CN1058007C - 糖精衍生物 - Google Patents
糖精衍生物 Download PDFInfo
- Publication number
- CN1058007C CN1058007C CN95195143A CN95195143A CN1058007C CN 1058007 C CN1058007 C CN 1058007C CN 95195143 A CN95195143 A CN 95195143A CN 95195143 A CN95195143 A CN 95195143A CN 1058007 C CN1058007 C CN 1058007C
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- China
- Prior art keywords
- group
- methyl
- formula
- alkyl
- hydrogen
- Prior art date
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- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical class C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- -1 cyano, methylsulphonyl Chemical group 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 6
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical group 0.000 claims abstract description 5
- 125000006432 1-methyl cyclopropyl group Chemical group [H]C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 241000196324 Embryophyta Species 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 230000002363 herbicidal effect Effects 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 5
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 4
- 235000010086 Setaria viridis var. viridis Nutrition 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- 150000002085 enols Chemical class 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 2
- 241000405414 Rehmannia Species 0.000 claims 1
- 244000230342 green foxtail Species 0.000 claims 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract description 4
- 125000001424 substituent group Chemical group 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 abstract 1
- 125000002252 acyl group Chemical group 0.000 abstract 1
- 125000003342 alkenyl group Chemical group 0.000 abstract 1
- 125000006193 alkinyl group Chemical group 0.000 abstract 1
- 125000004414 alkyl thio group Chemical group 0.000 abstract 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003513 alkali Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 235000019439 ethyl acetate Nutrition 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000335053 Beta vulgaris Species 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 4
- 150000003818 basic metals Chemical group 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000004359 castor oil Substances 0.000 description 4
- 229960001777 castor oil Drugs 0.000 description 4
