CN1317240A - 作为除草剂的吡唑-4-基杂芳酰基衍生物 - Google Patents
作为除草剂的吡唑-4-基杂芳酰基衍生物 Download PDFInfo
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- CN1317240A CN1317240A CN01111300A CN01111300A CN1317240A CN 1317240 A CN1317240 A CN 1317240A CN 01111300 A CN01111300 A CN 01111300A CN 01111300 A CN01111300 A CN 01111300A CN 1317240 A CN1317240 A CN 1317240A
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- Prior art keywords
- alkyl
- alkoxyl
- halogen
- hydrogen
- methyl
- Prior art date
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- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 41
- 150000002367 halogens Chemical class 0.000 claims abstract description 40
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 32
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- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 30
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 16
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- 238000001035 drying Methods 0.000 description 5
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D411/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms
- C07D411/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D411/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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Abstract
本发明涉及式Ⅰ的吡唑-4-基杂芳酰基衍生物及其农业上可利用的盐,其中取代基具有下述含意:L和M是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基,这些基团是未取代或由一至五个卤原子或C1-C4-烷氧基取代;卤素、氰基、硝基;X是氧或可以由一或二个氧原子取代的硫;n是0、1、2;Q、R1、R2、R3和R4具有权利要求1中给出的含意。本发明还涉及制备此吡唑-4-基杂芳酰基衍生物的方法,包含之的组合物以及此衍生物和包含之的组合物用于防治杂草的应用。
Description
本发明涉及新颖的除草活性吡唑-4-基杂芳酰基衍生物、制备吡唑-4-基杂芳酰基衍生物的方法、包含这些衍生物的组合物及这些衍生物或含有这些衍生物的组合物防治杂草的应用。
除草活性的吡唑基芳酰基衍生物公开于文献中,例如WO9504054、WO9401431和EP629623和EP344774中。
然而,这些已知化合物的除草性能及其与作物相容性令人满意程度有限。
本发明的目的是提供具有改进性能的新颖的吡唑-4-基杂芳酰基衍生物。
我们发现,此目的通过式Ⅰ的吡唑-4-基杂芳酰基衍生物及其农业上可用的盐实现
其中取代基具有下列含意:
L和M是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基,这些基团是未取代或由一至五个卤原子或C1-C4-烷氧基取代;卤素、氰基、硝基;
X是氧或可以由一或二个氧原子取代的硫;
n是0、1、2;
R1是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基,这些基团可以是未取代的或由一至五个卤原子或C1-C4-烷氧基取代;卤素;
可以由下列基团单或多取代的苯基:C1-C4-烷基、氢、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、硝基、氰基、C1-C4-烷氧基羰基;
R2是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基,这些基团可以是未取代的或由一至五个卤原子或C1-C4-烷氧基取代;卤素;
可以由下列基团单或多取代的苯基:C1-C4-烷基、氢、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、硝基、氰基、C1-C4-烷氧基羰基;R2和R3可以形成一个键;
R3是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基,这些基团可以是未取代的或由一至五个卤原子或C1-C4-烷氧基取代;卤素;
可以由下列基团单或多取代的苯基:C1-C4-烷基、氢、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、硝基、氰基、C1-C4-烷氧基羰基;R3和R2可以形成一个键;
R4是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基,这些基团可以是未取代的或由一至五个卤原子或C1-C4-烷氧基取代;卤素;
可以由下列基团单或多取代的苯基:C1-C4-烷基、氢、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、硝基、氰基、C1-C4-烷氧基羰基;
其中
R5是C1-C4-烷基,
R6是氢、C1-C4-烷基或C1-C4-卤代烷基,且
R7是氢、C1-C4-烷基磺酰基、苯基磺酰基或烷基苯基磺酰基。
式Ⅰ化合物可如下制备:式Ⅱ化合物与式Ⅲ的苯甲酸衍生物反应,并将产物进行重排反应,给出式Ⅰ的吡唑-4-基杂芳酰基衍生物。
在上面的反应方案1中,在所述的化学式中的T具有卤素或OH的含意,且L、M、X、R1、R2、R3、R4、R5、R6和n具有上面给出的含意。
反应程序的第一步,即酰化是用一般已知的方式进行的,例如在有或无辅助碱存在下,向环己二酮(cyclohexnedione)Ⅱ的溶液或悬浮液中,加入式Ⅲ的酰氯(T=Cl)或用DCC(双环碳化二亚胺)或由文献已知的类似试剂(例如三苯基膦/DEAD=偶氮二羧酸二乙酯,2-吡啶二硫化物/三苯基膦)活化的式Ⅲ的羧酸(T=OH)。采用等摩尔量的反应剂和辅助碱是有利的。在某些情况下,相对于Ⅱ,采用少量过量例如1.2至1.5摩尔当量的辅助碱会是有益的。
有用的辅助碱是叔烷基胺、吡啶或碱金属碳酸盐。所用的溶剂例如可以是二氯甲烷、二噁烷、***、甲苯、乙腈或乙酸乙酯。
在加入酰氯时,优选将反应混合物冷却至0至10℃,之后在20-100℃下,特别是25至50℃下搅拌此混合物,直到反应完毕。后处理是用常规方式进行的,例如,将反应混合物倒入水中,并萃取有用的产物,例如用二氯甲烷。在有机相干燥并去除溶剂后,粗制的烯醇酯可以无需作进一步纯化而直接用于重排反应。5-羟基吡唑的苯甲酸酯的制备实例例如可见于EP-A-282 944或US4,643,757中。
有利地是在20至40℃下,在溶剂中和在辅助碱存在下,且如果需要,借助于作为催化剂的氰基化合物,将5-羟基吡唑基苯甲酸酯重排成式Ⅰ化合物。
可以使用的溶剂的实例例如是乙腈、二氯甲烷、叔戊醇、二噁烷、1,2-二氯乙烷、乙酸乙酯或甲苯。优选的溶剂是乙腈和二噁烷。有用的辅助碱是叔烷基胺、吡啶或碱金属碳酸盐,相对于5-羟基吡唑苯甲酸酯,它们优选采用等摩尔或至多四倍过量。优选的辅助碱是二倍量的三乙胺和碱金属碳酸盐。
有用的催化剂是***、丙酮合氰化氢和三甲基甲硅烷基氰化物,相对于烯醇酯,优选采用1至50摩尔%的量。优选的是,以5至15、特别是10摩尔%的量加入丙酮合氰化氢。
5-羟基吡唑的苯甲酸酯重排反应的实例例如可见于EP-A282 944或US4,643,757中。
后处理是用本身已知的方式进行的,例如反应混合物用稀无机酸例如用浓度为5%的盐酸或硫酸来酸化,并用有机溶剂例如二氯甲烷或乙酸乙醇萃取。纯化时,将萃取液用冷的浓度为5至10%的碱金属碳酸盐溶液萃取,式Ⅰa-Ⅰe的终产物在含水相中沉淀出来,或用二氯甲烷或乙酸乙酯再萃取,干燥,随后去除溶剂。
用作起始原料的式Ⅱ的5-羟基吡唑是已知的且可以由本身已知的方式制备(参见,例如EP-A240 001和实用化学杂志(J.Prakt.Chem.)315(1973),382)。1,3-二甲基-5-羟基吡唑是有商品出售的化合物。
式Ⅲ的苯甲酸衍生物可以如下制备:
式Ⅲ的苯甲酰卤、例如苯甲酰氯(T=Cl)用本身已知的方式,通过式Ⅲ的苯甲酸(T=OH)与亚硫酰氯反应而制备。
式Ⅲ的苯甲酸(T=OH)可以用已知的方式,通过酸水解或碱水解相应的式Ⅲ的酯(T=C1-C4-烷氧基)而制备。
式Ⅲ中间体在一些情况下可以由那些由文献已知的化合物如由取代的苯酚羧酸Ⅳ或硫代羧酸V为起始原料来合成。迄今尚未知的化合物Ⅳ或Ⅴ可以通过由文献已知的反应来合成(参考文献:有机化学方法(HoubenWeyl,Methoden der Organischen Chemie)第Ⅵ、Ⅸ和E11卷)。
给出式Ⅲ中间体的另外的反应通过由文献已知的方法进行(例如,合成(Synthesis)1975,451;有机化学杂志(J.Org.Chem.)1974,39-1811;美国化学学会杂志(J.Am.Chem.Soc.)1954,76,1068;杂环化合物(Heterocyclic Compouds),卷:多硫和含硫和氧五元和六元杂环;有机化学杂志(J.Org.Chem.)1979,44,1977)。
Z=Br,OH,OSO2CH3,OSO2p-CH3-C6H4
这表明,例如反应方案2A所示,2,3-二氢苯并-1,4-氧硫杂环己二烯衍生物可以通过芳族化合物(X=O、S;T=OH、C1-C4-烷氧基)上的分子内亲核取代反应来合成(文献:杂环化学杂志(J.Heterocycl.Chem.)20,1983,867)。途径B和C描述了合成2-烷氧基-2,3-二氢苯并-1,4-氧硫杂环己二烯衍生物的方法,它描述于文献中(文献:美国化学学会杂志(J.Am.Chem.Soc.)76,1954,1068;有机化学杂志(J.Org.Chem.)44,1979,1977)。如反应方案2的D和E中所示,酚类或硫醇美可以用烷基溴烷基化,例如反应方案2的D和E中所示在碱溶液中进行。可以方便地以等摩尔量使用反应剂和碱。碱过量会是有利的。优选的溶剂是醇类如乙醇或DMF,且优选的碱是醇盐例如乙醇钠或NaH。反应可以在常压或加压下进行。优选的压力范围是1至10巴。反应混合物优选在20-150℃搅拌,特别是在60-80℃。后处理例如是用这样的方式进行的,将反应混合物倒入稀碱如氢氧化钠溶液中,且有价值的产物可以通过萃取获得,例如使用乙酸乙酯,干燥并去除溶剂。
然而,此步骤可以接着使用甲基硫代磺酸钾的醇溶液来交换Z。优选的溶剂是乙醇、甲醇和异丙醇。反应混合物优选在20-100℃下进行搅拌,特别是在60-80℃。
后处理例如是通过加入水、将有价值的产物抽吸滤出,或使用例如二氯甲烷来萃取、并干燥来进行。
给出二氢苯并氧硫杂环己二烯或二氢苯并二硫杂环己二烯骨架的环化反应是在惰性溶剂中通过加入路易斯酸来进行的。优选的路易斯酸是三氯化铝,且优选的惰性溶剂是硝基甲烷或二氯甲烷。反应混合物保持在20-50℃下。后处理例如是通过加入稀无机酸如盐酸,有价值的产物用抽吸滤出或用***萃取,干燥并去除溶剂来进行。
这些化合物可以用由文献已知的方法氧化和/或脱氢来进一步官能化(Houben Weyl的有机合成方法(Methoden Der Organischen Synthese),第Ⅳ/1a和b卷)。
另外,式Ⅲ的苯甲酸还可以通过在钯、镍、钴或铑过渡金属催化剂和碱存在下,使相应的式ⅩⅧ的溴-或碘-取代的化合物与一氧化碳和水反应而获得
其中
T是OH、C1-C4-烷氧基,且
L、M、X、R1至R4和n具有上面所述的含意。
