CN1119188A - 作为除草剂的4-苯氧基香豆素 - Google Patents

作为除草剂的4-苯氧基香豆素 Download PDF

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CN1119188A
CN1119188A CN95107592A CN95107592A CN1119188A CN 1119188 A CN1119188 A CN 1119188A CN 95107592 A CN95107592 A CN 95107592A CN 95107592 A CN95107592 A CN 95107592A CN 1119188 A CN1119188 A CN 1119188A
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dichlorophenoxy
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tonka bean
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S·I·阿尔瓦拉多
P·A·马克
B·J·达尔克
E·M·赖利
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Wyeth Holdings LLC
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American Cyanamid Co
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract

本发明提供了在作物，特别是禾本科作物存在下，控制单子叶杂草的方法，本发明也提供了用作除草剂的4-(2，6-二取代苯氧基)香豆素衍生物及其制备方法。

Description

作为除草剂的4-苯氧基香豆素
本发明涉及控制单子叶杂草生长的方法，本发明也涉及用作除草剂的4-(2，6-二取代苯氧基)香豆素衍生物及其制备方法。
选择性地控制杂草的生长是全世界作物生产中的一个经常性的问题，特别在有诸如禾本科作物的单子叶作物存在时控制单子叶杂草的生长尤为烦人。所述的杂草不仅在使禾本科作物繁殖的相同或相似种植条件下会繁殖，而且对控制这些杂草最有效的除草剂也会对禾本科作物产生植物毒性作用。因此，目前一直在寻找在种植禾本科作物时选择性控制不需要的单子叶杂草的新的有效方法。
本发明的一个目的是提供在包括单子叶作物的植物存在下有效地控制单子叶杂草、且对所述作物无害的方法。
本发明的再一个目的是提供在作物生产中，特别是在禾本科作物生产中用作选择性除草剂的4-(2，6-二取代苯氧基)香豆素衍生物。
本发明的有利之处在于4-(2，6-二取代苯氧基)香豆素衍生物在水稻种植的条件下可以尤为有效地控制青草和其它单子叶杂草的生长，同时对水稻没有或几乎没有植物毒性作用。
本发明涉及控制单子叶年生、多年生和水生植物的方法，包括给含有所述植物的种子或其它繁殖器官的土壤或水施加除草有效量的式I化合物：(I)其中
X和X′各自是卤素、C1～C4烷基或C2～C4链烯基；
W、Y和Z各自是O或S；
R是1～3个选自H、卤素、C1～C4烷基、C3～C6环烷基、C1～C4卤代烷基或C1～C4烷氧基的任何结合形式；
R1是1～4个选自H、卤素、OH、CN、NO2、SH、任意地被一个或多个卤素或OR2取代的C1～C6的烷基、C3～C6环烷基、C1～C6烷硫基、C2～C6链烯基、C2～C6卤代链烯基、C2～C6炔基、C2～C6卤代炔基、OR2、OCH2COOR3、OCH2OR4、OCOOR5、OCONHR6、OCOR7、S(O)nR8、COR9、CH(OR10)2、任意地用一至三个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基、或任意地被一至三个卤素、CN、C1～C4烷基、C1～C4卤代烷基或C1～C4烷氧基取代的苄基的任何结合形式；
R2是H、C1～C4烷基、C1～C4卤代烷基、C2～C6链烯基。C2～C6炔基、C2～C6卤代链烯基或C2～C6卤代炔基；
R3、R4、R5、R6和R7各自是H、C1～C4烷基、C1～C4卤代烷基、C3～C6环烷基、任意地被1～3个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基、或任意地用1～3个卤素、C1～C4烷基、C1～C4卤代烷基或C1～C4烷氧基取代的苄基；R8是C1～C4烷基、C1～C4卤代烷基或任意地用1～3个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基；
