CN1048845A - 某些乙醛酰己烯二酮 - Google Patents

某些乙醛酰己烯二酮 Download PDF

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CN1048845A
CN1048845A CN90104755A CN90104755A CN1048845A CN 1048845 A CN1048845 A CN 1048845A CN 90104755 A CN90104755 A CN 90104755A CN 90104755 A CN90104755 A CN 90104755A CN 1048845 A CN1048845 A CN 1048845A
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alkyl
formula
substituting group
different halogen
optionally
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CN1028988C (zh
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汉斯-约希姆·彼辛格
海姆德·巴尔鲁沙特
埃利克·拉达兹
沃尔夫岡·福鲁思多福
鲁得维·夏洛得
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Abstract

通式I的乙醛酰基-环己烯二酮可作为除草剂 有效地防治双子叶杂草。

Description

本发明涉及新的2-乙醛酰-环己-1-烯-3，5-二酮，类，它们的制备方法和作为除草剂的用途。
化合物A（1-羟基-2-异丁酰-4，4，6，6-四甲基-环己-1-烯-3，5-二酮）和B（1-羟基-2-异戊酰-4，4，6，6-四甲基-环己-1-烯-3，5-二酮）已从桃金娘科植物，澳洲茶树属植物和Xanthostemon属植物中分离出（R.O.Hellyer，Aust，J.Chem.21，2825（1968），但没有公开这些化合物的用途。A.C.Jain和T.R.Seshadri（in  Proc  Indian  Acad.Sci.42A，279（1955）公开了化合物C（1-羟基-2-乙酰-4，4，6，6-四甲基-己环-1-烯-3，5-二酮），但也没有描述该化合物的用途。
Figure 901047554_IMG5
此外，从美国专利说明书No.4，202，840、欧洲专利说明书No.249，151A和英国专利说明书No.2，215，333A得知，这类化合物中的某些化合物显示出除草活性。但得到满意的除草活性所需的这些除草剂的剂量相当高，另外，还不能观察到这些化合物的选择性。
现在我们已惊奇地发现，与上述天然产物有点相关的某些化合物在较低的剂量下显示出极好的除草活性，且对阔叶杂草具有良好的选择活性。
因此，本发明提供了通式Ⅰ的化合物，
式中，X为OH，OR7，NH2，NHR7，NR7R8，
NOH，NOR7，OCOR7，OCONHR7，
OCONHCOR7，OCONHSO2R7，
NHCONHCOR7，OCOSR7，NHCOSR7，
SCOR7，SR7，SCONHR7，SCONHCOR7，
SCONHSO2R7或SCOSR7;
R1至R4各自为氢，直链或支链C1-6烷基，C2-6链烯基或C2-6链炔基，这些烃基可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6取代基取代;或者
R1和R2和/或R3和R4一起形成直链或支链、饱和或不饱和的C2-6亚甲基，该桥可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6的取代基取代;