催化剂镍、钴、铑和特别是钯可以以金属形式或是以其已知价位的常规盐的形式存在,如卤素化合物形式,例如PdCl2、RhCl3·H2O,乙酸盐,例如Pd(OAc)2,氰化物等。还可以存在与叔膦配合的金属配合物、金属烷基羰基化物、金属羰基化物,例如CO2(CO)8、Ni(CO)4,与叔膦配合的金属羰基配合物,例如(PPh3)2Ni(CO)2,或与叔膦配合的过渡金属盐。最后提到的实施方式是优选的,特别是在钯作为催化剂的情况下。在此处的膦配位体可在很宽范围内变化。例如它们可以下列化学式表示:或
其中k是1、2、3或4,且基团R12至R15是低分子量烷基例如C1-C6-烷基、芳基、C1-C4-烷基芳基例如苄基、苯乙基或芳氧基。芳基是例如萘基、蒽基且优选是未取代或取代的苯基,其中对于取代基而言,只考虑其对羧基反应是否具有惰性,除此之外,取代基可以有各种变化,且包括所有的惰性C-有机基团如C1-C6-烷基基团,例如甲基,羧基基团如COOH、COOM(M是例如碱金属盐、碱土金属盐或铵盐),或经氧键连的C-有机基团,如C1-C6-烷氧基基团。
膦配合物可以用本身已知的方式制备,例如用在开头所提到的文献中所描述的方法。例如常规的商品化金属盐如PdCl2或Pd(OCOCH3)2用作起始原料,加上膦例如P(C6H5)3、P(n-C4H9)3、PCH3(C6H5)2、1,2-双(二苯基膦基)乙烷。
以过渡金属为基准,膦的量通常是0至20、特别是0.1至10摩尔当量,特别是1至5摩尔当量。
过渡金属的量不是关键性的。当然,由于费用的原因,以起始原料Ⅱ或Ⅲ为基准,其使用量很小,例如是0.1至10摩尔%,特别是1至5摩尔%。
制备苯甲酸Ⅲ(T=OH)时,以起始原料Ⅵ为基准,反应是用一氧化碳和至少等摩尔量的水进行的。反应试剂水也可以同时作为溶剂使用,即,其最大的量不是关键性的。
然而,取决于所用的起始原料和催化剂,使用另一种惰性溶剂或用于羧化反应的碱来替代用作溶剂的反应物水作为溶剂或许会是有利的。
适合的惰性溶剂是用于羧化反应的常规溶剂,如烃,例如甲苯、二甲苯、己烷、戊烷、环己烷,醚类,例如甲基叔丁基醚、四氢呋喃、二噁烷、二甲氧基乙烷,取代的酰胺类如二甲基甲酰胺,全取代的脲类如四-C1-C4-烷基脲,或腈类如苯甲腈或乙腈。
在此方法的优选实施方案中,过量使用反应物之一,特别是碱,这样便无需另外加入溶剂。
适合于此方法的碱是所有的能够结合反应所释放的碘化氢或溴化氢的惰性碱。在此可以提到的实例是叔胺如叔烷基胺,例如三烷基胺如三乙胺,环胺如N-甲基哌啶或N,N’-二甲基哌嗪,吡啶,碱金属碳酸盐或碳酸氢盐,或四烷基取代的脲衍生物如四-C1-C4-烷基脲,例如四甲基脲。
碱的量不是关键性的,通常使用的是1至10,特别是1至5摩尔。当碱同时作为溶剂使用时,通常以这样的方式来选择其量,一方面要使各种反应物溶解,另一方面为了切实可行之原因,应避免不必要的太大过量,以节省费用,和能够采用小的反应容器以及确保反应物间的最大接触。
反应期间,以Ⅵ为基准,将一氧化碳压力调节至总是存在过量的CO。优选的是,一氧化碳压力是在室温下为1至250巴,特别是5至150巴的CO。
羰基化作用通常是在20至250℃,特别是30至150℃下连续或分批进行的。在批量操作的情况下,有利地是将一氧化碳连续注入反应混合物中,以保持常压。
如果用作起始原料的芳基卤素化合物ⅩⅧ不是已知的,则可以容易地通过已知合成法的适当组合和通过上述反应程序而制备。
对于通式Ⅰ的吡唑基杂芳酰基衍生物的意欲用途而言,下列基团是适合的取代基:
L和M是氢,
C1-C6-烷基,如甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1,1-二甲基丙基、1,2-二甲基丙基、2,2-二甲基丙基、1-乙基丙基、己基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基或1-乙基-2-甲基丙基;
特别是甲基、乙基、1-甲基乙基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基和1,1-二甲基丙基;
C2-C6-链烯基,如2-丙烯基、2-丁烯基、3-丁烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基、2-戊烯基、3-戊烯基、4-戊烯基、3-甲基-2-丁烯基、1-甲基-2-丁烯基、2-甲基-2-丁烯基、1-甲基-3-丁烯基、2-甲基-4-丁烯基、3-甲基-3-丁烯基、1,1-二甲基-2-丙烯基、1,2-二甲基-2-丙烯基、1-乙基-2-丙烯基、2-己烯基、3-己烯基、4-己烯基、5-己烯基、1-甲基-2-戊烯基、2-甲基-2-戊烯基、3-甲基-2-戊烯基、4-甲基-2-戊烯基、1-甲基-3-戊烯基、2-甲基-3-戊烯基、3-甲基-3-戊烯基、4-甲基-3-戊烯基、1-甲基-4-戊烯基、2-甲基-4-戊烯基、3-甲基-4-戊烯基、4-甲基-4-戊烯基、1,1-二甲基-2-丁烯基、1,1-二甲基-3-丁烯基、1,2-二甲基-2-丁烯基、1,3-二甲基-3-丁烯基、2,2-二甲基-3-丁烯基、2,3-二甲基-2-丁烯基、2,3-二甲基-3-丁烯基、1-乙基-2-丁烯基、1-乙基-3-丁烯基、2-乙基-2-丁烯基、2-乙基-3-丁烯基、1,1,2-三甲基-2-丙烯基、1-乙基-1-甲基-2-丙烯基和乙基-2-甲基-2-丙烯基;
特别是1-甲基-2-丙烯基、1-甲基-2-丁烯基、1,1-二甲基-2-丙烯基和1,1-二甲基-2-丁烯基;
C2-C6-炔基,如炔丙基、2-丁炔基、3-丁炔基、2-戊炔基、3-戊炔基、4-戊炔基、1-甲基-3-丁炔基、2-甲基-3-丁炔基、1-甲基-2-丁炔基、1,1-二甲基-2-丙炔基、1-乙基-2丙炔基、2-己炔基、3-己炔基、4-己炔基、5-己炔基、1-甲基-2-戊炔基、1-甲基-3-戊炔基、1-甲基-4-戊炔基、3-甲基-4-戊炔基、4-甲基-2-戊炔基、1,1-二甲基-2-丁炔基、1,1-二甲基-3-丁炔基、1,2-二甲基-3-丁炔基、2,2-二甲基-3-丁炔基、1-乙基-2-丁炔基、1-乙基-3-丁炔基、2-乙基-3-丁炔基和1-乙基-1-甲基-2-丙炔基;
C1-C4-烷氧基,如甲氧基、乙氧基、正丙氧基、1-甲基乙氧基、正丁氧基、1-甲基丙氧基、2-甲基丙氧基和1,1-二甲基-乙氧基,
特别是C1-C3-烷氧基,如甲氧基、乙氧基和异丙氧基,
其中这些基团可以是未取代或由一至五个卤素如氟、氯、溴和碘,优选氟和氯或如上所述的C1-C4-烷氧基取代。
优选的吡唑-4-基杂芳酰基衍生物是这样的式Ⅰa所示的化合物,
其中L是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、氰基或硝基,
和M是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、氰基或硝基,和
Q、X、R1至R4和n具有上面提到的含意。
其中L是C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、氰基或硝基,
和M是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、氰基或硝基,和
Q、X、R1至R4和n具有上面提到的含意。
其它优选的式Ⅰ的吡唑-4-基杂芳酰基衍生物是那些其中基团L和M是氢、甲基、甲氧基、氯、氰基、硝基或三氟甲基的化合物。
其中L是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、氰基或硝基,
和M是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、氰基或硝基,
和Q、R1至R4和n具有上面提到的含意。
其它优选的吡唑-4-基杂芳酰基衍生物是这样的式Ⅰd所示的化合物,
其中L是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、氰基或硝基,
和Q、R1、R4和n具有上面提到的含意。
其它优选的吡唑-4-基杂芳酰基衍生物是这样的式Ⅰd所示的化合物,
其中L是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、氰基或硝基,
和M是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、氰基或硝基,和m是0、1或2,
和Q、R1、R4和n具有上面提到的含意。
其中L是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、氰基或硝基,
和M是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、氰基或硝基,和m是0、1或2,
和Q、R1至R4和n具有上面提到的含意。
其它优选的吡唑-4-基杂芳酰基衍生物是那些其取代基由优选的取代基组合的式Ⅰ至Ⅰd所示的化合物。
特别优选的式Ⅰ化合物列于下文表1-2中。
表1:下述结构的化合物
序号 | R5 | R6 | R7 | n | R1 | R2 | R3 | R4 | X | L | M |
1.1 | CH3 | CH3 | H | 0 | H | H | H | H | O | H | H |
1.2 | CH3 | CH3 | H | 2 | H | H | H | H | O | H | H |
1.3 | CH3 | CH3 | H | 0 | H | H | H | H | S | H | H |
1.4 | CH3 | CH3 | H | 2 | H | H | H | H | S | H | H |
1.5 | CH3 | CH3 | H | 0 | H | H | H | H | SO2 | H | H |
1.6 | CH3 | CH3 | H | 2 | H | H | H | H | SO2 | H | H |
1.7 | CH3 | CH3 | H | 0 | CH3 | H | H | H | O | H | H |
1.8 | CH3 | CH3 | H | 2 | CH3 | H | H | H | O | H | H |
1.9 | CH3 | CH3 | H | 0 | CH3 | H | H | H | S | H | H |
1.10 | CH3 | CH3 | H | 2 | CH3 | H | H | H | S | H | H |
1.11 | CH3 | CH3 | H | 0 | CH3 | H | H | H | SO2 | H | H |
1.12 | CH3 | CH3 | H | 2 | CH3 | H | H | H | SO2 | H | H |
1.13 | CH3 | CH3 | H | 0 | CH3 | H | CH3 | H | O | H | H |
1.14 | CH3 | CH3 | H | 2 | CH3 | H | CH3 | H | O | H | H |
1.15 | CH3 | CH3 | H | 0 | CH3 | H | CH3 | H | S | H | H |
1.16 | CH3 | CH3 | H | 2 | CH3 | H | CH3 | H | S | H | H |
1.17 | CH3 | CH3 | H | 0 | CH3 | H | CH3 | H | SO2 | H | H |
1.18 | CH3 | CH3 | H | 2 | CH3 | H | CH3 | H | SO2 | H | H |
1.19 | CH3 | CH3 | H | 0 | CH3 | CH3 | H | H | O | H | H |
序号 | R5 | R6 | R7 | n | R1 | R2 | R3 | R4 | X | L | M |
1.20 | CH3 | CH3 | H | 2 | CH3 | CH3 | H | H | O | H | H |
1.21 | CH3 | CH3 | H | 0 | H | H | CH3 | CH3 | O | H | H |
1.22 | CH3 | CH3 | H | 2 | H | H | CH3 | CH3 | O | H | H |
1.23 | C2H5 | H | H | 0 | H | H | H | H | O | H | H |
1.24 | C2H5 | H | H | 2 | H | H | H | H | O | H | H |
1.25 | C2H5 | H | H | 0 | H | H | H | H | S | H | H |
1.26 | C2H5 | H | H | 2 | H | H | H | H | S | H | H |
1.27 | C2H5 | H | H | 0 | H | H | H | H | SO2 | H | H |
1.28 | C2H5 | H | H | 2 | H | H | H | H | SO2 | H | H |