- 235000019438 castor oil Nutrition 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- GBLHYNVHXROBTQ-UHFFFAOYSA-N methyl 6-chlorosulfonyl-2-methyl-3-nitrobenzoate Chemical compound COC(=O)C1=C(C)C([N+]([O-])=O)=CC=C1S(Cl)(=O)=O GBLHYNVHXROBTQ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 244000299507 Gossypium hirsutum Species 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical group COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
- C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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Abstract
本发明涉及式I的糖精衍生物及其农业上的常规盐
其中取代基具有下列含义:
L和M是氢、C1-C4-烷基、C1-C4-烷氧基、C1-C4-烷硫基、氯、氰基、甲磺酰基、硝基或三氟甲基;
Z是氢、C1-C4-烷基、C3-C8-环烷基、C3-C6-链烯基、C3-C5-炔基、C1-C4-酰基、苄基或苯基,苯环未被取代或由卤素或C1-C4-烷基取代;
R1是环丙基、1-甲基环丙基、1-甲硫基环丙基或叔丁基。
Description
本发明涉及式I的糖精衍生物及其农业上的常规盐其中取代基具有下列含义:L和M是氢、C1-C4-烷基、C1-C4-烷氧基、C1-C4-烷硫基、氯、氰基、甲磺酰基、硝基或三氟甲基;Z是氢、C1-C4-烷基、C3-C8-环烷基、C3-C6-链烯基、C3-C5-炔基、C1-C4-酰基、苄基或苯基,其中的苯环未被取代或由卤素或C1-C4-烷基取代;R1是环丙基、1-甲基环丙基、1-甲硫基环丙基或叔丁基。
本发明还涉及含有式I化合物的除草组合物,和用糖精衍生物I防治莠草生长的方法。
现有技术中未曾提到糖精衍生物具有除草作用。然而,很久以前,人们就知道未取代的糖精(O-磺基-苯甲酰亚胺,即,式I中的L、M、Q和Z=H)是合成甜味剂。4-羟基糖精是另一种已知的甜味剂(德国专利公开3 607 343)。糖精衍生物在病虫害防治上的应用也是已知的,例如日本专利公告(JP publication)72/00419,73/35457(杀菌剂),在医药上的应用也是已知的,例如EP-A 594 257和该文中提到的参考文献。
带有含磺酰胺环的杂环化合物作为除草剂已有公开,这里可以提到的典型代表是苯达松
本发明的一个目的是提供新颖的除草剂,对于除草目的而言,其基本结构是迄今为至未知的。我们发现,此目的可以通过本文开头所定义的化合物I来实现。
在上面提到的结构式中,L和M具有本文开头给出的含义,且Z是氢、C1-C4-烷基、C3-C8-环烷基、C3-C6-链烯基、C3-C5-炔基、C1-C4-酰基、苄基或苯基,其中的苯环未被取代或由卤素或C1-C4-烷基取代。
该反应方案中的第一步是通过用镁和少量的CCl4来处理式A1氰基酮的甲醇溶液,并让其反应,给出烯醇镁。氰基酮的类似C酰化作用描述于(例如)EP-A 496 630和EP-A 496 631中。
除去甲醇后,将所得的式A2烯醇镁溶于甲苯或乙腈中,优选溶于乙腈中,然后将等量于A1的式III酰氯以其乙腈溶液滴加入内。在25℃至50℃下搅拌1-16小时后,反应完毕。收集时,将它置于减压下浓缩,所剩的残留物用溶剂如乙酸乙酯或二氯甲烷收集,并用10%的HCl来分解镁盐。用水洗涤有机相后,将它用干燥剂如硫酸镁干燥,并浓缩。产物通过用烃如石油醚、环已烷或正戊烷处理而从所剩的残留物中沉淀出来。
用作原料的式A1氰基酮一般是已知化合物。它们可以通过(例如)将氰基乙酸与丁基锂反应,然后与酰氯R1-COCl反应来获得。
酰氯R1-COCl是以本身已知的方式,由相应的羧酸R1-COOH与亚硫酰二氯反应而获得的。羧酸R1-COOH是从文献中已知的:新戊酸和环丙烷羧酸是市售的化合物。1-甲基环丙烷羧酸可以通过其市售的乙酯水解或是以已知的方式用α-环丙烷羧酸锂甲基化〔Warner+Le,JOC 47,(1982),893〕而获得。1-甲硫基环丙烷羧酸是以已知的方式由1-甲硫基环丙烷腈获得,1-甲硫基环丙烷腈可由甲基巯基乙腈和二溴乙烷在氨基钠存在下制备〔德国专利公开21 20 908=CA 76:72099〕。
糖精羧酸在某些情况下是已知的(4-COOH:Zincke,Liebigs Ann.427(1922)231;5-COOH:Jacobsen,Chem.Ber.13(1880),1554;6-COOH:Weber,Chem.Ber.25(1892),1740)。此外,4-氯糖精-5-羧酸的制备描述于德国专利公开36 07 343中。
糖精羧酸也可以通过在增高的压力下,在过渡金属催化剂铂、镍、钴或铑和碱的存在下,使相应的式A3溴代-或碘代-糖精衍生物,其中L、M和Z具有上面提到的含义,或如果Z≠H时,使式A4化合物,与一氧化碳和水或C1-C6-醇反应而获得。