R5为直链或支链C1-20烷基，C2-20链烯基或C2-20链炔基，C3-20环烷基，苯基或萘基，或饱和或不饱和的具有1个或多个杂原子的杂环基，上述基团可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6的取代基取代;
R6为直链或支链C1-20烷基，C3-20环烷基，苯基或萘基，或饱和或不饱和的具有1个或多个杂原子的杂环基，上述基团可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，COOH，NO2，NH2，SO3H和SH取代基取代;
R7和R8各自具有与R5相同的定义。
作为取代基的烷基或作为其它取代基（如烷氧基）的一部分的烷基可以是例如下列取决于碳原子数的直链或支链基团之一：甲基，乙基，丙基，丁基，戊基，己基，庚基，辛基，壬基，癸基，十一烷基和十二烷基，包括安们的异构体，例如异丙基，异丁基，叔丁基和异戊基。卤素可以是氟、氯、溴或碘。链烯基可以是例如丙烯-1-基，烯丙基，丁烯-1-基，丁烯-2-基，或丁烯-3-基以及具有多于1个双键的基团。链炔基可以是例如丙炔-2-基，炔丙基，丁炔-1-基或丁炔-2-基。环烷基包括取决于碳原子数的下列基团：环丙基、环丁基、环戊基、环己基、环庚基、环辛基和环壬基。饱和的或不饱和的杂环基宜由含1至4个相同或不同的杂原子（例如氮、氧或硫）的饱和或不饱和的五员或六员杂环化合物衍生而得。上述杂环化合物的适合例子有四氢呋喃、呋喃、四氢噻吩、噻吩、吡咯烷、吡咯、吡咯啉、吡唑、咪唑、三唑、四唑、吡唑啉、噁唑、噻唑、异噁唑、异噻唑、吡喃、二氢吡喃、四氢吡喃、噻喃、二氢噻喃、四氢噻喃、吡啶、哌啶、哒嗪、二氢哒嗪、四氢哒嗪、嘧啶、二氢嘧啶、四氢嘧啶、吡嗪、二氢吡嗪、四氢吡嗪、吗啉、噻嗪、二氢噻嗪、四氢噻嗪、哌嗪和三嗪。
通式Ⅰ的化合物在室温（20℃）下是油状物、胶状物，或主要是结晶固体材料。这些化合物具有不同的生化活性且可在农业或有关领域中用于防除不需要的植物，尤其是在例如谷类作物中有选择性用于防除阔叶杂草。
用下列优选的通式Ⅰ的化合物可较好地防除不需要的植物，式中
X为OH，OR7，OCOR7，NH2，NHR7，NR7R8或SR7;
R1至R4各自为氢原子或直链或支链C1-6烷基，该烷基可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6取代基取代;或
R1/R2和/或R3/R4一起形成直链或支链，饱和或不饱和的C3-5亚甲桥，该桥可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6的取代基取代;
R5为直链或支链C1-8烷基，C2-8链烯基或C2-8链炔基或C3-8环烷基，上述基团各自可选择性地被1个或多个、相同或不相同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6的取代基取代;或者R5为苯基或萘基，或饱和的或不饱和的具有1至4个选自氮、氧和硫的杂原子的五员或六员杂环基，上述基团各自可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6的取代基取代;
R6为直链或支链C1-6烷基，C3-6环烷基，苯基或萘基，或饱和的或不饱和的具有1至4个选自氮、氧和硫的杂原子的五员或六员杂环基，上述基团可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，COOH，NO2，NH2，SO3H和SH的取代基取代;
R7和R8各自具有与R5相同的定义。
优选的用于防除各种阔叶杂草的通式（Ⅰ）的化合物是下述化合物，式中
X为OH，OR7，OCOR7，NH2，NR7R8，或SR7;
R1至R4各自为氢或直链或支链C1-4烷基，该烷基可选择性地被1个或多个、相同或不同的选自卤素和OH，OR6，COOR6，NH2和NR6 2取代基取代;
