 100 60 0 95
1 POST 10 10 70 100 60 15 30 10 0 15107. 1 PRE 0 90 100 100 100 90 100 60 0 75
1 POST 15 30 100 100 95 15 20 15 0 15108. 1 PRE 10 20 100 100 100 55 100 70 0 10
1 POST 30 65 35 100 100 0 0 10 15 15109. 1 PRE 0 0 100 10 0 55 10 0 0 0
1 POST 40 65 10 95 95 0 0 0 0 0110. 1 PRE 10 20 100 100 100 90 100 30 5 10
1 POST 95 100 100 100 90 100 100 85 20 15111. 1 PRE 100 95 100 100 100 100 100 90 20 95
1 POST 100 100 100 100 100 100 100 100 80 95112. 1 PRE 15 90 100 100 100 100 100 45 10 45
1 POST 100 100 100 100 100 100 100 20 80 100113. 1 PRE 50 98 - 100 100 95 100 75 0 10
1 POST 75 90 100 100 100 100 100 30 15 90114. 1 PRE 90 100 100 100 100 100 100 95 25 99
1 POST 50 35 95 95 99 70 100 70 0 45115. 1 PRE 75 65 100 100 100 100 100 100 35 80
1 POST 100 100 100 100 100 100 100 100 15 80116. 1 PRE 100 100 100 100 100 98 100 85 15 98
1 POST 95 95 100 100 100 100 100 65 15 80117. 1 PRE 100 100 100 100 100 100 100 99 65 100
1 POST 100 100 100 100 100 100 100 100 55 100118. 1 PRE 100 100 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100 45 100
表VI(续)
应用化合物 比例 类型编号 (Ib./A) CKL MG PIG VEL SMT BYG FOX ION NUT WO119. 4 PRE 10 0 100 100 0 85 100 45 0 15
4 POST 0 0 0 0 0 0 0 0 0 0120. 4 PRE 0 0 95 100 85 95 100 80 0 15
4 POST 0 0 0 0 0 0 0 0 0 0122. 1 PRE 100 100 100 100 100 100 100 100 100 99
1 POST 100 100 100 100 100 100 100 100 100 100124. 1 PRE 85 100 100 100 100 100 - 100 100 70
1 POST 10 0 100 100 100 35 15 100 35 0125. 4 PRE 0 0 100 100 55 95 100 - 10 10
4 POST 0 0 70 100 0 0 20 0 0 0126. 1 PRE 95 100 - 100 100 100 100 100 100 100
1 POST 65 35 30 100 70 75 100 85 0 0128. 1 PRE 100 100 - 100 100 100 100 100 98 100
1 POST 55 98 100 100 100 100 100 98 75 90129. 1 PRE 100 100 - 100 100 100 100 100 100 100
1 POST 80 100 100 100 100 100 95 65 40 80131. 1 PRE 100 100 - 100 100 100 100 100 100 95
1 POST 25 100 100 100 65 95 30 100 60 0132. 4 PRE 80 100 - 100 100 100 100 85 98 95
4 POST 25 100 100 100 60 85 98 25 0 35134. 1 PRE 100 90 - 100 100 100 100 65 20 60
1 POST 75 50 100 80 100 0 25 15 0 0136. 1 PRE 35 55 - 100 100 100 100 100 30 85
1 POST 35 40 100 100 100 0 100 60 0 0137. 1 PRE 75 100 - 100 100 100 100 100 0 95
1 POST 70 70 100 75 100 0 15 10 40 0138. 1 PRE 85 100 - 100 100 100 100 100 0 95
1 POST 70 55 100 100 100 70 98 55 25 0
* “-”表示未试验
表VII
除草活性
应用化合物 比例 类型编号 (Ib./A) BID NS SMT VEL BYG CRB EOX MF33. 1 PRE 50 0 100 100 100 95 100 80
1 POST 40 100 100 100 95 20 75 2052. 2 PRE 100 - 100 100 95 100 100 100
1 POST 100 100 100 100 40 20 10 093. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 10094. 1 PRE 95 40 100 100 0 100 90 0
1 POST 40 100 70 100 20 40 25 095. 1 PRE 100 100 100 100 95 100 100 100