1.29 | C2H5 | H | H | 0 | CH3 | H | H | H | O | H | H |
1.30 | C2H5 | H | H | 2 | CH3 | H | H | H | O | H | H |
1.31 | C2H5 | H | H | 0 | CH3 | H | H | H | S | H | H |
1.32 | C2H5 | H | H | 2 | CH3 | H | H | H | S | H | H |
1.33 | C2H5 | H | H | 0 | CH3 | H | H | H | SO2 | H | H |
1.34 | C2H5 | H | H | 2 | CH3 | H | H | H | SO2 | H | H |
1.35 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | O | H | H |
1.36 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | O | H | H |
1.37 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | S | H | H |
1.38 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | S | H | H |
1.39 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | SO2 | H | H |
1.40 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | SO2 | H | H |
1.41 | C2H5 | H | H | 0 | CH3 | CH3 | H | H | O | H | H |
1.42 | C2H5 | H | H | 2 | CH3 | CH3 | H | H | O | H | H |
1.43 | C2H5 | H | H | 0 | H | H | CH3 | CH3 | O | H | H |
1.44 | C2H5 | H | H | 2 | H | H | CH3 | CH3 | O | H | H |
1.45 | CH3 | H | H | 0 | H | H | H | H | O | H | CH3 |
1.46 | CH3 | H | H | 2 | H | H | H | H | O | H | CH3 |
1.47 | CH3 | H | H | 0 | H | H | H | H | S | H | CH3 |
1.48 | CH3 | H | H | 2 | H | H | H | H | S | H | CH3 |
1.49 | CH3 | H | H | 0 | H | H | H | H | SO2 | H | CH3 |
1.50 | CH3 | H | H | 2 | H | H | H | H | SO2 | H | CH3 |
1.51 | CH3 | H | H | 0 | CH3 | H | H | H | O | H | CH3 |
1.52 | CH3 | H | H | 2 | CH3 | H | H | H | O | H | CH3 |
1.53 | CH3 | H | H | 0 | CH3 | H | H | H | S | H | CH3 |
1.54 | CH3 | H | H | 2 | CH3 | H | H | H | S | H | CH3 |
序号 | R5 | R6 | R7 | n | R1 | R2 | R3 | R4 | X | L | M |
1.55 | CH3 | H | H | 0 | CH3 | H | H | H | SO2 | H | CH3 |
1.56 | CH3 | H | H | 2 | CH3 | H | H | H | SO2 | H | CH3 |
1.57 | CH3 | H | H | 0 | CH3 | H | CH3 | H | O | H | CH3 |
1.58 | CH3 | H | H | 2 | CH3 | H | CH3 | H | O | H | CH3 |
1.59 | CH3 | H | H | 0 | CH3 | H | CH3 | H | S | H | CH3 |
1.60 | CH3 | H | H | 2 | CH3 | H | CH3 | H | S | H | CH3 |
1.61 | CH3 | H | H | 0 | CH3 | H | CH3 | H | SO2 | H | CH3 |
1.62 | CH3 | H | H | 2 | CH3 | H | CH3 | H | SO2 | H | CH3 |
1.63 | CH3 | H | H | 0 | CH3 | CH3 | H | H | O | H | CH3 |
1.64 | CH3 | H | H | 2 | CH3 | CH3 | H | H | O | H | CH3 |
1.65 | CH3 | H | H | 0 | H | H | CH3 | CH3 | O | H | CH3 |
1.66 | CH3 | H | H | 2 | H | H | CH3 | CH3 | O | H | CH3 |
1.67 | C2H5 | H | H | 0 | H | H | H | H | O | H | CH3 |
1.68 | C2H5 | H | H | 2 | H | H | H | H | O | H | CH3 |
1.69 | C2H5 | H | H | 0 | H | H | H | H | S | H | CH3 |
1.70 | C2H5 | H | H | 2 | H | H | H | H | S | H | CH3 |
1.71 | C2H5 | H | H | 0 | H | H | H | H | SO2 | H | CH3 |
1.72 | C2H5 | H | H | 2 | H | H | H | H | SO2 | H | CH3 |
1.73 | C2H5 | H | H | 0 | CH3 | H | H | H | O | H | CH3 |
1.74 | C2H5 | H | H | 2 | CH3 | H | H | H | O | H | CH3 |
1.75 | C2H5 | H | H | 0 | CH3 | H | H | H | S | H | CH3 |
1.76 | C2H5 | H | H | 2 | CH3 | H | H | H | S | H | CH3 |
1.77 | C2H5 | H | H | 0 | CH3 | H | H | H | SO2 | H | CH3 |
1.78 | C2H5 | H | H | 2 | CH3 | H | H | H | SO2 | H | CH3 |
1.79 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | O | H | CH3 |
1.80 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | O | H | CH3 |
1.81 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | S | H | CH3 |
1.82 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | S | H | CH3 |
1.83 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | SO2 | H | CH3 |
1.84 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | SO2 | H | CH3 |
1.85 | C2H5 | H | H | 0 | CH3 | CH3 | H | H | O | H | CH3 |
1.86 | C2H5 | H | H | 2 | CH3 | CH3 | H | H | O | H | CH3 |
1.87 | C2H5 | H | H | 0 | H | H | CH3 | CH3 | O | H | CH3 |
1.88 | C2H5 | H | H | 2 | H | H | CH3 | CH3 | O | H | CH3 |
1.89 | CH3 | H | H | 0 | H | H | H | H | O | H | Cl |
序号 | R5 | R6 | R7 | n | R1 | R2 | R3 | R4 | X | L | M |
1.90 | CH3 | H | H | 2 | H | H | H | H | O | H | Cl |
1.91 | CH3 | H | H | 0 | H | H | H | H | S | H | Cl |
1.92 | CH3 | H | H | 2 | H | H | H | H | S | H | Cl |
1.93 | CH3 | H | H | 0 | H | H | H | H | SO2 | H | Cl |
1.94 | CH3 | H | H | 2 | H | H | H | H | SO2 | H | Cl |
1.95 | CH3 | H | H | 0 | CH3 | H | H | H | O | H | Cl |
1.96 | CH3 | H | H | 2 | CH3 | H | H | H | O | H | Cl |
1.97 | CH3 | H | H | 0 | CH3 | H | H | H | S | H | Cl |
1.98 | CH3 | H | H | 2 | CH3 | H | H | H | S | H | Cl |
1.99 | CH3 | H | H | 0 | CH3 | H | H | H | SO2 | H | Cl |
1.100 | CH3 | H | H | 2 | CH3 | H | H | H | SO2 | H | Cl |
1.101 | CH3 | H | H | 0 | CH3 | H | CH3 | H | O | H | Cl |
1.102 | CH3 | H | H | 2 | CH3 | H | CH3 | H | O | H | Cl |
1.103 | CH3 | H | H | 0 | CH3 | H | CH3 | H | S | H | Cl |
1.104 | CH3 | H | H | 2 | CH3 | H | CH3 | H | S | H | Cl |
1.105 | CH3 | H | H | 0 | CH3 | H | CH3 | H | SO2 | H | Cl |
1.106 | CH3 | H | H | 2 | CH3 | H | CH3 | H | SO2 | H | Cl |
1.107 | CH3 | H | H | 0 | CH3 | CH3 | H | H | O | H | Cl |
1.108 | CH3 | H | H | 2 | CH3 | CH3 | H | H | O | H | Cl |
1.109 | CH3 | H | H | 0 | H | H | CH3 | CH3 | O | H | Cl |
1.110 | CH3 | H | H | 2 | H | H | CH3 | CH3 | O | H | Cl |
1.111 | C2H5 | H | H | 0 | H | H | H | H | O | H | Cl |
1.112 | C2H5 | H | H | 2 | H | H | H | H | O | H | Cl |
1.113 | C2H5 | H | H | 0 | H | H | H | H | S | H | Cl |
1.114 | C2H5 | H | H | 2 | H | H | H | H | S | H | Cl |
1.115 | C2H5 | H | H | 0 | H | H | H | H | SO2 | H | Cl |
1.116 | C2H5 | H | H | 2 | H | H | H | H | SO2 | H | Cl |
1.117 | C2H5 | H | H | 0 | CH3 | H | H | H | O | H | Cl |
1.118 | C2H5 | H | H | 2 | CH3 | H | H | H | O | H | Cl |
1.119 | C2H5 | H | H | 0 | CH3 | H | H | H | S | H | Cl |