催化剂镍、钴、铑和特别是铂可以以金属的形式或以其已知价态的常规盐形式存在,如以其氯化物的形式存在,例如PdCl2、PhCl3.H2O,乙酸盐例如Pd(OAc)2,氰化物等。还可以存在与叔膦的金属配合物、烷基羰基金属、羰基金属,例如CO2(CO)8、Ni(CO)4,与叔膦的羰基金属配合物,例如(PPh3)2Ni(CO)2或与叔膦配合的过渡金属盐。最后提到的实施方案在铂作催化剂的情况下是特别优选的。本文中膦配位体可有多种变化,例如它们可以由下式代表:其中n是数字1、2、3或4,且基团R7至R13是低分子量的烷基C1-C6-烷基、芳基或C1-C4-烷芳基例如苄基、苯乙基,或芳氧基。芳基例如是萘基、蒽基和优选的未取代或取代的苯基,对于取代基而言,唯一需要考虑的是取代基应对羧基化反应没有影响,除此之外,它们可以有多种多样的变化,且可以包括所有的惰性C-有机基团如C1-C6-烷基例如甲基,羧基如COOH、COOM(M例如是碱金属、碱土金属或铵盐),或经氧键合的C-有机基团,如C1-C6-烷氧基。
膦配合物的制备可以以已知的方式进行,如根据描述在本文开头提到的文献中的方式,例如,市售的金属盐如PdCl2或Pd(OCOCH3)2用作原料,并加入膦例如P(C6H5)3、P(n-C4H9)3、PCH3(C6H5)2或1,2-双(二苯基膦基)乙烷。
基于过渡金属,膦的量通常是0至20、特别是0.1至10摩尔当量,特别优选1至5摩尔当量。
对过渡金属的量无严格限制。当然由于费用的原因,将会采用相当小的量,例如,相对于原料A3或A4,采用0.1至10摩尔%、特别是1至5摩尔%。
以原料A3或A4为基础,与一氧化碳或至少等摩尔量的水进行反应制备糖精羧酸。反应组分水或C1-C6-烷基-醇也可以同时用作溶剂,即,最大的量无严格限制。
然而,根据原料和所用的催化剂的性质,采用另外的惰性溶剂或者用羧化反应所用的碱作为溶剂来代替反应组分是有利的。
适用于羧化反应的惰性溶剂是常规溶剂,如烃例如甲苯、二甲苯、已烷、戊烷、环已烷,醚例如甲基叔丁基醚、四氢呋喃、二噁烷、二甲氧基乙烷,取代的酰胺如二甲基甲酰胺,全取代的脲如四-C1-C4-烷基-脲,或腈如苄腈或乙腈。
在该方法的优选实施方案中,过量使用其中的一种反应组分特别是碱,这样就不需要另加溶剂。
适合于该方法的碱是所有的惰性碱,这些碱能够与反应中释放的碘化氢或溴化氢结合。可以提到的实例是叔胺如三乙胺,环胺如N-甲基-哌啶或N,N’-二甲基哌嗪、吡啶,碱金属或碱土金属氢氧化物、碳酸盐或碳酸氢盐,或四烷基取代脲衍生物如四-C1-C4-烷基-脲,例如四甲基脲。
碱的量不受严格限制,通常可以采用1至10、特别是1至5摩尔。当碱同时用作溶剂时,其量一般是成比例的,这样可使反应组分溶解,但为了节省费用、能够采用小的反应容器和保证反应组分间最大程度的接触等可行性原因,应避免使用过分过量的碱。
在反应期间,对一氧化碳的压力进行调节,使得相对于A3或A4而言,总是存在过量的CO。优选的是,在室温下的一氧化碳压力是1至250巴,特别是5至150巴的CO。在不同的温度下,压力可以相应的高或低。
一般而言,羰基化作用是在20至250℃、特别是在30至150℃下连续或分批进行的。在分批操作的情况下,一氧化碳适当地连续注入反应混合物中,以保持常压。
以常规的方式(例如)蒸馏将产物从所得的反应混合物中分离出来。
反应所需的原料A3或A4是已知的,或可以由本身已知的方式制备。它们可以或是通过碘取代的2-甲基苯磺酰胺的过锰酸盐氧化作用获得,或是通过Sandmeyer反应由氨基糖精获得。氨基糖精由已知方法将硝基糖精还原制备。硝基糖精是已知的(Kastle,“美国化学期刊(Amer.Chem.Journal)”11(1889),184或DRP 551423(1923)),或是用由文献已知的方式从适合的硝基苯衍生物合成(Liebigs Ann.699(193),85)或从苯磺酰胺合成。
此外,它们可以用与实施例1至12的制备过程相似的方式获得。
对于意欲的应用而言,优选具有如下L和M基团的式I的糖精衍生物:L和M是氢、甲基、甲氧基、甲硫基、氯、氰基、甲磺酰基、硝基或三氟甲基。
在式I中,R1特别优选环丙烷。
基团Z特别优选是所提到的C-有机基团之一,特别是甲基、乙基、乙酰基、苯基或炔丙基。
特别优选的活性化合物可见表1。
表1中提到的作为取代基的基团本身,另被看作是所涉及的取代基的特别优选的定义,这些基团相互独立地与所提到的其它取代基作具体的组合。
化合物I可以以其农业上可利用的盐的形式存在,盐的性质一般无关紧要。通常,那些对除草作用无不利影响的碱的盐是适合的。
适合的碱性盐特别是:碱金属的盐,优选钠和钾盐;碱土金属盐,优选钙、镁和钡盐;过渡金属的盐,优选锰、铜、锌和铁盐;以及铵盐,这些盐可以带一至三个C1-C4-烷基或羟基-C1-C4-烷基取代基和/或苯基或苄基取代基,优选二异丙基铵、四甲基铵、四丁基铵、三甲基苄基铵和三甲基-(2-羟基乙基)铵盐;鏻盐,锍盐,优选三(C1-C4)-烷基锍盐,和氧化锍盐,优选三(C1-C4)-烷基氧化锍盐。
化合物I,含有化合物I的除草组合物和其环境可耐受的(例如)碱金属、碱土金属或氨和胺的盐及含有这些盐的除草组合物,可以在作物如小麦、稻、玉米、大豆和棉花中高效地防治阔叶杂草和禾草,而不对作物造成明显的伤害。这种效果特别是出现在低施用量的情况下。
考虑到施用方法的多样性,化合物I或含有之的组合物也可以用于另外的作物,用于消灭莠草。适合的作物的实例是:洋葱、凤梨、花生、芦笋、甜菜(Beta vulgaris spp.altissima)、芜菁甜菜(Beta vulgaris spp.rapa)、蔓菁(Brassica rapa var.silvestris)、茶、红花、美洲山核桃、柠檬、甜橙、小果咖啡(中果咖啡、大果咖啡)、黄瓜、狗牙根、胡萝卜、油棕、欧洲草莓、大豆、陆地棉、(鸡脚棉、草棉、Gossypium vitifolium)、向日葵、巴西橡校、大麦、啤酒花、甘蓝、核桃、兵豆、亚麻、蕃茄、苹果属、木薯、紫花苜蓿、芭蕉属、烟草(黄花烟草)、油橄榄、稻、雪豆、菜豆、欧洲云杉、松属、豌豆、欧洲甜樱桃、桃、西洋梨、红醋栗、蓖麻、甘蔗、黑麦、马铃薯、芦黍(蜀黍)、可可、红车轴草、普通小麦、硬粒小麦、蚕豆、葡萄、玉米。