1 POST 100 100 100 100 95 100 100 95121. 1 PRE 100 - 100 100 100 100 100 75
1 POST 100 100 100 100 75 75 85 20123. 1 PRE 100 100 100 100 100 100 100 10
1 POST 75 - 75 100 20 20 90 0127. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 90 20 100 40130. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 60 100 20133. 1 PRE 100 100 100 100 95 100 100 100
1 POST 100 - 100 100 95 100 100 25135. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 - 100 100 100 100 100 95139. 3 PRE 100 100 100 100 100 100 100 100
3 POST 100 100 100 100 100 100 100 100140. 1 PRE - 100 100 100 98 - 100 -
1 POST - 100 15 100 100 - 70 -141. 1 PRE - 100 100 100 99 - 100 -
1 POST - 100 100 100 100 - 100 -142. 1 PRE 80 90 100 100 95 100 100 80
1 POST 90 100 100 100 25 40 50 0
表VII(续)
应用化合物 比例
类型编号 (Ib./A) BID NS SMT VEL BYG CRB FOX MF143. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100144. 1 PRE 100 100 100 100 100 100 100 100
1 POST 95 100 100 100 100 100 100 100145. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 - 100 100 100 100 100 100146. 1 PRE 100 100 100 - 100 - 100 100
1 POST 100 100 100 100 100 100 100 95147. 1 PRE 100 100 - 100 95 - 100 100
1 POST 100 100 100 100 98 85 80 70148. 1 PRE 90 90 0 100 0 0 0 0
1 POST 0 0 0 0 0 0 0 0149. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 95150. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 - 100 100 100 100 100 70151. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 - 100 100 100 100 100 90152. 1 PRE 100 60 80 100 40 0 0 0
1 POST 80 - 0 100 0 40 20 0153. 1 PRE 75 50 0 100 25 80 70 0
1 POST 75 80 0 20 10 0 20 0154. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100155. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100156. 1 PRE 90 100 100 100 0 100 100 90
1 POST 40 100 80 100 10 0 0 30157. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 90 60158. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100
表VII(续)
应用化合物 比例
类型编号 (Ib./A) BID NS SMT VEL BYG CRB FOX MF159. 1 PRE 95 100 100 100 10 100 100 10
1 POST 80 100 100 100 10 80 20 10160. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100161. 1 PRE 100 100 100 100 0 95 100 0
1 POST 35 100 100 100 40 80 50 0162. 1 PRE 100 100 100 100 50 100 100 95
1 POST 95 100 100 100 100 85 90 60163. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 80 90 50164. 1 PRE 100 100 100 100 85 95 100 95
1 POST 75 100 100 100 60 80 60 20165. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100166. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100167. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 95 100 95168. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100169. 1 PRE 100 100 100 100 80 100 100 10