1.120 | C2H5 | H | H | 2 | CH3 | H | H | H | S | H | Cl |
1.121 | C2H5 | H | H | 0 | CH3 | H | H | H | SO2 | H | Cl |
1.122 | C2H5 | H | H | 2 | CH3 | H | H | H | SO2 | H | Cl |
1.123 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | O | H | Cl |
1.124 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | O | H | Cl |
序号 | R5 | R6 | R7 | n | R1 | R2 | R3 | R4 | X | L | M |
1.125 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | S | H | Cl |
1.126 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | S | H | Cl |
1.127 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | SO2 | H | Cl |
1.128 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | SO2 | H | Cl |
1.129 | C2H5 | H | H | 0 | CH3 | CH3 | H | H | O | H | Cl |
1.130 | C2H5 | H | H | 2 | CH3 | CH3 | H | H | O | H | Cl |
1.131 | C2H5 | H | H | 0 | H | H | CH3 | CH3 | O | H | Cl |
1.132 | C2H5 | H | H | 2 | H | H | CH3 | CH3 | O | H | Cl |
1.133 | CH3 | H | H | 0 | H | H | H | H | O | Cl | Cl |
1.134 | CH3 | H | H | 2 | H | H | H | H | O | Cl | Cl |
1.135 | CH3 | H | H | 0 | H | H | H | H | S | Cl | Cl |
1.136 | CH3 | H | H | 2 | H | H | H | H | S | Cl | Cl |
1.137 | CH3 | H | H | 0 | H | H | H | H | SO2 | Cl | Cl |
1.138 | CH3 | H | H | 2 | H | H | H | H | SO2 | Cl | Cl |
1.139 | CH3 | H | H | 0 | CH3 | H | H | H | O | Cl | Cl |
1.140 | CH3 | H | H | 2 | CH3 | H | H | H | O | Cl | Cl |
1.141 | CH3 | H | H | 0 | CH3 | H | H | H | S | Cl | Cl |
1.142 | CH3 | H | H | 2 | CH3 | H | H | H | S | Cl | Cl |
1.143 | CH3 | H | H | 0 | CH3 | H | H | H | SO2 | Cl | Cl |
1.144 | CH3 | H | H | 2 | CH3 | H | H | H | SO2 | Cl | Cl |
1.145 | CH3 | H | H | 0 | CH3 | H | CH3 | H | O | Cl | Cl |
1.146 | CH3 | H | H | 2 | CH3 | H | CH3 | H | O | Cl | Cl |
1.147 | CH3 | H | H | 0 | CH3 | H | CH3 | H | S | Cl | Cl |
1.148 | CH3 | H | H | 2 | CH3 | H | CH3 | H | S | Cl | Cl |
1.149 | CH3 | H | H | 0 | CH3 | H | CH3 | H | SO2 | Cl | Cl |
1.150 | CH3 | H | H | 2 | CH3 | H | CH3 | H | SO2 | Cl | Cl |
1.151 | CH3 | H | H | 0 | CH3 | CH3 | H | H | O | Cl | Cl |
1.152 | CH3 | H | H | 2 | CH3 | CH3 | H | H | O | Cl | Cl |
1.153 | CH3 | H | H | 0 | H | H | CH3 | CH3 | O | Cl | Cl |
1.154 | CH3 | H | H | 2 | H | H | CH3 | CH3 | O | Cl | Cl |
1.155 | C2H5 | H | H | 0 | H | H | H | H | O | Cl | Cl |
1.156 | C2H5 | H | H | 2 | H | H | H | H | O | Cl | Cl |
1.157 | C2H5 | H | H | 0 | H | H | H | H | S | Cl | Cl |
1.158 | C2H5 | H | H | 2 | H | H | H | H | S | Cl | Cl |
1.159 | C2H5 | H | H | 0 | H | H | H | H | SO2 | Cl | Cl |
序号 | R5 | R6 | R7 | n | R1 | R2 | R3 | R4 | X | L | M |
1.160 | C2H5 | H | H | 2 | H | H | H | H | SO2 | Cl | Cl |
1.161 | C2H5 | H | H | 0 | CH3 | H | H | H | O | Cl | Cl |
1.162 | C2H5 | H | H | 2 | CH3 | H | H | H | O | Cl | Cl |
1.163 | C2H5 | H | H | 0 | CH3 | H | H | H | S | Cl | Cl |
1.164 | C2H5 | H | H | 2 | CH3 | H | H | H | S | Cl | Cl |
1.165 | C2H5 | H | H | 0 | CH3 | H | H | H | SO2 | Cl | Cl |
1.166 | C2H5 | H | H | 2 | CH3 | H | H | H | SO2 | Cl | Cl |
1.167 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | O | Cl | Cl |
1.168 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | O | Cl | Cl |
1.169 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | S | Cl | Cl |
1.170 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | S | Cl | Cl |
1.171 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | SO2 | Cl | Cl |
1.172 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | SO2 | Cl | Cl |
1.173 | C2H5 | H | H | 0 | CH3 | CH3 | H | H | O | Cl | Cl |
1.174 | C2H5 | H | H | 2 | CH3 | CH3 | H | H | O | Cl | Cl |
1.175 | C2H5 | H | H | 0 | H | H | CH3 | CH3 | O | Cl | Cl |
1.176 | C2H5 | H | H | 2 | H | H | CH3 | CH3 | O | Cl | Cl |
1.177 | CH3 | H | H | 0 | H | H | H | H | O | CH3 | CH3 |
1.178 | CH3 | H | H | 2 | H | H | H | H | O | CH3 | CH3 |
1.179 | CH3 | H | H | 0 | H | H | H | H | S | CH3 | CH3 |
1.180 | CH3 | H | H | 2 | H | H | H | H | S | CH3 | CH3 |
1.181 | CH3 | H | H | 0 | H | H | H | H | SO2 | CH3 | CH3 |
1.182 | CH3 | H | H | 2 | H | H | H | H | SO2 | CH3 | CH3 |
1.183 | CH3 | H | H | 0 | CH3 | H | H | H | O | CH3 | CH3 |
1.184 | CH3 | H | H | 2 | CH3 | H | H | H | O | CH3 | CH3 |
1.185 | CH3 | H | H | 0 | CH3 | H | H | H | S | CH3 | CH3 |
1.186 | CH3 | H | H | 2 | CH3 | H | H | H | S | CH3 | CH3 |
1.187 | CH3 | H | H | 0 | CH3 | H | H | H | SO2 | CH3 | CH3 |
1.188 | CH3 | H | H | 2 | CH3 | H | H | H | SO2 | CH3 | CH3 |
1.189 | CH3 | H | H | 0 | CH3 | H | CH3 | H | O | CH3 | CH3 |
1.190 | CH3 | H | H | 2 | CH3 | H | CH3 | H | O | CH3 | CH3 |
1.191 | CH3 | H | H | 0 | CH3 | H | CH3 | H | S | CH3 | CH3 |
1.192 | CH3 | H | H | 2 | CH3 | H | CH3 | H | S | CH3 | CH3 |
1.193 | CH3 | H | H | 0 | CH3 | H | CH3 | H | SO2 | CH3 | CH3 |
1.194 | CH3 | H | H | 2 | CH3 | H | CH3 | H | SO2 | CH3 | CH3 |
序号 | R5 | R6 | R7 | n | R1 | R2 | R3 | R4 | X | L | M |
1.195 | CH3 | H | H | 0 | CH3 | CH3 | H | H | O | CH3 | CH3 |
1.196 | CH3 | H | H | 2 | CH3 | CH3 | H | H | O | CH3 | CH3 |
1.197 | CH3 | H | H | 0 | H | H | CH3 | CH3 | O | CH3 | CH3 |
1.198 | CH3 | H | H | 2 | H | H | CH3 | CH3 | O | CH3 | CH3 |
1.199 | C2H5 | H | H | 0 | H | H | H | H | O | CH3 | CH3 |
1.200 | C2H5 | H | H | 2 | H | H | H | H | O | CH3 | CH3 |
1.201 | C2H5 | H | H | 0 | H | H | H | H | S | CH3 | CH3 |
1.202 | C2H5 | H | H | 2 | H | H | H | H | S | CH3 | CH3 |
1.203 | C2H5 | H | H | 0 | H | H | H | H | SO2 | CH3 | CH3 |
1.204 | C2H5 | H | H | 2 | H | H | H | H | SO2 | CH3 | CH3 |
1.205 | C2H5 | H | H | 0 | CH3 | H | H | H | O | CH3 | CH3 |
1.206 | C2H5 | H | H | 2 | CH3 | H | H | H | O | CH3 | CH3 |