R5，R7和R8各自为直链或支链C1-6烷基，该烷基可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6的取代基取代;或各自为苯基、萘基或噻吩基，上述基团各自可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6的取代基取代;
R6为直链或支链C1-4烷基或苯基，上述基团各自可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，COOH，NO2，NH2，SO3H和SH的取代基取代。
最好的芽前和芽后防除阔叶杂草的通式Ⅰ的化合物是下述化合物，式中，
X为OH，OR7，OCOR7或NH2;
R1至R4各自为氢或C1-2烷基;
R5、R7和R8各自为直链或支链C1-4烷基;该烷基可选择性地被1个或多个、相同或不同的选自卤素和OR6的取代基取代，或各自为苯基、萘基或噻吩基，上述基团各自可选择性地被1个或多个、相同或不同的选自卤素和R6，OR6和SO2R6的取代基取代;
R6为甲基或三氟甲基。
可以看出，某些取代基会使通式Ⅰ的化合物物产生互变异构形式。应理解，本发明可延伸到通式（Ⅰ）的化合物的所有各种形式和其任何比例的混合物。因此，通式Ⅰ的化合物，它们的互变异构体及其混合物均包括在本明之内，对以互变异构体形式存在的化合物的叙述应理解为包括它们的互变异构体或含所述化合物的互变异构混合物。
通式Ⅰ的中R1至R6为如上所定义的基团和X为OH的化合物可通过氧化通式Ⅱ的化合物制得，
式中R1至R6为如上所定义的基团，X为OH，通式（Ⅱ）的化合物可用美国专利说明书4，202，840所公开的方法合成。这些化合物可作为分离的原料使用，但宜就地制备这些化合物，然后在同一容器的反应中就地将其氧化。
该反应最好按下列方式进行：宜使用根皮苯乙酰苯本身或用例如烷基卤（如甲基碘）烷基化的产物进行反应，从而得到通式Ⅱ的原料。可使用任何适度的氧化剂，如碘，高锰酸盐（如高锰酸钾），二氧化硒和四氧化锇进行随后的氧化反应，但使用碘或高锰酸盐特别有利。特殊溶剂的使用并不显得重要，可使用极性溶剂和非质子传递溶剂以及这些溶剂的混合物。但已发现，当用碘进行氧化时，使用极性溶剂如低级（C1-6，较好的为C1-4）醇（例如甲醇和乙醇）可获得较好的结果。
反应通常在0至100℃的温度下，较合适的在5至70℃的温度下进行，10至50℃的反应温度适合于上述制备方法。
氧化完成后，可有任何适宜的常规步骤分离获得的通式Ⅰ的化合物。例如，可用蒸馏法除去溶剂（例如甲醇）和在第一步制备通式Ⅱ的中间体的反应中所用的过量的烷基卤，然后将残余物溶于水，酸化，用与水不混溶的有机溶剂萃取。可通过用温和的还原剂（如亚硫酸氢钠水溶液）洗涤有机层的方法除去任何过量的氧化剂。蒸去溶剂后所获得的残余物可用结晶法进一步提纯或直接用于进一步的衍生反应，例如1-羟基的酯化反应或用胺取代该基团。
制备通式Ⅰ中X为OH的化合物的另一方法是使通式Ⅲ的化合物
（式中R1至R4和R6如上所定义）与通式Ⅳ的酰氯反应，
式中R5和R6如上所定义。
通式Ⅲ的环己烷衍生物宜在酸净化剂，尤其是吡啶存在下与通式（Ⅳ）的酰氯反应。反应通常在0至100℃，适宜的为5至70℃的温度下进行。10至50℃的温度适宜于上述制备方法。在除去溶剂后，将残余物溶于叔胺中，用催化量的丙酮合氰化氢处理，得到通式Ⅰ的羟基化合物。
在反应完成后，可用任何适宜的常规方法分离通式Ⅰ的化合物。例如，真空蒸发溶剂，然后将残余物溶于水中，酸化后用乙酸乙酯萃取。可采用某些方法如硅胶柱色谱法进行最终提纯。
通式Ⅲ和Ⅳ的化合物或是已知的化合物或可用常规方法制备。
通式Ⅰ中X不为OH的化合物可采用本领域众所周知的方法（例如羟基的酯化或用胺取代基取代羟基）由相应的羟基化合物直接就地制备或由分离的羟基化合物制备。
本发明还提供了包含通式Ⅰ的化合物以及载体的除草组合物。在本发明的组合物中宜具有至少二种载体，其中至少一种是表面活性剂。
本发明还涉及用本发明的化合物或组合物处理某些区域（例如土壤或庄稼地里的植物）从而在该区域内抑止不需要的植物生长的方法。可以在芽前或芽后施用，所用的活性组分的剂量可以为例如0.01至10千克活性组分/公顷。