1 POST 75 100 100 100 10 90 25 10170. 1 PRE 0 0 0 0 0 0 0 0
1 POST 40 60 0 0 0 0 0 0171. 1 PRE 100 100 100 100 100 100 100 100
1 POST 75 - 100 100 100 100 100 60172. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100173. 1 PRE 95 100 100 100 80 100 100 50
1 POST 100 100 100 100 100 100 100 50174. 1 PRE 85 100 100 100 90 100 100 100
1 POST 100 100 100 100 100 100 100 100
表VII(续)
应用化合物 比例 类型编号 (Ib/A) BID NS SMT VEL BYG CRB FOX MF175. 1 PRE 25 100 100 100 0 100 100 100
1 POST 30 - 100 100 60 90 80 75176. 1 PRE 95 100 100 100 95 100 100 95
1 POST 95 - 100 100 95 100 95 75177. 1 PRE 90 100 100 100 95 100 100 40
1 POST 100 - 100 100 95 100 100 50178. 1 PRE 40 0 100 90 0 100 100 25
1 POST 100 100 100 100 75 60 90 50179. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 95 100180. 1 PRE 10 100 0 95 0 95 95 0
1 POST 75 80 0 40 0 90 40 0181. 1 PRE 100 100 100 100 75 100 100 95
1 POST 100 100 100 100 100 100 100 75182. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100183. 1 PRE 0 0 0 0 0 0 0 0
1 POST 10 20 20 0 0 0 0 0184. 1 PRE 100 0 100 100 95 100 100 100
1 POST 100 100 100 100 100 100 100 70185. 1 PRE 0 0 0 50 0 0 0 0
1 POST 50 75 0 35 0 20 0 0186. 1 PRE 95 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 60187. 1 PRE 90 100 100 100 95 100 100 95
1 POST 95 100 100 100 100 100 100 50188. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100189. 1 PRE 100 100 100 100 95 100 100 100
1 POST 95 100 100 100 95 100 100 100190. 1 PRE 100 100 100 100 90 100 100 95
1 POST 100 100 95 100 95 100 100 95
应用 表VII(续)化合物 比例
类型编号 (Ib./A) BID NS SMT VEL BYG CRB FOX MF191. 1 PRE 100 50 0 100 0 100 95 25
1 POST 80 95 20 95 20 50 40 0192. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100193. 1 PRE 100 100 95 100 95 100 100 95
1 POST 100 100 100 100 95 90 95 75194. 1 PRE 95 100 100 100 100 100 100 95
1 POST 100 100 100 100 100 100 100 95195. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100196. 1 PRE 100 100 - 100 95 100 100 100
1 POST 100 100 100 100 100 100 100 100197. 1 PRE 100 80 100 100 100 100 100 90
1 POST 100 100 100 100 100 95 100 95196. 1 PRE 75 90 0 100 0 60 0 0
1 POST 0 0 0 0 0 0 0 0199. 1 PRE 100 0 100 100 100 100 100 75
1 POST 100 100 100 100 100 95 100 95200. 1 PRE 100 100 100 100 100 100 100 100
1 POST 90 100 100 100 80 50 90 10201. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 95 100 100202. 1 PRE 50 85 100 100 10 95 100 90
1 POST 20 20 60 20 0 0 0 0203. 1 PRE 100 100 100 100 80 100 100 90
1 POST 100 100 100 100 95 95 100 95204. 1 PRE 95 100 100 100 95 100 100 100
1 POST 95 100 100 100 80 0 60 50205. 1 PRE 90 90 90 100 20 80 95 40
1 POST 10 100 90 50 0 0 0 0206. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100