然而,化合物I也可以采用在这样的作物上,所述的作物通过育种和/或基因工程的方法,业已对化合物I或其它除草剂的作用具有高抗性。
本发明除草组合物或活性化合物的施用可以在苗前或苗后进行。如果某些作物对活性化合物的耐受性差,则可采用这样的施用技术,在该技术中,除草组合物借助喷雾设备喷雾,如果可能的话,使敏感作物的叶片不受影响,而与之同时,使活性化合物达到生长在作物下面的莠草的叶片上或覆盖土壤的表面(苗后直接处理(post-directed)、铺施(lay-by))。
化合物I和含有它的除草组合物可以以可直接喷雾水溶液、粉末和悬浮液,或高浓度水悬剂、油悬剂或其它悬浮剂、或分散液、乳剂、油分散液、膏剂、喷粉组合物、撒施组合物或颗粒剂的形式,通过喷雾、弥雾、喷粉、撒施或浇泼施用。施用形式取决于使用的目的;在每一种情况下,应确保本发明混合物的分散尽可能的细微和均匀。
制备直接可喷雾溶液、乳剂、膏剂或油分散液的适合惰性辅助剂基本上是:中至高沸点的矿物油馏份如煤油或柴油,煤焦油和动植物油,脂族烃、环烃和芳烃,例如石蜡、四氢化萘、烷基化萘或其衍生物、烷基化苯及其衍生物,醇如甲醇、乙醇、丙醇、丁醇和环己醇,酮如环己酮,或强极性溶剂,例如胺,如N-甲基吡咯烷酮,或水。
含水的施用形式可以通过加水,由乳油、悬浮剂、膏剂、可湿性粉剂或水可分散颗粒剂制备。制备乳剂、膏剂或油分散剂时,通过加入润温剂、粘合剂、分散剂或乳化剂,将活性物直接或溶于油或溶剂后均化于水中。另外,也可以制备由活性物质、润湿剂、粘合剂、分散剂或乳化剂和可能的溶剂或油组成的浓缩物,它们适合用水稀释。
适合的表面活性物质是芳族磺酸例如木素磺酸、苯酚磺酸、萘磺酸和二丁基萘磺酸碱金属、碱土金属或铵盐,和脂肪酸、烷基磺酸和烷基芳基磺酸、烷基醚硫酸、月桂基醚硫酸和脂肪醇硫酸的碱金属、碱土金属或铵盐,以及硫酸化的十六-、十七-和十八醇或脂肪醇醚的盐,磺化萘和其衍生物与甲醛的缩合产物,萘或萘磺酸与苯酚和甲醛的缩合产物,聚氧乙烯辛基酚醚,乙氧基化的异辛基-、辛基-或壬基酚;烷基苯酚或三丁基苯基聚乙二醇醚,烷基芳基聚醚醇,异十三烷基醇,脂肪醇环氧乙烷缩合物,乙氧基化蓖麻油,聚氧乙烯-或聚氧丙烯烷基醚,月桂醇聚乙二醇醚乙酸酯,失水山梨醇酯,木素亚硫酸盐废液或甲基纤维素。
粉剂、撒施和喷粉组合物可以通过将活性物质与固体载体混合或一起研磨而生产。
颗粒剂(例如,涂敷、浸渍或均质颗粒剂)可以通过将活性化合物结合到固体载体上而制备。固体载体是矿石土如硅酸、硅胶、硅酸盐、滑石、高岭土、石灰石、石灰、白垩、红玄武土、黄土、陶土、白云石、硅藻土、硫酸钙和硫酸镁、氧化镁、塑料粉,和化肥如硫酸铵、磷酸铵、硝酸铵、尿素,和植物产品如面粉、树皮粉、木粉和坚果壳粉、纤维素粉,和其它固体载体。
制剂中通常含有0.01至95%(重量)、优选0.5至90%(重量)的活性化合物。为此目的所采用的活性化合物的纯度为90%至100%,优选95%至100%(根据NMR谱)。
例如可以如下使用本发明的化合物I:I.将20份重量的化合物I.03溶于由如下组成的混合物:80份重量的烷基化苯、10份重量的8至10摩尔环氧乙烷与1摩尔油酸N-单乙醇酰胺的加成物、5份重量的十二烷基苯磺酸钙盐和5份重量的40摩尔环氧乙烷与1摩尔蓖麻油的加成物。将溶液倒出,并将之细分散于100,000份重量的水中,获得含0.02%(重量)活性化合物的水分散液。II.将20份重量的化合物I.03溶于由如下组成的混合物:40份重量的环己酮、30份重量的异丁醇、20份重量的7摩尔环氧乙烷与1摩尔异辛基酚的加成物和10份重量的40摩尔环氧乙烷与1摩尔蓖麻油的加成物。将溶液倒出,并将之细分散于100,000份重量的水中,获得含0.02%(重量)活性化合物的水分散液。III.将20份重量的活性化合物I.03溶于由如下组成的混合物:25份重量的环己酮、65份重量沸点为210至280℃的矿物油馏份和10份重量的40摩尔环氧乙烷与1摩尔蓖麻油的加成物。将溶液倒出,并将之细分散于100,000份重量的水中,获得含0.02%(重量)活性化合物的水分散液。IV.将20份重量的活性化合物I.03与3份重量的二异丁基萘-α-磺酸钠盐、17份重量的来源于亚硫酸废液的木素磺酸钠盐和60份重量的粉状硅胶彻底混合,并在锤磨中磨碎。通过将混合物细分散于20,000份重量的水中,获得含有0.1%(重量)活性化合物的喷雾混合物。V.将3份重量的活性化合物I.03与97份重量细碎的高岭土混合。以这种方式,获得含有3%(重量)活性化合物的喷粉组合物。VI.将20份重量的活性化合物I.03与2份重量的十二烷基苯磺酸钙盐、8份重量的脂肪醇乙二醇醚、2份重量的酚-脲-甲醛缩合物的钠盐和68份重量的石蜡矿物油紧密混合。获得稳定的油分散剂。
为扩大作用谱和获得增效作用,糖精衍生物I可以与许多有代表性的其它除草剂或生长调节活性化合物混合或联合施用。例如,适合的基本组分是二嗪类、4H-3,1-苯并噁嗪衍生物、苯并噻二嗪酮类、2,6-二硝基苯胺类、N-苯基氨基甲酸酯类、硫代氨基甲酸酯类、卤代羧酸类、三嗪类、酰胺类、脲类、二苯醚类、三嗪酮类、尿嘧啶类、苯并呋喃衍生物、在2位上带有例如羧基或酰亚氨基(carbimino)的环己烷-1,3-二酮衍生物、喹啉羧酸衍生物、咪唑啉酮类、磺酰胺类、磺酰脲类、芳氧基或杂芳氧基苯氧丙酸及其盐、酯和酰胺,及其它。