1.207 | C2H5 | H | H | 0 | CH3 | H | H | H | S | CH3 | CH3 |
1.208 | C2H5 | H | H | 2 | CH3 | H | H | H | S | CH3 | CH3 |
1.209 | C2H5 | H | H | 0 | CH3 | H | H | H | SO2 | CH3 | CH3 |
1.210 | C2H5 | H | H | 2 | CH3 | H | H | H | SO2 | CH3 | CH3 |
1.211 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | O | CH3 | CH3 |
1.212 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | O | CH3 | CH3 |
1.213 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | S | CH3 | CH3 |
1.214 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | S | CH3 | CH3 |
1.215 | C2H5 | H | H | 0 | CH3 | H | CH3 | H | SO2 | CH3 | CH3 |
1.216 | C2H5 | H | H | 2 | CH3 | H | CH3 | H | SO2 | CH3 | CH3 |
1.217 | C2H5 | H | H | 0 | CH3 | CH3 | H | H | O | CH3 | CH3 |
1.218 | C2H5 | H | H | 2 | CH3 | CH3 | H | H | O | CH3 | CH3 |
1.219 | C2H5 | H | H | 0 | H | H | CH3 | CH3 | O | CH3 | CH3 |
1.220 | C2H5 | H | H | 2 | H | H | CH3 | CH3 | O | CH3 | CH3 |
1.221 | CH3 | H | p-CH3-C6H4-SO2- | 0 | H | H | H | H | O | H | CH3 |
1.222 | CH3 | H | p-CH3-C6H4-SO2- | 2 | H | H | H | H | O | H | CH3 |
序号 | R5 | R6 | R7 | n | R1 | R2 | R3 | R4 | X | L | M |
1.223 | CH3 | H | p-CH3-C6H4-SO2- | 0 | H | H | H | H | S | H | CH3 |
1.224 | CH3 | H | p-CH3-C6H4-SO2- | 2 | H | H | H | H | S | H | CH3 |
1.225 | CH3 | H | p-CH3-C6H4-SO2- | 0 | H | H | H | H | SO2 | H | CH3 |
1.226 | CH3 | H | p-CH3-C6H4-SO2- | 2 | H | H | H | H | SO2 | H | CH3 |
1.227 | CH3 | H | p-CH3-C6H4-SO2- | 0 | CH3 | H | H | H | O | H | CH3 |
1.228 | CH3 | H | p-CH3-C6H4-SO2- | 2 | CH3 | H | H | H | O | H | CH3 |
1.229 | CH3 | H | p-CH3-C6H4-SO2- | 0 | CH3 | H | H | H | S | H | CH3 |
1.230 | CH3 | H | p-CH3-C6H4-SO2- | 2 | CH3 | H | H | H | S | H | CH3 |
1.231 | CH3 | H | p-CH3-C6H4-SO2- | 0 | CH3 | H | H | H | SO2 | H | CH3 |
1.232 | CH3 | H | p-CH3-C6H4-SO2- | 2 | CH3 | H | H | H | SO2 | H | CH3 |
1.233 | CH3 | H | p-CH3-C6H4-SO2- | 0 | CH3 | H | CH3 | H | O | H | CH3 |
序号 | R5 | R6 | R7 | n | R1 | R2 | R3 | R4 | X | L | M |
1.234 | CH3 | H | p-CH3-C6H4-SO2- | 2 | CH3 | H | CH3 | H | O | H | CH3 |
1.235 | CH3 | H | p-CH3-C6H4-SO2- | 0 | CH3 | H | CH3 | H | S | H | CH3 |
1.236 | CH3 | H | p-CH3-C6H4-SO2- | 2 | CH3 | H | CH3 | H | S | H | CH3 |
1.237 | CH3 | H | p-CH3-C6H4-SO2- | 0 | CH3 | H | CH3 | H | SO2 | H | CH3 |
1.238 | CH3 | H | p-CH3-C6H4-SO2- | 2 | CH3 | H | CH3 | H | SO2 | H | CH3 |
1.239 | CH3 | H | p-CH3-C6H4-SO2- | 0 | CH3 | CH3 | H | H | O | H | CH3 |
1.240 | CH3 | H | p-CH3-C6H4-SO2- | 2 | CH3 | CH3 | H | H | O | H | CH3 |
1.241 | CH3 | H | p-CH3-C6H4-SO2- | 0 | H | H | CH3 | CH3 | O | H | CH3 |
1.242 | CH3 | H | p-CH3-C6H4-SO2- | 2 | H | H | CH3 | CH3 | O | H | CH3 |
1.243 | C2H5 | H | p-CH3-C6H4-SO2- | 0 | H | H | H | H | O | H | CH3 |
1.244 | C2H5 | H | p-CH3-C6H4-SO2- | 2 | H | H | H | H | O | H | CH3 |
序号 | R5 | R6 | R7 | n | R1 | R2 | R3 | R4 | X | L | M |
1.245 | C2H5 | H | p-CH3-C6H4-SO2- | 0 | H | H | H | H | S | H | CH3 |
1.246 | C2H5 | H | p-CH3-C6H4-SO2- | 2 | H | H | H | H | S | H | CH3 |
1.247 | C2H5 | H | p-CH3-C6H4-SO2- | 0 | H | H | H | H | SO2 | H | CH3 |
1.248 | C2H5 | H | p-CH3-C6H4-SO2- | 2 | H | H | H | H | SO2 | H | CH3 |
1.249 | C2H5 | H | p-CH3-C6H4-SO2- | 0 | CH3 | H | H | H | O | H | CH3 |
1.250 | C2H5 | H | p-CH3-C6H4-SO2- | 2 | CH3 | H | H | H | O | H | CH3 |
1.251 | C2H5 | H | p-CH3-C6H4-SO2- | 0 | CH3 | H | H | H | S | H | CH3 |
1.252 | C2H5 | H | p-CH3-C6H4-SO2- | 2 | CH3 | H | H | H | S | H | CH3 |
1.253 | C2H5 | H | p-CH3-C6H4-SO2- | 0 | CH3 | H | H | H | SO2 | H | CH3 |
1.254 | C2H5 | H | p-CH3-C6H4-SO2- | 2 | CH3 | H | H | H | SO2 | H | CH3 |
1.255 | C2H5 | H | p-CH3-C6H4-SO2- | 0 | CH3 | H | CH3 | H | O | H | CH3 |
序号 | R5 | R6 | R7 | n | R1 | R2 | R3 | R4 | X | L | M |
1.256 | C2H5 | H | p-CH3-C6H4-SO2- | 2 | CH3 | H | CH3 | H | O | H | CH3 |
1.257 | C2H5 | H | p-CH3-C6H4-SO2- | 0 | CH3 | H | CH3 | H | S | H | CH3 |
1.258 | C2H5 | H | p-CH3-C6H4-SO2- | 2 | CH3 | H | CH3 | H | S | H | CH3 |
1.259 | C2H5 | H | p-CH3-C6H4-SO2- | 0 | CH3 | H | CH3 | H | SO2 | H | CH3 |
1.260 | C2H5 | H | p-CH3-C6H4-SO2- | 2 | CH3 | H | CH3 | H | SO2 | H | CH3 |
1.261 | C2H5 | H | p-CH3-C6H4-SO2- | 0 | CH3 | CH3 | H | H | O | H | CH3 |
1.262 | C2H5 | H | p-CH3-C6H4-SO2- | 2 | CH3 | CH3 | H | H | O | H | CH3 |
1.263 | C2H5 | H | p-CH3-C6H4-SO2- | 0 | H | H | CH3 | CH3 | O | H | CH3 |
1.264 | C2H5 | H | p-CH3-C6H4-SO2- | 2 | H | H | CH3 | CH3 | O | H | CH3 |
1.265 | CH3 | CH3 | H | 0 | H | H | H | H | O | H | CH3 |
1.266 | CH3 | CH3 | H | 2 | H | H | H | H | O | H | CH3 |
1.267 | CH3 | CH3 | H | 0 | H | H | H | H | S | H | CH3 |
1.268 | CH3 | CH3 | H | 2 | H | H | H | H | S | H | CH3 |
1.269 | CH3 | CH3 | H | 0 | H | H | H | H | SO2 | H | CH3 |
1.270 | CH3 | CH3 | H | 2 | H | H | H | H | SO2 | H | CH3 |
1.271 | CH3 | CH3 | H | 0 | CH3 | H | H | H | O | H | CH3 |
序号 | R5 | R6 | R7 | n | R1 | R2 | R3 | R4 | X | L | M |
1.272 | CH3 | CH3 | H | 2 | CH3 | H | H | H | O | H | CH3 |
1.273 | CH3 | CH3 | H | 0 | CH3 | H | H | H | S | H | CH3 |
1.274 | CH3 | CH3 | H | 2 | CH3 | H | H | H | S | H | CH3 |
1.275 | CH3 | CH3 | H | 0 | CH3 | H | H | H | SO2 | H | CH3 |
1.276 | CH3 | CH3 | H | 2 | CH3 | H | H | H | SO2 | H | CH3 |
1.277 | CH3 | CH3 | H | 0 | CH3 | H | CH3 | H | O | H | CH3 |
1.278 | CH3 | CH3 | H | 2 | CH3 | H | CH3 | H | O | H | CH3 |
1.279 | CH3 | CH3 | H | 0 | CH3 | H | CH3 | H | S | H | CH3 |
1.280 | CH3 | CH3 | H | 2 | CH3 | H | CH3 | H | S | H | CH3 |
1.281 | CH3 | CH3 | H | 0 | CH3 | H | CH3 | H | SO2 | H | CH3 |
1.282 | CH3 | CH3 | H | 2 | CH3 | H | CH3 | H | SO2 | H | CH3 |