本发明还提供了本发明的化合物作为除草剂的用途。这些化合物特别适用于防除阔叶杂草。
通式Ⅰ的化合物可直接使用，但最好以组合物的形式使用，所述组合物除含本发明的化合物外，还含有一种或多种辅助剂和助剂，稳定的、已知是可用于制剂的固态和/或液态化合物，其剂型为常规剂型，例如乳油，可直接喷洒或稀释的溶液，乳液，可湿性粉剂，可溶性粉剂，粉尘剂，颗粒剂和微胶囊剂，可根据施用地点、占优势的空气条件等因素选择施用方式（如喷洒，喷雾，分散和倾倒）和组合物的形式。
本发明的除草组合物可采用常规方法，例如将活性组分与其它物质如填料，溶剂，固体载体，特别是表面活性剂一起充分混合和/或研磨的方法来制备。
所用溶剂可以是芳烃，优选的是C8-12馏分（例如二甲苯或其混合物，取代的萘、邻苯二甲酸酯，如邻苯二甲酸二丁酯或二辛酯），脂族烃（例如环己烷或烷属烃），一元醇和二元醇以及其醚和酯（例如乙醇，乙二醇单和二甲醚），酮（例如环己酮），强极性溶剂（例如N-甲基-2-吡咯烷酮，二甲亚砜，烷基甲酰胺），环氧化的植物油（例如环氧化的椰子油或豆油）和水。
可用于粉剂或可分散的粉尘剂的固体载体可以是无机填料，例如方解石、滑石、高岭土，蒙脱土和活性白土。加入高分散的硅胶或高分散的聚合物可改进物理性质。颗粒剂所用的载体可以是多孔性材料，例如浮石，碎砖，海泡石，膨润土，也可以是非吸收性载体，如方解石和砂子。另外，许多预先粉碎的无机或有机材料如白云石或压碎的植物废料也可使用。
适宜的表面活性物质可以是具有良好分散、乳化和润湿性能的非离子、阻离子或阳离子型表面活性剂，取决于所要配制的通式Ⅰ化合物的性质。也可使用表面活性剂的混合物。
适宜的表面活性剂可以是所谓水溶性皂以及水溶性合成表面活性物质。
肥皂通常是高级脂肪酸（C10-20）的碱金属盐、碱土金属盐或可任选取代的铵盐，例如，油酸或硬脂酸或由例如椰子油或动物脂油制得的天然脂肪酸的混合物的钠盐或钾盐。另外，也可使用脂肪酸的甲基牛磺酸盐。
但优选使用的是所谓合成表面活性剂，尤其是脂族磺酸盐，脂族硫酸盐，磺化苯并咔唑衍生物或烷基芳基磺酸盐。
脂族硫酸盐或脂族磺酸盐通常作为碱金属盐、碱土金属盐或可任选取代的铵盐使用，且具有含8至22个碳原子的烷基部分（烷基也可以是指芳基中的烷基部分），例如木素磺酸、磺酸十二烷酸酯或由天然脂肪酸制得的脂族醇的混合物的钠盐或钙盐。这也包括硫酸酯、磺酸和脂肪醇与环氧乙烷的加成物的盐。磺化苯并咪唑衍生物宜含2个磺酸基和一个含8至22个碳原子的脂肪酸基。烷基芳基磺酸盐是例如十二烷基苯磺酸、二丁基萘磺酸或萘磺酸与甲醛的缩合物的钠盐、钙盐或三乙铵盐。
另外，可使用磷酸盐（例如对壬基苯酚-（4-14）-环氧乙烷加合物的磷酸酯的盐）或磷脂。
非离子型表面活性剂宜为脂族或环脂族醇、饱和或不饱和脂肪、酸和烷基酚的聚乙二醚衍生物，它们具有3至10个乙二醇醚基，并在（脂族）烃基部分具有8至20个碳原子且在烷基酚的烷基部分具有6至18个碳原子。
其它适宜的非离子型表面活性剂是水溶性的含20-250个乙二醇醚基和10至100个聚丙二醇醚基的环氧乙烷与聚丙二二醇、乙二氨基聚丙二醇醚和烷基聚丙二醇（烷基部分含1至10个碳原子）的加聚物，所述物质中每个丙二醇单元宜含1-5个乙二醇单元。
非离子型表面活性剂的例子有壬基苯酚聚环氧乙醇，蓖麻油聚乙二醇醚，环氧乙烷和聚丙二醇加聚物，三丁基苯氧基聚环氧乙醇，聚乙二醇和辛基苯氧基聚环氧乙醇。
另外，可使用聚氧乙烯山梨糖醇的脂肪酸酯，如聚氧乙烯山梨糖醇三油酸酯。
阳离子型表面活性剂宜为季铵盐，该盐具有至少一个含8至22个碳原子的烷基，其它是低级的可选择卤化的烷基、苄基或羟烷基。所述盐宜为卤化物，甲基硫酸盐或烷基硫酸基，例如氯化十八烷基三甲基铵或溴化苄基二）2-氯乙基）乙基铵。