此外,可以单独使用化合物I或将化合物I与其它除草剂组合使用,另外也可以加入其它的作物保护剂,例如与防治害物或病原真菌或细菌的药剂一起使用。还可以与矿物盐溶液互混,采用这种方法来消除营养元素或痕量元素的缺乏。也可以加入无药害的油和油浓缩物。
制备实施例:1. 2-甲基-6-乙酰氨基苯甲酸
将90.6g(0.6mol)6-甲基邻氨基苯甲酸加到24.8g(0.62mol)NaOH的
500ml水溶液中,然后滴加63.4g(0.62mol)乙酸酐。搅拌一小时后,在
冷却的条件下用浓HCl酸化此混合物至pH 3,将沉积的沉淀物抽吸滤
出,用水洗涤之,并在50℃下减压干燥。
收率:107g(0.55mol)=理论值的92%,m.p.:189-190℃2. 2-甲基-3-硝基-6-乙酰氨基苯甲酸
首先在-5℃下量取271ml 98%的硝酸,然后分批加入106g(0.55mol)
在1.中制备的2-甲基-6-乙酰氨基苯甲酸。在10℃搅拌一小时后,
将反应混合物倒入540g冰和270ml水的混合物中。将沉积出的沉淀物
抽吸滤出,用水洗涤之,并在50℃下减压干燥。
收率:75.6g(0.317mol)=理论值的58%,m.p.:190-191℃
3-位上硝化的异构体在静置一段相对长的时间后,从滤液中沉积出
来。收率:21.3g(0.089mol)=理论值的16%,m.p.:180-182℃3. 2-甲基-3-硝基-6-氨基苯甲酸
首先取450ml 2N的NaOH,然后加入75.6g(0.317mol)2-甲基-3
-硝基-6-乙酰氨基苯甲酸。将反应混合物升温至95℃,并在此温
度下搅拌一小时。冷却至10℃后,加入425ml 2N HCl酸化,将沉积出
的沉淀物抽吸滤出,用水洗涤之,并在50℃减压下干燥。
收率:50.7g(0.258mol)=理论值的82%,m.p.:183-184℃4. 2-甲基-3-硝基-6-氨基苯甲酸甲酯
将49.7g(0.253mol)2-甲基-3-硝基-6-氨基苯甲酸溶于380ml
丙酮中,加入43g(0.51mol)碳酸氢钠。然后,将此混合物加热至沸腾,
直到CO2完全放出。在丙酮的沸点温度下,在两个小时的时间里,将
35.3g(0.28mol)硫酸二甲酯加到如此获得的2-甲基-3-硝基-6-
氨基苯甲酸钠盐悬浮液中,随后将混合物再回流三小时,然后让它冷
却。将反应的混合物倒入1.8l的水中后,用二氯甲烷萃取。将有机相
干燥后,将其浓缩。所得的固体的纯度(NMR)足以用于随后的反应。
收率:50g(0.238mol)=理论值的94%,m.p.:92-94℃5. 2-甲氧羰基-3-甲基-4-硝基苯磺酰氯
加热下将58.5g(0.278mol)2-甲基-3-硝基-6-氨基苯甲酸甲酯溶
于280ml冰乙酸中,然后将此溶液在15至20℃下倒入85ml浓HCl
中。在5至10℃下,滴加入19.3g(0.28mol)亚硝酸钠的60ml水溶液,
并将混合物在5℃下搅拌30分钟。此重氮盐溶液随后滴加入374g SO2
的含14g(溶于30ml水中的)CuCl2的750ml冰乙酸溶液中。氮气完
全放出后,将混合物再搅拌15分钟,然后倒入1.4l冰-水中。用1.2l
二氯甲烷萃取,将磺酰氯分离出来。有机相干燥和浓缩后,得到
73g(0.25mol)(理论值的90%)油状物,该油状物用NMR(在CDCl3
中)分析,为纯的2-甲氧羰基-3-甲基-4-硝基苯磺酰氯。6. 4-甲基-5-硝基糖精
首先取104ml 25%的氨水溶液,加入100ml水,然后在10℃下滴加
入48.7g(0.166mol)2-甲氧羰基-3-甲基-4-硝基苯磺酰氯的
70ml四氢呋喃溶液。在25℃下搅拌3小时后,在旋转蒸发器上浓缩,
除去水和TFH,所剩的残留物与乙酸乙酯一起搅拌,并将之抽吸滤出,
用乙酸乙酯洗涤。在减压下干燥后,得34g(0.131mol)(理论值的79%)
白色固体物,m.p.:312℃(分解)。7. 2,4-二甲基-5-硝基糖精
此物质可以通过在NaOH存在下,采用硫酸二甲酯甲基化6.中获得的
糖精而制备。8. 3-甲基-4-硝基-2-(N’-甲基)羧酰氨基-N-甲基苯磺酰胺
将50ml水倒入50ml 40%的甲胺溶液中,然后,在10℃下滴加入24.3g
(83mmol)2-甲氧羰基-3-甲基-4-硝基苯磺酰氯的35ml THF
溶液。在25℃下搅拌一小时后,在旋转蒸发器上除去所有的可挥发组
分。残留物用乙酸乙酯萃取,有机相用水洗涤,并干燥和浓缩。静置一
段相对长的时间后,使所剩的残留物结晶。
收率:10.3g(40mmol=理论值的48%),m.p.:125-126℃,
乙酸乙酯重结晶后m.p.:144-145℃。
根据NMR,该产物不是糖精衍生物,而是含有另外的磺酰胺基团的羧
酰胺。9. 4-甲基-5-氨基糖精
在加热下将33.6g(0.13mol)4-甲基-5-硝基糖精溶于1.2l升水中,加入5
g Pd/C(活性碳载10%的铂)。在剧烈搅拌下通入氢气(无压力氢化
作用)。在4.5小时的过程中,吸收9升的氢气。冷却到25℃后,滤
出催化剂,滤液在旋转蒸发器上浓缩至200ml体积,然后酸化至pH 1.
抽吸滤出沉积的沉淀物,并用水洗涤和在50℃下减压干燥。得23.4g
(0.11mol=理论值的85%)白色固体物,m.p.:272-273℃。10. 4-甲基-5-碘代糖精
首先取205ml冰乙酸、160ml水和40ml浓盐酸的混合物,然后在15
-20℃搅拌下加入23.4g(0.11mol)4-甲基-5-氨基糖精。在5-
10℃下将7.9g(0.115mol)亚硝酸钠滴加入所得的悬浮液中,在5℃下搅
拌30分钟。然后将以悬浮液形式存在的重氮盐分批加入到升温至50
℃的19.1g(0.115mol)碘化钾的170ml水溶液中,同时有氮气形成。冷