表VII(续)
应用化合物 比例 类型编号 (Ib./A) BID NS SMT VEL BYG CRB FOX MF207. 1 PRE 95 100 100 100 95 95 100 100
1 POST 100 100 100 100 100 85 100 95208. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 95 75 100 100209. 1 PRE 40 20 100 100 0 95 100 80
1 POST 85 100 95 100 60 60 85 40210. 1 PRE 100 100 100 100 95 100 100 100
1 POST 95 100 100 100 95 80 95 90211. 1 PRE 100 40 100 100 40 100 100 90
1 POST 90 60 100 95 60 10 40 10212. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100213. 1 PRE 0 0 0 100 0 0 0 0
1 POST 100 100 100 100 100 95 100 75214. 1 PRE 0 0 100 0 0 0 0 0
1 POST 0 0 0 0 0 0 0 0215. 1 PRE 95 90 100 100 35 90 100 90
1 POST 100 100 100 100 95 100 100 90216. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100217. 1 PRE 100 95 100 100 100 100 100 100
1 POST 100 100 100 100 100 75 100 100218. 1 PRE 100 90 100 100 100 100 100 95
1 POST 100 100 100 100 100 100 100 95219. 1 PRE 80 70 100 100 95 100 100 50
1 POST 100 100 100 100 95 100 100 70220. 1 PRE 80 0 95 100 80 100 100 40
1 POST 100 95 100 100 60 30 100 20221. 1 PRE 0 10 100 100 25 80 95 0
1 POST 100 100 100 100 70 95 100 25222. 1 PRE 0 0 0 0 0 0 0 0
1 POST 25 80 0 95 0 0 0 0
表VII(续)化合物 应用
比例 类型编号 (Ib./A) BID NS SMT VEL BYG CRB FOX MF223. 1 PRE 70 10 100 100 100 100 100 80
1 POST 100 100 100 100 100 100 100 50224. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100225. 1 PRE 0 0 0 75 0 0 0 0
1 POST 90 100 80 100 0 0 20 0226. 1 PRE 70 10 20 75 40 80 100 25
1 POST 90 100 100 90 25 0 60 10227. 1 PRE 95 90 80 100 70 100 100 80
1 POST 100 100 100 100 100 80 100 90228. 1 PRE 90 95 100 100 95 100 100 100
1 POST 75 100 100 100 95 90 70 70229. 1 PRE 95 100 0 95 0 70 90 0
1 POST 80 100 10 100 10 20 25 0230. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100231. 1 PRE 70 80 90 100 90 100 100 95
1 POST 0 0 0 0 0 0 0 0232. 1 PRE 85 100 100 100 100 100 100 100
1 POST 95 100 100 100 100 75 100 80233. 1 PRE 85 100 100 100 100 100 100 100
1 POST 40 100 100 95 100 25 90 40234. 1 PRE 95 100 100 100 10 90 100 90
1 POST 40 100 100 100 0 0 50 0235. 1 PRE 100 - - 100 95 100 100 100
1 POST 95 100 100 100 100 70 95 80236. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 85 75 80 20237. 1 PRE 100 100 100 100 95 100 100 100
1 POST 100 100 100 100 100 100 100 100238. 1 PRE 100 100 100 100 100 100 100 100
1 POST 100 100 100 100 100 100 100 100
表VII(续)
应用化合物 比例 类型编号 (Ib/A) BID NS SMT VEL BYG CRB FOX MF239. 1 PRE 95 100 100 100 25 100 100 10
1 POST 100 100 100 100 60 75 85 0240. 1 POST 100 100 100 100 100 100 100 100241. 1 POST 95 100 100 100 95 95 60 95242 1 POST 100 100 100 100 100 100 100 95243. 1 PRE 100 100 100 100 80 100 90 100