适合用于除草组合物的表面活性剂在下列出版物中有所描述：“McCutheon's  Detergents  and  Emulsifiers  Annual”，MC  Publishing  Corp.，Ridgewood，NJ，USA  1981;H.Stache，“Tensid-Taschenbuch”2nd  ed.，C.Hanser，Munich，Vienna，1981;M.and  J.Ash，“Encyclopedia  of  Surfactants”，Vol.Ⅰ-Ⅲ，Chemical  Publishing  Co.，New  York，NY，USA  1980-1981。
本发明的除草组合物宜含0.1至95%，较好的为0.1至80%（wt）的至少一种通式（Ⅰ）的化合物，1至99.9%（wt）的固态或液态助剂和0至25%，较好的为0.1至25%（wt）的表面活性剂。
优选的组合物形式和组分如下所示（所有的百分率为重量百分率）：
浓乳油
活性组分：1至20%，优选5至10%
表面活性物质：5至30%，优选10至20%
液态载体：50至94%，优选70至85%
悬浮浓缩液
活性组分：5至75%，优选10至50%
水：94至24%，优选88至30%
表面活性物质：1至40%，优选2至30%
可湿性粉剂：
活性组分：0.5至90%，优选1至80%
表面活性物质：0.5至20%，优选1至15%
固态载体：5至95%，优选15至90%
粉剂：
活性组分：0.1至10%，优选0.1至1%
固态固体：99.9至90%，优选99.9至99%
颗粒剂：
活性组分：0.5至30%，优选3至15%
固态载体：99.5至70%，优选97至85%
组合物宜配制成浓缩物的形式，这种浓缩物可由使用者在应用前稀释。使用时组合物可稀释至活性组分（a.i.）的浓度为0.001%。如上所述，应用剂量宜为0.01至10kga.i./公顷。
本发明的组合物还可含其它辅助剂（如稳定剂、消泡剂、粘度调节剂、增稠剂、粘结剂、肥料）或其它活性组分（例如具有抗菌或杀虫活性的化合物）或其它除草剂。
下列实施例将说明本发明。
实施例1
1-羟基-2-苯基乙醛酰-4，4，6，6-四甲基-环己-1-烯-3，5-二酮
方法A：
将根皮苯乙酰苯（27.0g，0.11mol）加入钠（12.7g，0.55mol）的甲醇（400ml）溶液中。接着滴加甲基碘（125g，0.88mol）并维持在20℃的温度下，将获得的混合物在室温下放置5天。然后分批加入碘（25.3g，0.1mol），同时连续添加甲醇钠，使PH值保持在7.5至8.0。蒸馏除去过量的甲醇和甲基碘后，将残余物溶于水中。加入2N盐酸以仔细地酸化溶液，然后用二乙醚（200ml）萃取三次。收集的有机层用10%亚硫酸氢钠水溶液洗涤一次，再用水洗涤一次，用无水硫酸镁干燥，然后蒸发。用异丙醇对残余物进行结晶，得到与标题化合物一致的微结晶物质（11.4g，理论产率的33%，熔点150-152℃）。
方法B：
将4，4，6，6-四甲基-1，3，5-环己三酮（100mg，0.55mmol）溶于吡啶（5ml）中。加入苯乙醛酰氯（93mg，0.55mmol），并将混合物在50℃保持2天。然后蒸发溶剂并将残余物溶于三乙胺（10ml）。加入催化量的丙酮合氰化氢（2滴，约0.1ml），搅拌反应混合物24小时。接着真空蒸发溶剂，将残余物溶于水（10ml）中，用2N盐酸酸化并用乙酸乙酯萃取溶液。分离的有机层用水洗涤，干燥，浓缩，然后装入填有硅胶的色谱柱，用二氯甲烷/丙酮（9∶1，V/V）洗脱，获得1-羟基-2-苯基-乙醛酰-4，4，6，6-四甲基-环己-1-烯-3，5-二酮（93mg，理论产率的54%，熔点为150-152℃）。
实施例2
1-氨基-2-苯基乙醛酰-4，4，6，6-四甲基环己-1-烯-3，5-二酮
将按实施例1制备的1-羟基-2-苯基乙醛酰-4，4，6，6-四甲基环己-1-烯-3，5-二酮（7.1g，0.23mol）溶于甲基叔丁基醚（70ml）中。在反应釜中将液氨（70ml）加入上述溶液中，搅拌混合物15小时。然后蒸除氨，用浓盐酸（8ml）的水（70ml）溶液洗涤得到的溶液。分离含水层，用二乙醚萃取二次，收集的有机层用氢氧化钠水溶液洗涤二次，用水洗涤一次，用无水硫酸镁干燥，然后蒸发。无色的微晶产物（4.0g，理论产率的57%）在139℃熔化并分解，该产物与标题化合物一致。