却至室温后,抽吸滤出沉积的产物,用水洗涤之,并在50℃下减压干
燥。得32.5g(0.1mol=理论值的91%)固体物,m.p.:257-258
℃。
燃烧分析给出38.5%的碘含量(理论值为39.3%)。
产物的纯度足以用于随后的反应。11. 4-甲基糖精-5-羧酸
将6.4g(0.002mol)4-甲基-5-碘代糖精溶于70ml四甲基脲和30ml
水,并用0.7g双(三苯基膦)铂氯化物处理,将混合物在300ml的高
压釜中加热至100℃,并在100帕一氧化碳的压力下搅拌36小时。收
集时,将混合物过滤,在高真空下蒸馏去除水和四甲基脲。残留物用甲
基叔丁基醚(MTBE)吸收,用NaHCO3溶液萃取,用HCl酸化后,
再次用MTBE萃取。浓缩后,得2.8g 4-甲基糖精-5-羧酸(理论
值的58%)。
1H NMR(DMSO,400.1 MHz):2.85(3H,s);8.05(1H,
d);8.2(1H,d);
13C NMR(DMSO,100.6 MHz):167.4(CO);161.3
(CO);141.6(季C);139.7(季C);138.7(季C);135.6
(CH);125.4(季C);118.5(CH);15.4(CH3)。12. 2,4-二甲基糖精-5-羧酸
首先取7.3g(0.02mol)3-甲基-4-碘代-2-(N’-甲基)羧酰氨基
-N-甲基苯磺酰胺放入300ml高压釜中,同时还加入0.69g的双(三
苯基膦)铂氯化物、30ml水和70ml四甲基脲,并将混合物加热到100
℃,在100帕的一氧化碳压力下搅拌36小时。
根据实施例12中所描述的方法进行收集后,得4.1g标题化合物2,4-
二甲基-糖精-5-羧酸(0.014mol=理论值的72%)。
1H NMR(DMSO,400.1 MHz):2.9(3H,s);3.15(3H,
s);8.2(2H,2d);14.0(1H,s
13C NMR(DMSO,100.6 MHz):167.3(CO);158.6
(CO);139.7(季C);139.1(季C);138.9(季C);135.5
(CH);124.6(季C);119.0(CH);22.9(CH3);15.6
(CH3)。13. 4-氨基-3-甲基-2-(N’-甲基)羧酰氨基-N-甲基苯磺酰胺
用与第9节中所描述的方法相似方式,将第8节中获得的3-甲基-4
-硝基-2-(N’-甲基)羧酰氨基-N-甲基苯磺酰胺在无压力的
情况下氢化。以93%的收率获得下列结构的苯胺衍生物,m.p.:217
上述化合物根据第10节中所描述的方法重氮化,并与KI反应转化成碘
代苯衍生物结构。
将3.8g(14.9mmol)2,4-二甲基糖精-5-羧酸悬浮在100ml甲苯中,
将混合物加热到80℃,并滴加入3.5g(29.8mmol)亚硫酰氯。回流二小
时后,热滗析溶液,并将反应混合物浓缩。得所需产物(3g,理论值
的74%),m.p.:149-150℃。16. 式I活性化合物的通用制备方法
在25℃下,将0.43g(18mmol)镁屑加至15mmol各个式AI氰基酮的
50ml甲醇溶液中,并滴加入1ml CCl4。搅拌二小时后,在减压下汽提
除去甲醇,残留物溶于乙腈中。然后在20-25℃下,滴加入15mmol
式III糖精碳酰氯的20ml乙腈溶液,并将混合物在25℃下搅拌16小
时。收集时,首先在减压下汽提除去乙腈,残留物用乙酸乙酯收集,滤
除不溶解的副产物,并将溶液用50ml 10%的HCl摇动萃取,然后用水
洗涤二次,经硫酸钠干燥,并浓缩。当用环已烷处理油状的残留物时,
会沉淀出式I产物,为结晶固体。
表1中的下列活性化合物可以通过相同的方式获得:
No. | R1 | Q位置 | L | M | Z | M.p.(℃) |
1.01 | 环-C3H5 | 4 | H | H | H | |
1.02 | 环-C3H5 | 5 | H | H | H | |
1.03 | 环-C3H5 | 6 | H | H | CH3 | >225 |
1.04 | 环-C3H5 | 4 | 5-CH3 | H | CH3 | |
1.05 | 环-C3H5 | 5 | H | 4-CH3 | C2H5 | |
1.06 | 环-C3H5 | 5 | 4-Cl | H | CH3 | |
1.07 | 环-C3H5 | 5 | H | 4-Cl | 炔丙基 | |
1.08 | 环-C3H5 | 6 | H | 4-CH3 | CH3 | |
1.09 | 环-C3H5 | 6 | H | 4-Cl | CH3 | |
1.10 | 环-C3H5 | 6 | 5-Cl | H | C6H5 | |
1.11 | 环-C3H5 | 6 | 5-CH3 | H | C2H5 | |
1.12 | 叔C4H9 | 4 | 5-CH3 | H | CH3 | |
1.13 | 叔C4H9 | 5 | H | H | CH3 | |
1.14 | 叔C4H9 | 5 | H | 4-Cl | 炔丙基 | |
1.15 | 叔C4H9 | 5 | 4-Cl | H | CH3 | |
1.16 | 叔C4H9 | 6 | H | H | H | |
1.17 | 叔C4H9 | 6 | 5-CH3 | H | CH3 | |
1.18 | 叔C4H9 | 6 | H | 7-Cl | H | |
1.19 | 叔C4H9 | 6 | H | 7-Cl | CH3 | |
1.20 | 叔C4H9 | 6 | 5-CH3 | H | C2H5 |
将植物种植在含有壤质砂土和大约3.0%腐殖质底物的塑料花盆中。根据不同品种分别播种供试植物的种子。