1.283 | CH3 | CH3 | H | 0 | CH3 | CH3 | H | H | O | H | CH3 |
1.284 | CH3 | CH3 | H | 2 | CH3 | CH3 | H | H | O | H | CH3 |
1.285 | CH3 | CH3 | H | 0 | H | H | CH3 | CH3 | O | H | CH3 |
1.286 | CH3 | CH3 | H | 2 | H | H | CH3 | CH3 | O | H | CH3 |
表2:下述结构式化合物
序号 | R5 | R6 | R7 | n | X | L | M |
2.1 | CH3 | CH3 | H | 0 | O | H | H |
2.2 | CH3 | CH3 | H | 2 | O | H | H |
2.3 | CH3 | CH3 | H | 0 | S | H | H |
2.4 | CH3 | CH3 | H | 2 | S | H | H |
2.5 | CH3 | CH3 | H | 0 | SO2 | H | H |
2.6 | CH3 | CH3 | H | 2 | SO2 | H | H |
2.7 | C2H5 | H | H | 0 | O | H | H |
2.8 | C2H5 | H | H | 2 | O | H | H |
2.9 | C2H5 | H | H | 0 | S | H | H |
2.10 | C2H5 | H | H | 2 | S | H | H |
2.11 | C2H5 | H | H | 0 | SO2 | H | H |
2.12 | C2H5 | H | H | 2 | SO2 | H | H |
2.13 | CH3 | H | H | 0 | O | H | CH3 |
2.14 | CH3 | H | H | 2 | O | H | CH3 |
2.15 | CH3 | H | H | 0 | S | H | CH3 |
2.16 | CH3 | H | H | 2 | S | H | CH3 |
2.17 | CH3 | H | H | 0 | SO2 | H | CH3 |
2.18 | CH3 | H | H | 2 | SO2 | H | CH3 |
2.19 | CH3 | CH3 | H | 0 | O | H | CH3 |
2.20 | CH3 | CH3 | H | 2 | O | H | CH3 |
2.21 | CH3 | CH3 | H | 0 | S | H | CH3 |
2.22 | CH3 | CH3 | H | 2 | S | H | CH3 |
2.23 | CH3 | CH3 | H | 0 | SO2 | H | CH3 |
2.24 | CH3 | CH3 | H | 2 | SO2 | H | CH3 |
2.25 | C2H5 | H | H | 0 | O | H | CH3 |
2.26 | C2H5 | H | H | 2 | O | H | CH3 |
2.27 | C2H5 | H | H | 0 | S | H | CH3 |
2.28 | C2H5 | H | H | 2 | S | H | CH3 |
2.29 | C2H5 | H | H | 0 | SO2 | H | CH3 |
2.30 | C2H5 | H | H | 2 | SO2 | H | CH3 |
2.31 | CH3 | H | H | 0 | O | H | Cl |
2.32 | CH3 | H | H | 2 | O | H | Cl |
2.33 | CH3 | H | H | 0 | S | H | Cl |
2.34 | CH3 | H | H | 2 | S | H | Cl |
2.35 | CH3 | H | H | 0 | SO2 | H | Cl |
2.36 | CH3 | H | H | 2 | SO2 | H | Cl |
2.37 | CH3 | CH3 | H | 0 | O | H | Cl |
2.38 | CH3 | CH3 | H | 2 | O | H | Cl |
2.39 | CH3 | CH3 | H | 0 | S | H | Cl |
2.40 | CH3 | CH3 | H | 2 | S | H | Cl |
2.41 | CH3 | CH3 | H | 0 | SO2 | H | Cl |
2.42 | CH3 | CH3 | H | 2 | SO2 | H | Cl |
2.43 | C2H5 | H | H | 0 | O | H | Cl |
2.44 | C2H5 | H | H | 2 | O | H | Cl |
2.45 | C2H5 | H | H | 0 | S | H | Cl |
2.46 | C2H5 | H | H | 2 | S | H | Cl |
2.47 | C2H5 | H | H | 0 | SO2 | H | Cl |
2.48 | C2H5 | H | H | 2 | SO2 | H | Cl |
2.49 | CH3 | H | H | 0 | O | CH3 | CH3 |
2.50 | CH3 | H | H | 2 | O | CH3 | CH3 |
2.51 | CH3 | H | H | 0 | S | CH3 | CH3 |
2.52 | CH3 | H | H | 2 | S | CH3 | CH3 |
2.53 | CH3 | H | H | 0 | SO2 | CH3 | CH3 |
2.54 | CH3 | H | H | 2 | SO2 | CH3 | CH3 |
2.55 | CH3 | CH3 | H | 0 | O | CH3 | CH3 |
2.56 | CH3 | CH3 | H | 2 | O | CH3 | CH3 |
2.57 | CH3 | CH3 | H | 0 | S | CH3 | CH3 |
2.58 | CH3 | CH3 | H | 2 | S | CH3 | CH3 |
2.59 | CH3 | CH3 | H | 0 | SO2 | CH3 | CH3 |
2.60 | CH3 | CH3 | H | 2 | SO2 | CH3 | CH3 |
2.61 | C2H5 | H | H | 0 | O | CH3 | CH3 |
2.62 | C2H5 | H | H | 2 | O | CH3 | CH3 |
2.63 | C2H5 | H | H | 0 | S | CH3 | CH3 |
2.64 | C2H5 | H | H | 2 | S | CH3 | CH3 |
2.65 | C2H5 | H | H | 0 | SO2 | CH3 | CH3 |
2.66 | C2H5 | H | H | 2 | SO2 | CH3 | CH3 |
2.67 | CH3 | H | p-CH3-C6H4-SO2- | 0 | O | H | CH3 |
2.68 | CH3 | H | p-CH3-C6H4-SO2- | 2 | O | H | CH3 |
2.69 | CH3 | H | p-CH3-C6H4-SO2- | 0 | S | H | CH3 |
2.70 | CH3 | H | p-CH3-C6H4-SO2- | 2 | S | H | CH3 |
2.71 | CH3 | H | p-CH3-C6H4-SO2- | 0 | SO2 | H | CH3 |
2.72 | CH3 | H | p-CH3-C6H4-SO2- | 2 | SO2 | H | CH3 |
2.73 | CH3 | H | p-CH3-C6H4-SO2- | 0 | O | H | CH3 |
2.74 | C2H5 | H | p-CH3-C6H4-SO2- | 0 | O | H | CH3 |
2.75 | C2H5 | H | p-CH3-C6H4-SO2- | 2 | O | H | CH3 |
2.76 | C2H5 | H | p-CH3-C6H4-SO2- | 0 | S | H | CH3 |
2.77 | C2H5 | H | p-CH3-C6H4-SO2- | 2 | S | H | CH3 |
2.78 | C2H5 | H | p-CH3-C6H4-SO2- | 0 | SO2 | H | CH3 |
2.79 | C2H5 | H | p-CH3-C6H4-SO2- | 2 | SO2 | H | CH3 |
制备实施例
A)起始原料和中间体的制备
1.3-(2-溴乙氧基)-2-甲基苯甲酸乙酯
将13.6克(0.2摩尔)甲醇钠溶解于200毫升乙醇中。之后加入36克(0.2摩尔)3-羟基-2-甲基苯甲酸乙酯,将此混合物回流2小时。随后滴加入61.4克(0.32摩尔)1,2-二溴乙烷,将此混合物回流20小时。当冷却时,反应混合物在旋转蒸发器中浓缩。残留物用乙酸乙酯收集,用稀氢氧化钠溶液洗涤3次。将有机相干燥,蒸发掉溶剂。有价值的产物通过柱色谱纯化。收率:14.6克油状物。NMR(270MHZ;CDCl3;δppm):7.4(d,1H),7.2(tr,1H),6.9(d,1H),4.4(tr,2H),4.3(q,2H),3.7(tr,2H),2.4(s,3H),1.5(tr,3H)
2.3-(2-甲基磺酰基硫基乙氧基)-2-甲基苯甲酸乙酯
将2克(7毫摩尔)3-(2-溴乙氧基)-2-甲基苯甲酸乙酯和1.1克(7.3毫摩尔)硫代甲基磺酸钾溶解于10毫升无水乙醇中。反应混合物回流20小时。之后蒸发掉溶剂,残留物用二氯甲烷收集,用水洗涤。有机相经硫酸钠干燥,去除溶剂。有价值的产物用柱色谱纯化。
收率:1.1克(50%)NMR(270MHZ;CDCl3;δppm):7.4(d,1H),7.2(tr,1H),7.0(d,1H),4.5(tr,2H),4.3(q,2H),3.6(tr,2H),3.4(s,3H),2.4(s,3H),1.4(tr,3H)
3.8-甲基-2,3-二氢苯并-1,4-氧硫杂环己二烯-7-羧酸乙酯
将1.0克(3.4毫摩尔)3-(2-甲基磺酰基硫基乙氧基)-2-甲基苯甲酸乙酯溶解于5毫升硝基甲烷中。加入0.42克(3.14毫摩尔)三氯化铝。此混合物在室温下搅拌45分钟。通过加入10毫升2N盐酸进行后处理,随后用MTB醚萃取。合并的有机相用水和碳酸钠溶液洗涤,并经硫酸钠干燥,蒸馏掉溶剂。
收率:0.7克(93%)NMR(270MHZ;CDCl3;δppm):7.5(d,1H),6.9(d,1H),4.5(tr,2H),4.3(q,2H),3.2(tr,2H),2.4(s,3H),1.4(tr,3H)
4.8-甲基-2,3-二氢苯并-1,4-氧硫杂环己二烯-7-羧酸
将4.0克(0.0168摩尔)8-甲基-2,3-二氢苯并-1,4-氧硫杂环己二烯-7-羧酸乙酯与1.0克(0.0252摩尔)氢氧化钠于40克甲醇/水中回流。此混合物在此温度下搅拌2小时,随后蒸发掉溶剂。残留物用水收集。混合物用***萃取,水相用2N盐酸酸化。沉淀出有价值的产物,将之抽吸滤出,并用少量的水洗涤。在40℃的真空干燥箱中干燥产物。
收率:2.9克(82%)NMR(270MHZ;d6 DMSO;δppm):12.3(bs,1H),7.3(d,1H),6.9(d,1H),4.4(tr,2H),3.2(tr,2H),2.4(s,3H)
5.8-甲基-2,3-二氢-4,4-二氧代苯并-1,4-氧硫杂环己二烯-7-羧酸
将2.8克(0.013摩尔)8-甲基-2,3-二氢苯并-1,4-氧硫杂环己二烯-7-羧酸与一尖刮勺钨酸钠一起加入30毫升乙酸中。将此混合物加热至50℃。滴加入3.3克(0.029摩尔)过氧化氢(浓度30%)。此反应溶液再在50-60℃保持4小时。溶液倒入冰水中。抽吸滤出沉淀物,用水洗涤,在40℃真空干燥箱中干燥。
收率:2.7克
熔点:234℃。
表3
序号 | T | R1 | R2 | R3 | R4 | X | M | L | n | 物理数据 |
3.1 | OC2H5 | H | H | H | H | O | CH3 | H | 0 | 1H-NMR(270MHz;CDCl3;以ppm计)7.5(d,1H),6.9(d,1H),4.5(tr,2H),4.3(q,2H),3.2(tr,2H),2.4(s,3H),1.4(tr,3H) |
3.2 | HO | H | H | H | H | O | CH3 | H | 0 | 1H-NMR(270MHz;d6-DMSO;以ppm计)12.3(bs,1H),7.3(d,1H),6.9(d,1H),4.4(tr,2H),3.2(tr,2H),2.4(s,3H) |
3.3 | HO | H | H | H | H | O | CH3 | H | 2 | m.p.[℃]:234 |
表3(续)
序号 | T | R1 | R2 | R3 | R4 | X | M | L | n | 物理数据 |