上述实施例1和2的化合物和按类似于上述实施例1至2的方法制备的通式Ⅰ的其它化合物的鉴定数据列于下面的表1。
本发明所包含的和可按类似于上述实施例1至2的方法制得的通式Ⅰ的化合物的其它实施例列于下面的表2。
Figure 901047554_IMG9
Figure 901047554_IMG10
Figure 901047554_IMG13
Figure 901047554_IMG14
Figure 901047554_IMG15
Figure 901047554_IMG18
Figure 901047554_IMG19
Figure 901047554_IMG20
Figure 901047554_IMG21
Figure 901047554_IMG22
生物活性
芽前处理的除草活性（pre-em）
将试验植物播撒在深2cm的盆中，在同一天用喷洒器以800升/公顷的喷洒量和2千克/公顷的剂量将除草剂喷洒在覆盖土壤的表面。然后将处理过的盆放在温室中。三周后与未处理的过的对照盆相比，测定除草效率，评价等级为1-9，1表示效率为100%，9表示完全无效。
在该评价等级中：
1  表示100%
2  表示100-97.5%
3  表示97.5-95%
4  表示95-90%
5  表示90-85%
6  表示85-75%
7  表示75-65%
8  表示65-32.5%
9  表示32.5-0%活性
芽后处理的除草活性（post-em）
将试验植物播种在深2cm的盆中并载培至2.5叶龄（单子叶植物/青草）或至1.5metaphyll。用喷洒器以800升/公顷的喷洒量和2千克/公顷的剂量将除草剂喷洒在叶子上。然后将处理过的盆放在温室中。三周后与未处理过的对照盆相比，测定除草效率，评价方法与芽前处理的评价方法相同。
对下列植物进行试验：
AVEFA  野燕麦
ALOMY  鼠尾看麦娘
ECHCG  无芒稗
SINAL  田白芥
LYPES  番茄
BEAVA  甜菜
CYPES  铁荸荠
这些试验的结果列于下面的表3中。
Figure 901047554_IMG25

Claims (10)

1、通式Ⅰ的化合物
Figure 901047554_IMG2
式中，X为OH，OR7，NH2，NHR7，NR7R8，NOH，NOR7，OCOR7，OCONHR7，OCONHCOR7，OCONHSO2R7，NHCONHCOR7，OCOSR7，NHCOSR7，SCOR7，SR7，SCONHR7，SCONHCOR7，SCONHSO2R7或SCOSR7；
R1至R4各自为氢或直链或支链C1-6烷基，C2-6链烯基或C2-6链炔基，这些烃基可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6取代基取代；
R1和R2和/或R3和R4一起形成直链或支链、饱和或不饱和的C2-6亚甲桥，该桥可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6取代基取代；
R5为直链或支链C1-2c烷基，C2-2c链烯基或C2-2c链炔基，C3-20环烷基，苯基或萘基，或饱和或不饱和的具有1个或多个杂原子的杂环基，上述基团可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6的取代基取代；
R6为直链或支链C1-2c烷基，C3-2c环烷基，苯基或萘基，或饱和或不饱和的具有1个或多个杂原子的杂环基，上述基团可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，COOH，NO2，NH2，SO3H和SH取代基取代；
R7和R8各自具有与R5相同的定义。
2、权利要求1所述的化合物，
式中，X为OH，OR7，OCOR7，NH2，NHR7，NR7R8或SR7;