对于苗前处理,将悬浮或乳化于水中的活性成分采用细分布的喷嘴在播种后直接施用。在盆中浇少量的水以促进发芽和生长,随后用透明的塑料圆盖覆盖直到植物开始长根,覆盖能使供试植物均匀发芽,除非被活性成分损害。
对于苗后处理,根据生长方式,首先使供试植物生长到3至15cm的高度,然后再用悬浮或乳化在水中的活性成分处理。为了达到上述目的,可把供试植物直接播种和培养于同一个容器中或使它们先分别发芽然后在处理前几天移栽入供试容器中。
根据不同品种将植物保持在10-25℃或20-35℃下。在试验进行的2至4周内精心管理植物并评价其对各种处理的反应。
根据0至100的标准评价,其中100意为无植物萌发或至少植物的地上部分完全损坏,0意为没有损害或生长正常。
Claims (6)
1.式I的糖精衍生物或其农业上的盐其中取代基具有下列含义:L和M是氢、C1-C4-烷基、C1-C4-烷氧基、C1-C4-烷硫基、氯、氰基、甲磺酰基、硝基或三氟甲基;Z是氢、C1-C4-烷基、C3-C8-环烷基、C3-C6-链烯基、C3-C5-炔基、C1-C4-酰基、苄基或苯基,其中的苯环未被取代或由卤素或C1-C4-烷基取代;R1是环丙基、1-甲基环丙基、1-甲硫基环丙基或叔丁基。
2.根据权利要求1的式I糖精衍生物,其中Z是甲基、乙基、炔丙基或苯基。
3.根据权利要求1和2的式I糖精衍生物,其中L和M是氢、甲基、甲氧基、甲硫基、氯、氰基、甲磺酰基、硝基或三氟甲基。
4.一种除草组合物,它含有至少一种根据权利要求1的式I糖精衍生物和常规的惰性添加剂。
5.一种防治莠草生长的方法,它包含使除草有效量的根据权利要求1的式I糖精衍生物作用于植物或其栖生地。
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DEP4428000.9 | 1994-08-08 | ||
DE4428000A DE4428000A1 (de) | 1994-08-08 | 1994-08-08 | Saccharinderivate |
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EP (1) | EP0775125B1 (zh) |
JP (1) | JPH10503775A (zh) |
KR (1) | KR970704717A (zh) |
CN (1) | CN1058007C (zh) |
AT (1) | ATE198330T1 (zh) |
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BR (1) | BR9508556A (zh) |
CA (1) | CA2197121A1 (zh) |
DE (2) | DE4428000A1 (zh) |
HU (1) | HU221859B1 (zh) |
TW (1) | TW319767B (zh) |
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CN101735167B (zh) * | 2009-12-16 | 2011-11-23 | 江苏省农用激素工程技术研究中心有限公司 | 6-硝基糖精的制备方法 |
BR112014011622A2 (pt) | 2011-11-16 | 2017-05-09 | Basf Se | composto, composição, uso de um composto e método para o controle de vegetação indesejada |
US20150291570A1 (en) | 2012-04-27 | 2015-10-15 | Basf Se | Substituted N-(tetrazol-5-yl)- and N-(triazol-5-yl)arylcarboxamide compounds and their use as herbicides |
WO2014184019A1 (en) | 2013-05-15 | 2014-11-20 | Basf Se | N-(1,2,5-oxadiazol-3-yl)carboxamide compounds and their use as herbicides |
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EP0496630A1 (en) * | 1991-01-25 | 1992-07-29 | Rhone-Poulenc Agriculture Ltd. | 2-Cyano-1,3-dione herbicides |
EP0496631A1 (en) * | 1991-01-25 | 1992-07-29 | Rhone-Poulenc Agriculture Ltd. | 2-Cyano-1,3-dione herbicides |
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CH537408A (de) * | 1970-06-11 | 1973-05-31 | Sandoz Ag | Verfahren zur Herstellung neuer herbizid wirksamer Verbindungen |
DE2358541A1 (de) * | 1973-11-22 | 1975-06-05 | Gerhard Ritzerfeld | Verfahren zur erstellung lithographischer druckformfolien und belichtungsund entwicklungsgeraet zur durchfuehrung dieses verfahrens |