3.43.5 | OCH3OH | HH | HH | HH | HH | SS | CH3CH3 | HH | 00 | m.p.[℃]:57m.p.[℃]:179 |
3.6 | OH | H | H | H | H | SO2 | CH3 | H | 2 | 1H-NMR(250MHz,d6-DMSO):13.8(bs),8.11(d),7.98(d),4.40(m),2.80(s) |
3.7 | OC2H5 | H | H | H | H | O | Cl | H | 0 | 1H-NMR(CDCl3):7.3(2×d),4.4(q),4.5(tr),3.2(tr),1.4(tr) |
3.8 | OH | H | H | H | H | O | Cl | H | 0 | m.p.[℃]:209℃ |
3.9 | OH | H | H | H | H | O | Cl | H | 2 | m.p.[℃]:225 |
表4
序号 | T | R1 | R4 | X | M | L | n | 物理数据 |
4.1 | OC2H5 | H | H | O | CH3 | H | 0 | 1H-NMR(270MHz,CDCl3):7.44(d),6.85(d),6.50(d),5.25(d),4.32(q),2.36(s),1.36(tr) |
4.2 | OH | H | H | O | CH3 | H | 0 | m.p.[℃]:174 |
4.3 | OH | H | H | O | CH3 | H | 2 | m.p.[℃]:205 |
4.4 | OC2H5 | H | H | O | Cl | H | 0 | m.p.[℃]:92 |
4.5 | OH | H | H | O | Cl | H | 0 | m.p.[℃]:201 |
终产物的制备
4-(8-甲基-2,3-二氢-4,4-二氧代苯并[1,4]氧硫杂环己二烯-7-基-羰基)-1-乙基-5-羟基吡唑
将0.9克(3.72毫摩尔)的8-甲基-2,3-二氢-4,4-二氧代苯并-1,4-氧硫杂环己二烯-7-羧酸与0.42克(3.72毫摩尔)1-乙基吡唑酮一起加入20毫升乙腈中。之后加入0.81克(3.9毫摩尔)DCC,将混合物在室温下搅拌几小时。随后加入0.75克(7.44毫摩尔)三乙胺和0.2毫升三甲基甲硅烷基氰化物,混合物在室温下搅拌3小时。
后处理通过加入100毫升2%碳酸钠溶液,并通过抽吸过滤来去除沉淀物来进行。滤液用乙酸乙酯洗涤,用2N HCl调节至pH4,并萃取有价值的产物。
将有机相干燥,在旋转蒸发器中浓缩。
产物通过重结晶来纯化。
收率:0.3克固体。
熔点:184℃。
表5
序号 | R1 | R2 | R3 | R4 | R5 | R6 | R7 | X | M | L | n | 物理数据 |
5.1 | H | H | H | H | C2H5 | H | H | O | CH3 | H | 2 | m.p.[℃]:184 |
5.2 | H | H | H | H | CH3 | H | H | O | CH3 | H | 0 | m.p.[℃]:112 |
5.3 | H | H | H | H | C2H5 | H | H | SO2 | CH3 | H | 2 | 1H-NMR(270 MHz,d6-DMSO):7.97(d),7.80(d),7.45(s),4.41(s),3.90(q),2.59(s),1.26(tr) |
5.4 | H | H | H | H | CH3 | H | H | S | CH3 | H | 0 | m.p.[℃]:114 |
5.5 | H | H | H | H | C2H5 | H | H | S | CH3 | H | 0 | m.p.[℃]:81 |
5.6 | H | H | H | H | C2H5 | H | H | O | Cl | H | 0 | m.p.[℃]:114 |
表6
序号 | R5 | R6 | R7 | R1 | R4 | X | M | L | n | 物理数据 |
6.1 | nPropyl | H | H | H | H | O | CH3 | H | 0 | 1H-NMR(270MHz,CDCl3):8.96(bs),7.43(s),7.09(d),6.81(d),6.50(d),5.26(d),3.98(tr),2.22(s),1.89(m),0.95(tr) |
6.2 | CH3 | H | H | H | H | O | CH3 | H | 0 | m.p.[℃]:56℃ |
化合物Ⅰ及其农业上有用的盐适合作为除草剂,它们可以是异构体混合物的形式和纯异构体二种形式。包含式Ⅰ的除草组合物在控制非耕作区的植物方面非常有效,特别是在高施用量的情况下。它们可以在作物如小麦、稻、玉米、大豆和棉花中防治阔叶杂草和禾本科杂草,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。
根据施用方法的不同,化合物Ⅰ或含有之的组合物也可以用于许多其它作物,用于消灭莠草。适合的作物是例如下列:
洋葱、凤梨、花生、芦笋、甜菜(Beta vulgaris spp.altissima)、芜菁甜菜(Beta vulgaris spp.rapa)、Brassica napus var.napus、Brassica napusvar.napobrassica、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、巴西橡胶、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。
此外,化合物Ⅰ也可以应用在通过育种(包括基因工程的方法)而对除草剂的作用具有耐性的作物上。
本发明除草剂或活性成分可以在苗前或苗后施用。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器喷雾,使敏感作物的叶片尽可能不受影响,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和含有之的制剂例如可以以可直接喷雾水溶液、粉末、悬浮液、高浓度的水、油或其他悬浮液或分散液、乳液、油分散液、膏剂、粉、撒施材料或颗粒的形式通过喷雾、弥雾、喷粉、撒施或浇注使用。使用形式取决于应用目的;在任何情况下应该保证本发明的活性成分尽可能细的分散。
适合的惰性添加剂主要是:中等至高沸点的石油馏分如煤油和柴油,还有煤焦油以及动植物油类,脂族、环状和芳族烃例如石蜡、四氢化萘、烷基化的萘和其衍生物,烷基化的苯和其衍生物,醇类如甲醇、乙醇、丙醇、丁醇和环己醇,酮类如环己酮,强极性溶剂类例如胺如N-甲基吡咯烷酮或水。
含水的使用形式可以由乳油、悬浮液、膏剂、可湿性粉剂或以水可分散颗粒剂通过添加水而制备的。为了制备乳液、膏剂或油分散液,该基质本身或溶解在油或溶剂的基质,可以借助于润湿剂、粘附剂、分散剂或乳化剂在水中均化。此外,同样可以由活性成分、润湿剂、粘附剂、分散剂或乳化剂和如果需要的话溶剂或油制备适合于用水稀释的浓缩物。
适合的表面活性成分(辅助剂)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的碱金属、碱土金属盐和铵盐,和脂肪酸、烷基磺酸和烷基芳基磺酸、烷基硫酸、月桂基醚硫酸和脂肪醇硫酸的碱金属、碱土金属盐和铵盐,以及硫酸化的十六-、十七-和十八醇或脂肪醇醚的盐,磺化萘和其与甲醛的衍生物的缩合产物,萘或萘磺酸与苯酚和甲醛的缩合产物,聚氧乙烯辛基酚醚、乙氧基烷化的异辛基-、辛基-或壬基苯酚、烷基苯基聚二醇醚,或三丁基苯基聚乙二醇醚,烷基芳基聚醚醇、异三癸基醇、脂肪醇/环氧乙烷缩合物,乙氧基化蓖麻油,聚氧乙烯烷基醚或聚氧丙烯烷基醚,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。
粉末剂、撒施材料和粉剂可以通过活性成分与固态载体的混合或混磨来制备。
颗粒剂例如包衣、浸渍和匀质颗粒可以通过将活性成分粘合在固态载体上来制备。固态载体是矿质土类如二氧化硅、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、硫酸镁、氧化镁、磨细的塑料、肥料,如硫酸铵、磷酸铵、硝酸铵、尿素和植物源产品如谷类作物粉、树皮粉、木材粉和坚果核粉,纤维素粉末或其他固态载体。
活性成分Ⅰ在即可使用的制剂中的浓度可以在宽的范围内变化。一般所使用的制剂包含约0.001至98重量%、优选0.01至95重量%的活性成分。所采用的活性成分的纯度是90至100%,优选95至100%(根据NMR-光谱)。
下面配制剂的实施例说明这种制剂的制备:
Ⅰ、将20份重量的序号为5.1的化合物溶解在一种混合物中,该混合物由80份重量的烷基化苯、10份重量的8~10摩尔环氧乙烷与1摩尔油酸-N-单乙醇酰胺的加成产物、5份重量的十二烷基苯磺酸的钙盐和5份重量的40摩尔环氧乙烯与1摩尔蓖麻油的加成产物组成。通过将溶液倒入100000份重量的水中并细分散得到一种水分散液,其包含0.02重量%的活性成分。
Ⅱ、将20份重量的序号为5.1的化合物溶解在一种混合物中,该混合物由40份重量的环己酮、30份重量的异丁醇、20份重量40摩尔异辛基苯酚的加成产物和10份重量的40摩尔环氧乙烷与1摩尔蓖麻油的加成产物组成。通过将溶液倒入100000份重量的水中并细分散得到一种水分散液,其包含0.02重量%的活性成分。
Ⅲ、将20份重量的序号为5.1的化合物溶解在一种混合物中,该混合物由25份重量的环己酮、65份重量的沸点为210~280℃的石油馏分和10份重量的40摩尔环氧乙烷与1摩尔蓖麻油的加成产物组成。通过将该溶液倒入100000份重量的水中并细分散得到一种水分散液,其包含0.02重量%的活性成分。
Ⅳ、将20份重量的序号为5.1的化合物与3份重量的二异丁基萘-α-磺酸的钠盐、17份重量来自亚硫酸盐废液的木素磺酸的钠盐和60份重量的粉状硅胶均匀地混合,并在锤磨机中粉磨。通过该混合物在20000份重量水中的均匀分散得到一种喷洒混合物,其包含0.1重量%的活性成分。
Ⅴ、将3份重量的序号为5.1的化合物与97份重量的细高岭土混合。按照这种方式得到一种撒粉剂,其包含3重量%的活性成分。
Ⅵ、将20份重量的序号为5.1的化合物与2份重量的十二烷基苯磺酸钙、8份重量的脂肪醇-聚乙二醇醚、2份重量的苯酚/尿素/甲醛缩合物的钠盐和68份重量的石蜡质的矿物油均匀地混合。由此得到一种稳定的油分散液。
Ⅶ、将1份重量的序号为5.1的化合物溶解在一种混合物中,该混合物由70份重量的环己酮、20份重量的乙氧基化的异辛基苯酚和10份重量的乙氧基化的蓖麻油组成。由此得到一种稳定的乳油。
Ⅷ、将1份重量的序号为5.1的化合物溶解在一种混合物中,该混合物由80份重量的环己酮和20份重量的Emulphor-EL(乙氧基化蓖麻油)组成。由此得到一种稳定的乳油。
为了扩展作用谱和得到增效的效果,吡唑-4-杂芳基衍生物Ⅰ可以与众多的具有代表性的其他除草剂或生长调节剂活性成分混合和一起使用。例如可以作为混合组分的是1,2,4-噻二唑类、1,3,4-噻二唑类、酰胺类、氨基磷酸类和其衍生物、氨基***类、N-酰苯胺类、(杂)芳基氧基链烷酸类和其衍生物、苯甲酸和其衍生物、苯并噻二嗪酮类、2-芳酰基-1,3-环己二酮类、杂芳基-芳基-酮类、苄基异噁唑烷酮类、间-CF3-苯基衍生物、氨基甲酸酯类、喹啉羧酸和其衍生物、氯乙酰苯胺类、环己-1,3-二酮衍生物、二嗪类、二氯丙酸和其衍生物、二氢苯并呋喃类、二氢呋喃-3-酮类、二硝基苯胺类、二硝基苯酚类、二苯基醚类、联吡啶类、卤代羧酸和其衍生物、脲类、3-苯基尿嘧啶类、咪唑类、咪唑啉酮类、N-苯基-3,4,5,6-四氢邻苯二甲酰亚胺类、噁二唑类、环氧乙烷类、苯酚类、芳氧基-或杂芳氧基苯氧基丙酸酯类、苯基乙酸和其衍生物、苯基丙酸和其衍生物、吡唑类、苯基吡唑类、哒嗪类、吡啶羧酸和其衍生物、嘧啶基醚类、磺酰胺类、磺酰脲类、三嗪类、三嗪酮类、***啉酮类、***甲酰胺类和尿嘧啶类。
此外,有利的是化合物Ⅰ单独或与其他的除草剂一起与其他的作物保护剂混合使用,例如与杀虫剂或防治植物病原真菌或细菌的药剂一起使用。此外,感兴趣的是与无机盐溶液的可混合性,采用这种方法来消除营养和微量元素的缺乏。同样可以加入无植物毒性的油和油浓缩物。
取决于意欲的目的、季节、靶体植物和生长期,活性成分的施用量是每公顷0.001至3.0,优选0.01至1.0公斤活性物质。
应用实施例
式Ⅰ的吡唑-4-基杂芳酰基衍生物的除草作用可以通过下述温室试验说明:
所用的栽培容器是塑料花盆,盆中装有腐殖质含量约为3.0%的壤砂土作为基质。根据不同的种类,分别播种不同试验植物的种子。
在苗前处理的情况下,在播种后,将悬浮或乳化于水中的活性成分用分布性能良好的喷嘴直接施用。花盆稍微浇些水,以促使萌发和生长,然后,覆盖上透明塑料地膜,直到植物生根。如果不是受活性化合物影响的话,覆盖应会使试验植物均匀的萌发。