R9是H、OH、C1～C4烷基、C1～C4烷氧基、任意地用1～3个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基、任意地用1～3个卤素、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苄基或是NR11R12；
R10是H、C1～C4烷基或-(CH2)m-；
R11和R12各自是H、C1～C4烷基、C2～C4链烯基或者R11和R12与其它原子连结在一起形成任意地被氧所间隔的5-元或6-元环；n是整数0、1或2；以及m是整数2或3
本发明也涉及在作物存在下选择性地控制单子叶杂草，它包括给杂草种子或繁殖器官所处的且已种植或移植了作物的土壤或水中施加除草有效量的如上所述的式I化合物。
本发明进一步涉及式I的除草化合物、含有式I化合物的组合物以及制备所述化合物的方法。
由于顽固的和传播性杂草的存在可使作物生产降低30％～60％。在各种作物，特别是禾本科作物，种植和收成中，特别的杂草问题是单子叶杂草，如雨久花属(monochoria)、慈菇属(saggitaria)、莎草属和青草，这是在生产如谷类、小麦、大麦、稻、燕麦之类的禾本科作用中的持久性的问题。更具体地说，种稻时，诸如稗和水草之类的杂草的存在和繁殖会明显降低谷物的得率和质量。由于控制单子叶杂草的除草剂一般对禾本科作物有潜在的植物损伤，从而使问题复杂化。
现已发现，给杂草种子或繁殖器官所处的土壤或水中施加式I的4-苯氧基香豆素衍生物可以有效地控制诸如雨久花属、慈菇属、莎草科和青草之类的单子叶年生、多年生和水生杂草。
令人惊奇的是，在诸如玉米、小麦、大麦、稻、燕麦之类的禾本科作物存在下可以选择性地控制所述的单子叶杂草而对所述的作物几乎没有或完全没有植物毒性。有利的是，式I的4-苯氧基香豆素可在芽前施加于单子叶杂草，可在灌水的稻田中于移植后施加到水稻秧苗上，这样可以有效地控制杂草，而稻作物几乎不受或完全不受相当的伤害。
本发明的用作除草剂4-苯氧基香豆素是式I化合物：(I)其中
X和X′各自是卤素、C1～C4烷基或C2～C4链烯基；
W、Y和Z各自是O或S；
R是1～3个选自H、卤素、C1～C4烷基、C3～C6环烷基、C1～C4卤代烷基或C1～C4烷氧基的任何结合形式；
R1是1～4个选自H、卤素、OH、CN、NO2、SH、任意地被一个或多个卤素或OR2取代的C1～C6的烷基、C3～C6环烷基、C1～C6烷硫基、C2～C6链烯基、C2～C6卤代链烯基、C2～C6炔基、C2～C6卤代炔基、OR2、OCH2COOR3、OCH2OR4、OCOOR5、OCONHR6、OCOR7、S(O)nR8、COR9、CH(OR10)2、任意地用一至三个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基、或任意地被一至三个卤素、CN、C1～C4烷基、C1～C4卤代烷基或C1～C4烷氧基取代的苄基的任何结合形式；
R2是H、C1～C4烷基、C1～C4卤代烷基、C2～C6链烯基。C2～C6炔基、C2～C6卤代链烯基或C2～C6卤代炔基；
R3、R4、R5、R6和R7各自是H、C1～C4烷基、C1～C4卤代烷基、C3～C6环烷基、任意地被1～3个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基、或任意地用1～3个卤素、C1～C4烷基、C1～C4卤代烷基或C1～C4烷氧基取代的苄基；R8是C1～C4烷基、C1～C4卤代烷基或任意地用1～3个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基；
R9是H、OH、C1～C4烷基、C1～C4烷氧基、任意地用1～3个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基、任意地用1～3个卤素、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苄基或是NR11R12；
R10是H、C1～C4烷基或-(CH2)m-；
R11和R12各自是H、C1～C4烷基、C2～C4链烯基或者R11和R12与其它原子连结在一起形成任意地被氧所间隔的5-元或6-元环；n是整数0、1或2；以及m是整数2或3
应当明白，R和R1代表苯环3、4和5位上(若为R)以及稠合苯环的5、6、7和8位上(若为R1)的取代基。在每种情况下，芳环可以在全取代或全部未取代的范围里(对于R1来说)，(对于R的情况)可以被X和X’二取代。当苯环被X和X，代表二取代时，R指H。当式I的4-苯氧基香豆素的稠合苯环位置完全不被取代时，则R1代表H。
术语卤代烃基代表含有1至2n＋1个卤素原子的烷基，CnH2n＋1。卤原子是Cl、Br、F或I。