FR2525593A1 (fr) * | 1982-04-23 | 1983-10-28 | Rhone Poulenc Agrochimie | Derives d'acides phenoxybenzoiques, leur preparation et leur utilisation pour le desherbage des cultures |
CA2063602A1 (en) * | 1990-05-10 | 1991-11-11 | Hannu Savisalo | Method and a device for separating plastic particles from suspensions |
EP0506373B1 (en) * | 1991-03-29 | 1995-11-29 | Tokuyama Corporation | Cyanoketone derivative and herbicide containing it as an active component |
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-
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- 1995-07-27 JP JP8506955A patent/JPH10503775A/ja active Pending
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- 1995-07-27 DE DE59508928T patent/DE59508928D1/de not_active Expired - Lifetime
- 1995-07-27 HU HU9700385A patent/HU221859B1/hu not_active IP Right Cessation
- 1995-07-27 WO PCT/EP1995/002977 patent/WO1996005183A1/de not_active Application Discontinuation
- 1995-07-27 EP EP95929016A patent/EP0775125B1/de not_active Expired - Lifetime
- 1995-07-27 CA CA002197121A patent/CA2197121A1/en not_active Abandoned
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- 1995-07-27 KR KR1019970700835A patent/KR970704717A/ko not_active Application Discontinuation
- 1995-07-27 AT AT95929016T patent/ATE198330T1/de not_active IP Right Cessation
- 1995-07-27 CN CN95195143A patent/CN1058007C/zh not_active Expired - Fee Related
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EP0496630A1 (en) * | 1991-01-25 | 1992-07-29 | Rhone-Poulenc Agriculture Ltd. | 2-Cyano-1,3-dione herbicides |
EP0496631A1 (en) * | 1991-01-25 | 1992-07-29 | Rhone-Poulenc Agriculture Ltd. | 2-Cyano-1,3-dione herbicides |
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HUT77550A (hu) | 1998-05-28 |
DE4428000A1 (de) | 1996-02-15 |
JPH10503775A (ja) | 1998-04-07 |
CN1158124A (zh) | 1997-08-27 |
ZA956579B (en) | 1997-02-07 |
DE59508928D1 (de) | 2001-02-01 |
US5716905A (en) | 1998-02-10 |
WO1996005183A1 (de) | 1996-02-22 |
EP0775125A1 (de) | 1997-05-28 |
HU221859B1 (hu) | 2003-02-28 |
AU3254095A (en) | 1996-03-07 |
EP0775125B1 (de) | 2000-12-27 |
BR9508556A (pt) | 1997-11-11 |
CA2197121A1 (en) | 1996-02-22 |
ATE198330T1 (de) | 2001-01-15 |
TW319767B (zh) | 1997-11-11 |
KR970704717A (ko) | 1997-09-06 |
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