1 POST 100 100 100 100 100 95 50 80244. 1 PRE 60 95 0 95 40 100 80 85
1 POST 70 100 100 100 10 10 35 20245. 1 PRE 0 80 0 90 0 95 80 0
1 POST 90 100 85 100 10 25 30 0246. 1 PRE 60 90 40 100 0 80 20 10
1 POST 75 95 95 50 0 0 10 0* “-”表示未试验
本发明的戊二酰亚胺也可用作杀藻剂。这些化合物宜用于防止或控制藻类的生长。所需戊二酰亚胺的实际用量当然随要保护的介质、要防治的藻类、所用的具体戊二酰亚胺和本领域技术人员已知的其它因素而异。
当本发明的戊二酰亚胺用于控制藻类时,能以任何防除不需要的植物所述的制剂形式使用。这些制剂包括液态溶液,如浓乳剂和稀喷洒剂,和干粉,如可湿性粉剂和粉尘剂。
采用下列步骤测定本发明化合物的杀藻活性和抑藻活性。在微滴定板(板A)的各孔中加入受试化合物的100μl如下所述的改性Allen介质的系列稀释液。另外,其中一个孔仅含改性的Allen介质(无化合物),作为对照。然后在滴定板的每个孔中接种混合藻类培养物。 4小时后,从各孔中取出5μl等分试样并将其放在含100μl Allen改性介质的另一不同微滴定板的孔(板B)中。两块滴定板用透明的塑料罩盖上,并同一些湿纸巾一起放在透明的塑料袋中,上述纸巾能产生高湿度并防止由板上蒸发。
将装滴定板的塑料袋在室温下放在强光条件(200-700英尺烛光)下。5或14天后由板A测定抑制生长所需的最低抑制浓度(MIC)。抑制生长的作用被定义为静作用。8至10天后,由板B测定化合物的4-小时灭杀作用(杀死生物体)。为了由微滴定板读出静活性或灭杀活性,用体视镜在低放大率下观察各孔中的生长或不生长。也可用读板器读出生长和非生长。
下列步骤用于制备改性的Allen 介质。
制备如下7种溶液:
NaNO3 10.0g在400ml去离子水中
CaCl2 1.0g在400ml去离子水中
MgSO4·7H2O 3.0g在400ml去离子水中
K2HPO4 3.0g在400ml去离子水中
KH2PO4 7.0g在400ml去离子水中
NaCl 1.0g在400ml去离子水中
FeCl3 1.0g在400ml去离子水中
上述各种溶液均过滤灭菌。
往940ml灭菌的去离子水中加入1滴FeCl3溶液和10.0ml所有的其它种溶液。该介质的环境条件下的PH值约为6.1,用碳酸钙表示的水硬度约为65PPm。用灭菌的1N KOH或HCl将PH值调至表VIII的PH值,用灭菌的NaHCO3溶液(将56.03gNaHCO3溶于1.0升煮沸和蒸馏的水中,然后过滤并灭菌)调至表VIII的水硬度。
混合藻培养物取自工业冷却塔(Spring House,PA)并根据已知方法保存于实验室中,混合的培养物含绿藻和兰绿菌。
在750英尺烛光的光度条件下本发明的化合物于改性的Allen介质中的杀藻活性(ppm)示于表VIII中。
表VIII
杀藻活性化合物 PH6.1 PH8
序号 天数 393ppm* 200ppm
静 灭杀 静试验1 10 5 <0.015 <2 -**试验2 10 5 0.25 - -
85 5 0.125 - -
51 5 0.25 - -试验3 2 14 32
12 14 32
19 14 125
27 14 125
34 14 125
38 14 63
41 14 63
45 14 <2
46 14 4
49 14 32
56 14 250
57 14 32
62 14 63
64 14 125
76 14 125
78 14 250
80 14 63
81 14 63
87 14 125
91 14 63
92 14 125
99 14 250
110 14 63
114 14 <2
148 14 125* 用碳酸钙表示的ppm水硬度**未试验
应当明白,在不偏离本发明的精神和范围的情况下,可对本发明进行修改和变动。
Claims (37)
R为(C1-C4)烷基、(C1-C4)卤代烷基或苯基;
R2为H,或与R一起形成稠合苯环;
X为H、Cl、Br、CN或F;
Y为H、卤素、CH3、SCH3、硝基或OCH3;
但当Y为氢时,R为三氟甲基,R2为氢且Z不是氢;
T为H或F:
Z为H、OH、卤原子、CN、SH、(C1-C6)烷基、(C1-C6)卤代烷基、-OSO2(C1-C6)烷基、-OSO2苯基、羧基、甲酰基、苯氧羰基、(C1-C6)烷氧基、(C3-C6)链烯氧基、(C3-C6)链炔氧基、氰基(C1-C6)烷氧基、苯基(C1-C6)烷氧基、(C1-C6)烷硫基、(C1-C6)烷酰氧基、(C1-C6)烷酰硫基、(C1-C6)烷氧羰基(C1-C4)烷硫基、(C1-C6)烷氧羰基(C1-C4)烷氧基、(C1-C6)烷氧羰基〔(C1-C6)烷氧基〕(C1-C6)烷氧基、(C1-C6)烷氧基(C1-C6)烷氧基、(苯硫基)(C1-C6)烷氧基、羧基(C1-C6)烷氧基、四氢呋喃氧基、吡啶(C1-C6)烷氧基、四氢呋喃(C1-C6)烷氧基、(C1-C6)烷基羰基、(C1-C6)烷氧羰基、〔(C1-C6)烷硫基〕羰基、(C1-C6)烷氧羰基(C1-C6)烷氧羰基、(C1-C6)烷氧基(C1-C6)烷氧羰基、氰基(C1-C6)烷氧羰基、(C3-C6)链烯氧基羰基、(C3-C6)链炔氧基羰基、卤代(C3-C6)链炔氧羰基、(C3-C6)环烷氧羰基、四氢异噁唑基羰基、呋喃基(C1-C6)烷氧羰基、吡啶基(C1-C6)烷氧羰基、四氢呋喃氧羰基、三(C1-C6)烷基甲硅烷基(C1-C6)烷氧基羰基、二(C1-C6)烷氧膦酰(C1-C6)烷氧羰基、二(C1-C6)烷基亚氨基氧羰基、一(C1-C6)烷基氨基羰基、一(C3-C6)链炔氨基羰基、苯基氨基羰基、一(C1-C6)烷氧基氨基羰基、(C1-C6)烷氧基(C1-C6)烷基、(C3-C6)链烯氧基(C1-C6)烷基、(C3-C6)链炔氧基(C1-C6)烷基、(C1-C6)烷酰氧基(C1-C6)烷基、(C1-C6)烷硫基(C1-C6)烷基、苯氧基(C1-C6)烷基、苯硫基(C1-C6)烷基、(C1-C6)烷氧羰基(C1-C6)烷氧基(C1-C6)烷基、(C1-C6)烷基醛肟基、(C3-C6)链烯醛肟基、(C3-C6)链炔醛肟基、苯基(C1-C6)烷基醛肟基、二氧环戊基、环氧(C1-C6)烷氧基、二(C1-C6)烷基-2-噁唑啉基、一(C1-C6)烷酰氨基(C3-C6)环烷氧基;或者