R1至R4各自为氢或直链或支链C1-6烷基，该烷基可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6取代基取代;或者
R1/R2和/或R3/R4一起形成直链或支链，饱和或不饱和的C3-5亚甲桥，该桥可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6的取代基取代;
R5为直链或支链C1-8烷基，C2-8链烯基或C2-8链炔基或C3-8环烷基，上述基团各自可选择性地被1个或多个、相同或不相同的选自卤素和CN，OH，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6的取代基取代;或者R5为苯基或萘基，或饱和的或不饱和的具有1至4个选自氮、氧和硫的杂原子的五员或六员杂环基，上述基团可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6的取代基取代;
R6为直链或支链C1-6烷基，C3-6环烷基，苯基或萘基，或饱和的或不饱和的具有1至4个选自氮、氧和硫的杂原子的五员或六员杂环基，上述基团可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，COOH，NO2，NH2，SO3H和SH的取代基取代;
R7和R8各自具有与R5相同的定义。
3、权利要求1或2所述的化合物，
式中X为OH，OR7，OCOR7，NH2，NR7R8，或SR7;
R1至R4各自为氢或直链或支链C1-4烷基，该烷基可选择性地被1个或多个、相同或不同的选自卤素和OH，OR，COOR6，NH2和NR6 2取代基取代;
R5，R6和R8各自为直链或支链C1-6烷基，该烷基可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6的取代基取代，或各自为苯基、萘基或噻吩基，上述基团各自可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，R6，OR6，COOR6，NO2，NH2，NR6 2，SO3H，SO2R6和SR6的取代基取代;
R6为直链或支链C1-4烷基或苯基，上述基团各自可选择性地被1个或多个、相同或不同的选自卤素和CN，OH，COOH，NO2，NH2，SO3H和SH的取代基取代。
4、权利要求1至3中任一项所述的化合物，
式中，X为OH，OR7，OCOR7或NH2;
R1至R4各自为氢或C1-2烷基;
R5、R7和R8各自为直链或支链C1-4烷基;该烷基可选择性地被1个或多个、相同或不同的选自卤素和OR6的取代基取代，或各自为苯基、萘基或噻吩基，上述基团可选择性地被1个或多个、相同或不同的选自卤素和R6，OR6和SO2R6的取代基取代;
R6为甲基或三氟甲基。
5、制备权利要求1所述的通式Ⅰ的化合物的方法，该方法包括：
（a）氧化通式Ⅱ的化合物，
Figure 901047554_IMG3
（式中R1-R6如权利要求1所定义），或
（b）使通式Ⅲ的化合物
Figure 901047554_IMG4
（式R1至R4和R6如权利要求1所述义）与通式Ⅳ的酰卤反应
（式中R5和R6如权利要求1所定义），如果需要，然后将得到的通式Ⅰ中X为OH的化合物转化成通式Ⅰ中X不为OH的化合物。
6、权利要求5所述的方法，其中反应a）使用碘或高锰酸盐作氧化剂进行反应。
7、权利要求5或6所述的方法，其中氧化反应就地进行。
8、一种除草组合物，该组合物含权利要求1至4中任一项所述的化合物以及载体。
9、抑止某一区域上的不需要的植物生长的方法，该方法包括用权利要求1至4中任一项所述的化合物或权利要求8所述的组合物处理某一区域。
10、权利要求1-4中任一项所述的化合物或权利要求8所述的组合物在抑止不需要的植物生长方面的用途。
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