进行苗后处理时,先让试验植物长出,根据不同的植物习性,让其长到3至15cm高,此时方用悬浮或乳化于水中的活性成分处理。对于这种目的,试验植物或是直接播种并在同一花盆中生长,或是先以秧苗分别生长,再在处理前几天,将它们移栽到试验花盆中。苗前处理的施用量是0.0625至0.0313kg/ha a.s.(活性成分)。
根据种类的不同,将植物放置在10-25℃或20-35℃下。试验期历经2至4周。在此期间,悉心照料植物,并评价它们对各处理的反应。
以0至100的等级进行评分。在此情况下,100是指没有植物出苗或至少完全毁灭地上部分,而0是指无伤害或生长正常。
在温室中使用的植物是由下列品种组成的:
学名 俗名
Chenopodium album(CHEAL) 红心藜
Echinochloa crus-galli(ECHCG) 稗
Solanum nigrum(SOLNI) 龙葵
Triticum aestivum(TRZAW) 冬小麦
Zea mays(ZEAMX) 玉米
Claims (9)
其中取代基具有下列含意:
L和M是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基,这些基团是未取代或由一至五个卤原子或C1-C4-烷氧基取代;卤素、氰基、硝基;
X是可以由一或二个氧原子取代的硫;
n是0、1、2;
R1是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基,这些基团可以是未取代的或由一至五个卤原子或C1-C4-烷氧基取代;卤素;
可以由下列基团单或多取代的苯基:C1-C4-烷基、氢、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、硝基、氰基、C1-C4-烷氧基羰基;
R2是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基,这些基团可以是未取代的或由一至五个卤原子或C1-C4-烷氧基取代;卤素;
可以由下列基团单或多取代的苯基:C1-C4-烷基、氢、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、硝基、氰基、C1-C4-烷氧基羰基;R2和R3可以形成一个键;
R3是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基,这些基团可以是未取代的或由一至五个卤原子或C1-C4-烷氧基取代;取代的苯基;卤素;R3和R2可以形成一个键;
可以由下列基团单或多取代的苯基:C1-C4-烷基、氢、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、硝基、氰基、C1-C4-烷氧基羰基;R3和R2可以形成一个键;
R4是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基,这些基团可以是未取代的或由一至五个卤原子或C1-C4-烷氧基取代;卤素;
可以由下列基团单或多取代的苯基:C1-C4-烷基、氢、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、硝基、氰基、C1-C4-烷氧基羰基;
Q是式Ⅱ的吡唑环,连接在4-位,
其中
R5是C1-C4-烷基,
R6是氢、C1-C4-烷基或C1-C4-卤代烷基,且
R7是氢、C1-C4-烷基磺酰基、苯基磺酰基或烷基苯基磺酰基。
2.根据权利要求1的吡唑-4-基杂芳酰基衍生物,它由下式Ⅰa表示
其中L是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、氰基或硝基,
和M是氢、C1-C6-烷基、C2-C6-链烯基、C2-C6-炔基、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、卤素、氰基或硝基,和
Q、X、R1至R4和n具有权利要求1中给出的含意。
4.根据权利要求1的式Ⅰ的吡唑-4-基杂芳酰基衍生物,其中基团L和M是氢、甲基、甲氧基、氯、氰基、硝基或三氟甲基。
8.一种除草剂组合物,包含至少一种权利要求1中所述的式Ⅰ的吡唑-4-基杂芳酰基衍生物和常规惰性添加剂。
9.一种防治莠草的方法,其中包含使除草有效量的权利要求1中所述的式Ⅰ的吡唑-4-基杂芳酰基衍生物作用于植物上或其栖生地。
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DE19607041.4 | 1996-02-24 | ||
DE19607041A DE19607041A1 (de) | 1996-02-24 | 1996-02-24 | Pyrazol-4-yl-hetaroylderivate |
DE1996112685 DE19612685A1 (de) | 1996-03-29 | 1996-03-29 | Pyrazol-4-yl-hetaroylderivate |
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EP (1) | EP0888343B1 (zh) |
JP (1) | JP2000506124A (zh) |
KR (1) | KR19990087188A (zh) |
CN (2) | CN1075497C (zh) |
AR (1) | AR005955A1 (zh) |
AT (1) | ATE218564T1 (zh) |
AU (1) | AU729651B2 (zh) |
BR (1) | BR9707635A (zh) |
CA (1) | CA2247203A1 (zh) |
CZ (1) | CZ230398A3 (zh) |
DE (1) | DE59707423D1 (zh) |
EA (1) | EA001515B1 (zh) |
EE (1) | EE03615B1 (zh) |
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PL (1) | PL328506A1 (zh) |
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US5962725A (en) | 1996-09-05 | 1999-10-05 | Agouron Pharmaceuticals, Inc. | Intermediate compounds useful for making HIV protease inhibitors such as nelfinavir |
US5925759A (en) * | 1996-09-05 | 1999-07-20 | Agouron Pharmaceuticals, Inc. | Methods of making HIV-protease inhibitors and intermediates for making HIV-protease inhibitors |
UA67727C2 (uk) * | 1996-09-05 | 2004-07-15 | Агурон Фармасевтікелс, Інк. | Проміжні сполуки для одержання інгібіторів віл-протеази і способи одержання інгібіторів віл-протеази |
US6084107A (en) * | 1997-09-05 | 2000-07-04 | Agouron Pharmaceuticals, Inc. | Intermediates for making HIV-protease inhibitors |
EP1080089B1 (de) * | 1998-05-18 | 2003-11-05 | Basf Aktiengesellschaft | Pyrazolyldioxothiochromanoyl-derivate |
JP2002531560A (ja) * | 1998-12-04 | 2002-09-24 | ビーエーエスエフ アクチェンゲゼルシャフト | ピラゾリルベンゾイル誘導体の製造方法および新規なピラゾリルベンゾイル誘導体 |
AU1861600A (en) * | 1998-12-04 | 2000-06-26 | Basf Aktiengesellschaft | Thiochromanoylpyrazolone derivatives |
AR031786A1 (es) * | 2000-12-11 | 2003-10-01 | Basf Ag | 5-((pirazol-4-il)carbonil)benzazolonas |
PL2686315T3 (pl) | 2011-03-15 | 2015-05-29 | Bayer Ip Gmbh | Amidy kwasu N-(1,2,5-oksadiazol-3-ilo)-, N-(tetrazol-5-ilo)- i N-(triazol-5-ilo)bicykloarylo-karboksylowego oraz ich zastosowanie jako środków chwastobójczych |
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US4643757A (en) * | 1985-05-20 | 1987-02-17 | Nissan Chemical Industries, Ltd. | Herbicidal 4-benzoyl-1-methyl-5-hydroxypyrazoles |
JPH0730031B2 (ja) * | 1986-04-02 | 1995-04-05 | 日産化学工業株式会社 | 2―ピラゾリン―5―オン類の製造法 |
IL85659A (en) * | 1987-03-17 | 1992-03-29 | Nissan Chemical Ind Ltd | 4-benzoylpyrazole derivatives,method for their preparation and herbicidal compositions containing them |
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CA2247203A1 (en) | 1997-08-28 |
HUP9901104A2 (hu) | 1999-08-30 |
US5925767A (en) | 1999-07-20 |
GEP20012582B (en) | 2001-11-26 |
EE9800270A (et) | 1999-02-15 |
KR19990087188A (ko) | 1999-12-15 |
EP0888343A1 (de) | 1999-01-07 |
TR199801648T2 (xx) | 1998-11-23 |
AR005955A1 (es) | 1999-07-21 |
CN1211249A (zh) | 1999-03-17 |
IL125149A (en) | 2000-11-21 |
CN1075497C (zh) | 2001-11-28 |
JP2000506124A (ja) | 2000-05-23 |
IL125149A0 (en) | 1999-01-26 |
WO1997030993A1 (de) | 1997-08-28 |
EP0888343B1 (de) | 2002-06-05 |
DE59707423D1 (de) | 2002-07-18 |
NZ331052A (en) | 2000-02-28 |
AU1793197A (en) | 1997-09-10 |
EA199800760A1 (ru) | 1999-02-25 |
PL328506A1 (en) | 1999-02-01 |
SK103598A3 (en) | 1999-03-12 |
BR9707635A (pt) | 1999-07-27 |
HUP9901104A3 (en) | 2001-02-28 |
EA001515B1 (ru) | 2001-04-23 |
AU729651B2 (en) | 2001-02-08 |
CZ230398A3 (cs) | 1999-01-13 |
SK283200B6 (sk) | 2003-03-04 |
ATE218564T1 (de) | 2002-06-15 |
EE03615B1 (et) | 2002-02-15 |
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