其中
L为氧或硫;
R3为氢或(C1-C3)烷基;且式(1)中,R4为氢、(C1-C8)烷基、(C3-C6)链烯基、(C3-C6)链炔基、(C1-C6)烷氧基(C1-C6)烷基、(C3-C6)环烷基、(C3-C6)环烷基(C1-C6)烷基、(C1-C6)烷硫基(C1-C6)烷基、苯基(C1-C6)烷基、氰基(C1-C6)烷基、(C1-C6)烷氧羰基(C1-C6)烷基、(C1-C6)烷氧羰基、四氢化糠基、四氢呋喃基、四氢呋喃基(C1-C6)烷基、二(C1-C6)烷氨基(C1-C6)烷基、二(C1-C6)烷氨基羰基(C1-C6)烷基或(C1-C6)烷酰基;
式(2)中,R4为(C1-C6)烷基;
式(3)中,R4为(C1-C6)烷基或(C3-C6)链炔基;
式(7)中,R4为(C1-C6)烷酰基或(C3-C6)链炔基;
式(8)中,R4为(C1-C6)烷基;
式(9)中,R4为(C1-C6)烷基羰基;
式(10)中,R4为(C1-C6)烷基或(C3-C6)链炔基。
2.权利要求1的组合物,其中活性化合物中的
R为(C1-C4)烷基、(C1-C4)卤代烷基或苯基;
R2为H,或与R一起形成稠合苯环;
X为H、Cl、Br或F;
Y为H、Cl、Br或CH3;
T为H或F;且Z为(C1-C6)烷氧基、(C3-C6)链烯氧基、(C3-C6)链炔氧基、苯基(C1-C6)烷氧基、(C1-C6)烷硫基、(C1-C6)烷酰氧基、(C1-C6)烷酰硫基、(C1-C6)烷氧羰基(C1-C4)烷硫基、(C1-C6)烷氧羰基(C1-C4)烷氧基、氰基(C1-C6)烷氧基、(C1-C6)烷氧基(C1-C6)烷氧基、(苯硫基)(C1-C6)烷氧基、羧基(C1-C6)烷氧基、四氢呋喃氧基、吡啶(C1-C6)烷氧基、四氢呋喃(C1-C6)烷氧基、(C3-C6)环烷氧基、(C3-C6)环烷基、(C1-C6)烷氧基或(C1-C6)烷氧羰基〔(C1-C6)烷氧基〕(C1-C6)烷氧基。
3.权利要求2的组合物,其中活性化合物中的R为CH3、CHF2或CF3,R2为H,X为Cl或F,Y为Br、F或Cl,T为H,Z为(C1-C6)烷氧基、(C3-C6)链烯氧基、(C3-C6)链炔氧基、四氢呋喃氧基、(C3-C6)环烷基(C1-C6)烷氧基或(C1-C6)烷氧基(C1-C6)烷氧基。
4.权利要求3的组合物,其中活性化合物中的R为CF3,R2为氢,X为氟,Y为氯,Z为烯丙氧基、异丙氧基、仲丁氧基、炔丙氧基、1-甲基炔丙氧基、环戊氧基、环丙甲氧基、3-四氢呋喃氧基或甲氧基甲氧基。
5.权利要求3的组合物,其中活性化合物中的R为CHF2,R2为氢;X为氟,Y为氯,Z为炔丙氧基。
6.权利要求3的组合物,其中活性化合物中的R为CF3,R2为氢,X为氟,Y为溴,Z为炔丙氧基。
7.权利要求1的组合物,其中活性化合物中的
R为(C1-C4)烷基、(C1-C4)卤代烷基或苯基;
R2为H,或与R一起形成稠合苯环;
X为H、Cl、Br或F;
Y为H、Cl、Br、F或CH3;
T为H或F;
Z为羧基、甲酰基、(C1-C6)烷氧羰基、(C1-C6)烷氧羰基(C1-C6)烷氧羰基、氰基(C1-C6)烷氧羰基、(C1-C6)烷氧基(C1-C6)烷氧羰基、〔(C1-C6)烷硫基〕羰基、(C1-C6)烷羰基、(C3-C6)链烯氧羰基、卤代(C3-C6)链炔氧羰基、(C3-C6)链炔氧羰基、(C3-C6)环烷氧羰基、四氢呋喃氧羰基、三(C1-C6)烷基甲硅烷基(C1-C6)烷氧羰基、二(C1-C6)烷氧基膦酰基(C1-C6)烷氧羰基、二(C1-C6)烷基亚氨基氧羰基、一烷基氨基羰基、一(C1-C6)烷氧氨基羰基、一(C1-C6)链炔氨基羰基或苯基氨基羰基。
8.权利要求7的组合物,其中活性化合物中的R为CH3、CHF2或CF3,R2为H,X为Cl或F,Y为Br、F或Cl,T为H,Z为CO2H、(C1-C6)烷氧羰基、(C3-C6)环烷氧羰基、(C3-C6)链烯氧羰基或(C3-C6)链炔氧羰基。
9.权利要求8的组合物,其中活性化合物中的R为CF3,R2为氢,X为氟,Y为氯,Z为羧基、甲氧羰基、正丙氧羰基、异丙氧羰基、仲丁氧羰基、环丁氧羰基或乙氧羰基。
10.权利要求8的组合物,其中活性化合物中的R为CF3,R2为氢,X为氟,Y为溴,Z为异丙氧羰基。
11.权利要求8的组合物,其中活性化合物中的R为CHF2,R2为氢,X为氟,Y为氯,Z为异丙氧羰基。
12.权利要求8的组合物,其中活性化合物中的R为CH3,R2为氢,X为氟,Y为氯,Z为异丙氧羰基。
13.权利要求1的组合物,其中活性化合物中的
R为(C1-C4)烷基、(C1-C4)卤代烷基或苯基;
X为H、Cl、Br或F;
Y为H、Cl、Br、F或CH3;
T为H或F;
Z为(C1-C6)烷基、(C1-C6)烷氧基(C1-C6)烷基、(C3-C6)链烯氧基(C1-C6)烷基、(C3-C6)链炔氧基(C1-C6)烷基、(C1-C6)烷酰氧基(C1-C6)烷基、〔(C1-C6)烷硫基〕(C1-C6)烷基、苯氧基(C1-C6)烷基、苯硫基(C1-C6)烷基、(C1-C6)烷氧羰基(C1-C6)烷氧基(C1-C6)烷基、(C1-C6)烷基醛肟基、(C3-C6)链烯醛肟基、(C3-C6)链炔醛肟基或苯基(C1-C6)烷基醛肟基。
14.权利要求13的组合物,其中活性化合物中的R为CH3、CHF2或CF3,R2为H,X为Cl或F,Y为Br、F或Cl,T为H,Z为(C1-C6)烷基、(C1-C6)烷氧甲基、(C3-C6)链烯氧甲基、(C3-C6)链炔氧甲基、(C1-C6)烷基醛肟基或(C1-C6)链炔醛肟基。
15.权利要求14的组合物,其中活性化合物中的R为CH3,R2为氢,X为氟,Y为氯,Z为异丙氧甲基、1-(甲基)炔丙氧甲基、甲基醛肟基、异丙基醛肟基、炔丙基醛肟基或叔丁基醛肟基。
16.权利要求1的组合物,其中活性化合物中的R为(C1-C4)烷基、(C1-C4)卤代烷基或苯基,R2为H或与R一起形成稠合苯环,Z和Y形成5-或6-员杂环,该杂环与苯环结构稠合,形成具有下述结构的双环基团;其中
L为O或S;
X为H或F;
R3为H或(C1-C3)烷基;且
式(1)中,R4为氢、(C1-C8)烷基、(C3-C6)链烯基、(C3-C6)链炔基、(C1-C6)烷氧基(C1-C6)烷基、(C1-C6)烷硫基(C1-C6)烷基、(C3-C6)环烷基、(C3-C6)环烷基(C1-C6)烷基、苯基(C1-C6)烷基、氰基(C1-C6)烷基、(C1-C6)烷氧羰基(C1-C6)烷基、四氢化糠基、四氢呋喃基、四氢呋喃(C1-C6)烷基、二(C1-C6)烷氨基(C1-C6)烷基、二(C1-C6)烷氨基羰基(C1-C6)烷基、(C1-C6)烷氧羰基或(C1-C6)烷酰基;
式(2)中,R4为(C1-C6)烷基;
式(3)中,R4为(C1-C6)烷基或(C3-C6)链炔基;
式(7)中,R4为(C1-C6)烷酰基或(C3-C6)链炔基;
式(8)中,R4为(C1-C6)烷基;
式(9)中,R4为(C1-C6)烷基羰基;
式(10)中,R4为(C1-C6)烷基或(C3-C6)链炔基。
18.权利要求17的组合物,其中活性化合物中的X为H或F,R为CH3、CHF2或CF3,R3为H、CH3或CH2CH3,R4为炔丙基、烯丙基、乙氧甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、1-乙基丙基、2-甲氧乙基、甲氧甲基、甲硫甲基、1-氰基乙基、1-甲基炔丙基、2-甲基烯丙基、氰基甲基、环丙甲基、环戊基、二甲氨基羰甲基、2-四氢呋喃甲基、3-四氢呋喃基、2-氯烯丙基或3,3-二氯烯丙基。
19.权利要求18的组合物,其中活性化合物中的L为氧,R为CH3,R3为H,R4为炔丙基,X为F。
20.权利要求18的组合物,其中活性化合物中的R为CF3,R3为CH3,R4为炔丙基,L为氧,X为H或F。
21.权利要求18的组合物,其中活性化合物中的R为CF3,R3和X为H,L为氧,R4为炔丙基、正丙基、1-甲基炔丙基、烯丙基、仲丁基、甲氧甲基或2-甲氧乙基。
22.权利要求18的组合物,其中活性化合物中的R为CF3,R3为H,X为F,L为氧,R4为炔丙基、氰基甲基、烯丙基、甲氧甲基、乙氧甲基、正丙基、异丙基、正丁基、异丁基、仲丁基、1-氰基乙基、2-甲基烯丙基、甲基硫甲基、2-乙基丙基、环丙甲基、环戊基、二甲氨基羰甲基、2-四氢呋喃甲基、3-四氢呋喃基、2-氯烯丙基、3,3-二氯烯丙基或乙基。
23.权利要求18的组合物,其中活性化合物中的R为CHF2,R3为H,L为氧,X为F,R4为烯丙基。
24.权利要求18的组合物,其中活性化合物中的R为CF3,R3为CH2CH3,L为氧,X为F,R4为炔丙基。
25.权利要求18的组合物,其中活性化合物中的R为CF3,R3为H,L为S,X为F,R4为炔丙基。
27.权利要求26的组合物,其中活性化合物中的R为CF3,X为F,R4为正丙基。
28.权利要求1-27中任何一项的组合物,其中还含有表面活性剂。
29.权利要求1-27中任何一项的组合物,其中的化合物占整个组合物重量的1%-98%。
30.一种控制不需要的植物生长的方法,该方法包括向植物或其生长介质上施用权利要求1-27中任一项所述的化合物。
31.权利要求30的方法,其中化合物施用率为0.0001-12磅/英亩(1.12×10-5克/米2-1.344克/米2)。
32.权利要求31的方法,其中化合物施用率为0.001-5磅/英亩(11.2×10-5克/米2-0.56克/米2)。
33.权利要求32的方法,其中化合物施用率为0.002-2磅/英亩(22.4×10-5克/米2-0.224克/米2)。
34.权利要求30的方法,其中化合物是芽前施用的。
35.权利要求30的方法,其中化合物是芽后施用的。
36.一种在被藻污染的区域阻止藻生长的方法,该方法包括在该区域施用足以阻止藻生长的量的权利要求1-27中任一项所定义的组合物。
37.权利要求36的方法,其中的化合物为N-(4’-氯-2’氟-5’-炔丙氧苯基)-3-(三氟甲基)戊二酰亚胺、N-〔5’-(异丙氧)羰基-4’-氯-2’-氟苯基〕-3-(三氟甲基)戊二酰亚胺、4-炔丙基-6-(N-(3-三氟甲基)戊二酰亚胺基)-2 H-1,4-苯并恶嗪-3(4H)-酮、N-(4’-氯-2’-氟-5’-炔丙氧苯基)-3-五氟乙基)戊二酰亚胺、N-(4’-氯-2’-氟-5’-异丙氧苯基)-3-(五氟乙基)戊二酰亚胺或N-〔4’-氯-2’-氟-5’-(甲氧氨基羰基)苯基〕-3-(三氟甲基)戊二酰亚胺。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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US40132989A | 1989-08-31 | 1989-08-31 | |
US401,329 | 1989-08-31 | ||
US56378090A | 1990-08-09 | 1990-08-09 | |
US563,780 | 1995-11-27 |
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CN1049846A CN1049846A (zh) | 1991-03-13 |
CN1036564C true CN1036564C (zh) | 1997-12-03 |
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JP (1) | JPH03163060A (zh) |
KR (1) | KR100196790B1 (zh) |
CN (1) | CN1036564C (zh) |
AR (1) | AR248393A1 (zh) |
AT (1) | ATE131156T1 (zh) |
AU (1) | AU638482B2 (zh) |
BR (1) | BR9004333A (zh) |
CA (1) | CA2023492A1 (zh) |
DE (1) | DE69023987T2 (zh) |
DK (1) | DK0415642T3 (zh) |
ES (1) | ES2081939T3 (zh) |
FI (1) | FI904284A0 (zh) |
GR (1) | GR3018421T3 (zh) |
HU (1) | HUT54461A (zh) |
IE (1) | IE903148A1 (zh) |
IL (1) | IL95529A0 (zh) |
NO (1) | NO903758L (zh) |
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PT (1) | PT95173B (zh) |
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JPH05208975A (ja) * | 1991-12-02 | 1993-08-20 | Mitsubishi Kasei Corp | テトラヒドロフラン誘導体およびこれを有効成分とする除草剤 |
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- 1990-08-22 EP EP90309223A patent/EP0415642B1/en not_active Expired - Lifetime
- 1990-08-22 DK DK90309223.7T patent/DK0415642T3/da active
- 1990-08-22 DE DE69023987T patent/DE69023987T2/de not_active Expired - Fee Related
- 1990-08-22 ES ES90309223T patent/ES2081939T3/es not_active Expired - Lifetime
- 1990-08-27 AR AR90317692A patent/AR248393A1/es active
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- 1990-08-30 HU HU905703A patent/HUT54461A/hu unknown
- 1990-08-30 FI FI904284A patent/FI904284A0/fi not_active Application Discontinuation
- 1990-08-30 AU AU62020/90A patent/AU638482B2/en not_active Ceased
- 1990-08-31 CN CN90107393A patent/CN1036564C/zh not_active Expired - Fee Related
- 1990-08-31 PT PT95173A patent/PT95173B/pt not_active IP Right Cessation
- 1990-08-31 JP JP2230445A patent/JPH03163060A/ja active Pending
- 1990-08-31 KR KR1019900013702A patent/KR100196790B1/ko not_active IP Right Cessation
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CN103588722A (zh) * | 2012-08-17 | 2014-02-19 | 苏州中科天马肽工程中心有限公司 | 6-硝基-2h-1,4-苯并恶嗪-3(4h)-酮的合成方法 |
CN105473562A (zh) * | 2013-06-21 | 2016-04-06 | 巴斯夫欧洲公司 | 制造4-炔丙基化氨基苯并噁嗪酮类的方法 |
CN105473562B (zh) * | 2013-06-21 | 2019-05-03 | 巴斯夫欧洲公司 | 制造4-炔丙基化氨基苯并噁嗪酮类的方法 |
Also Published As
Publication number | Publication date |
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GR3018421T3 (en) | 1996-03-31 |
IE903148A1 (en) | 1991-03-13 |
DE69023987D1 (de) | 1996-01-18 |
EP0415642B1 (en) | 1995-12-06 |
PT95173A (pt) | 1991-05-22 |
FI904284A0 (fi) | 1990-08-30 |
EP0415642A1 (en) | 1991-03-06 |
DK0415642T3 (da) | 1996-01-02 |
DE69023987T2 (de) | 1996-10-10 |
PT95173B (pt) | 1997-06-30 |
CA2023492A1 (en) | 1991-03-01 |
NO903758L (no) | 1991-03-01 |
ATE131156T1 (de) | 1995-12-15 |
CN1049846A (zh) | 1991-03-13 |
NO903758D0 (no) | 1990-08-28 |
JPH03163060A (ja) | 1991-07-15 |
AR248393A1 (es) | 1995-08-18 |
NZ235090A (en) | 1996-06-25 |
KR910004564A (ko) | 1991-03-28 |
BR9004333A (pt) | 1991-09-03 |
IL95529A0 (en) | 1991-06-30 |
ES2081939T3 (es) | 1996-03-16 |
HUT54461A (en) | 1991-03-28 |
AU638482B2 (en) | 1993-07-01 |
AU6202090A (en) | 1991-03-07 |
KR100196790B1 (ko) | 1999-06-15 |
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