较好的式I化合物是那些其中X和X′各自是Cl、Br或CH3，W、Y和Z是O。更好的化合物是X和X’各自是Cl、Br或CH3；W、Y和Z是O；R是H，R1是1、2或3个卤素。C1～C4烷基、C1～C4卤代烷基、C1～C9烷氧基、C1～C4卤代烷氧基或NO2的化合物。最好的化合物是其中X和X’各自是Cl、Br或CH3；W、Y和Z是O；R是H，R1是5-C1～C4烷基、5-卤代、5-C1～C4卤代烷基或5-NO2的化合物。
可以从容易得到的式III的2-羟基乙酰苯或其式II的水杨酸前体制得式I的4-(2，6-二取代-苯氧基)香豆素化合物。用如Heimark等在the Journal of Labelled Compounds and Radiopharma-ceuticals，1986，Vol.23，No.2.中所述的标准文献操作，在甲基锂的存在下，可将式II的酸转化成相应的式Ⅲ的乙酰苯。在至少2摩尔当量诸如氢化钠之类的碱存在下使式III乙酰苯与碳酸乙酯反应可得式IV的4-羟基香豆素。使用诸如POCl3加清除剂胺的标准过程可以将所述的羟基香豆素转化成相应的式V的4-氯香豆素衍生物。式V的氯代香豆素然后与式VI的2，6-二取代苯酚或硫代苯酚反应，得到所需的式I产品，其中Y是氧(式Ia)。为了得到Y是S的式I产物(Ib)，可将Ia的香豆素与Lawesson试剂或P2S5反应。反应流程如流程I所示。
                                  流程I
另一种方法是，将式II水杨酸转化成相应的式VII酰氯。如D.R.Buck等在Journal of Medicinal Chemistry，1975，Vol.18，No.4，391～394页中所述的，在碱的存在下用丙二酸二乙酯处理酰氯，形成中间体，后者可任意地在溶剂存在下经由加热的脱除羧乙氧基，得到所需的式IV的4-羟基香豆素。如上述流程I所示，可以将式IV羟基香豆素转化成式I的4-(2，6-二取代苯氧基)香豆素化合物。所述的反应顺序如流程II所示。
                                  流程II
Figure A9510759200161
也可以根据H.Cairns等在the Journal of Medicinal Chem-istry，1972，Vol.15，No.6.，pp.583～589，中所述的，通过用乙炔二羧酸二甲酯处理可从式VIII的酚得到式IX富马酸，这样也可有效地制备式I的4-(2，6-二取代苯氧基)香豆素除草剂。令人惊奇的是，用五氧化磷和甲磺酸的混合物处理式IX富马酸会高收率地生成式II的色酮-2-羧酸。然后，根据V.A.Zagorevskii和E.K.Orlova在Zhurnal Obschei Khimii，Vol.33，No.6，1963，pp.1857～1863.中所述，在催化量二甲基甲酰胺的存在下用亚硫酰氯处理可将式X中间体转化成式V氯代香豆素。这样制得的4-氯香豆素可以根据上述流程I制成所需的式I4-(2，6-二取代苯氧基)香豆素。反应顺序如流程III所示。
                                  流程III
本发明的4-苯氧基香豆素是式I的化合物，其中的X、X′、W、Y、R和R1如上所述，且条件是R1之一需至少是氢以外的基团。所述的化合物对于控制种种单子叶年生和多年生杂草是有效的除草剂。此外，这些化合物对生长在干地和湿地的杂草控制是有效的。以约0.006Kg/公顷～4.0Kg/公顷的施用率，较好的是以约0.06Kg/公顷～2.0Kg/公顷的施用率，可以得到有效的控制。当然，以高于4.0Kg/公顷的比率显然可用来有效地控制不需要的单子叶杂草，但是，由于过量除草剂会增高成本且对环境无益，故应避免使用高于所需有效水平的除草剂用量。
令人惊奇的是，现已发现本发明的式I苯氧基香豆新化合物是在作物生产中有用的选择性除草剂。特别是式I苯氧基香豆素化合物是在作物生产中有用的选择性除草剂。特别是式I化合物在诸如玉米、小麦、燕麦、大麦、稻之类禾本科作物存在下可以有效地控制如青草、莎草、雨久花属和慈菇属的传播性单子叶杂草。特别是，式I化合物对于在灌水的稻田中有移植稻的存在下控制青草杂草尤其有价值。
在农业实践中，本发明的化合物以包括农业上可接受的固体或液体载体和除草有效量的式I的苯氧基香豆素化合物的组合物形式施用。例如，可以诸如悬浮浓缩物、水剂浓缩物、可乳化的浓缩物、浓缩乳剂等之类的液体组合物形式，或以诸如可湿性粉未、可分散的颗粒、颗粒制剂、粉剂等的固体组合物形式施用。可望将本发明的化合物与其它的杀虫按有顺序地或同时地作为罐装混合物或单一组合物进行合并使用。特别是式I的苯氧基香豆素可与诸如氨碳酰脲、磺酰脲、二硝基苯胺、咪唑啉酮、硫代氨基甲酸酯、吡咯并嘧啶磺酰胺、α-卤代乙酰氨之类的共-除草剂合并使用。特别的例子是包括式I的苯氧基香豆素和氨磺酰脲、二硝基苯胺、磺酰脲或咪唑啉酮合并使用。虽然不是必需的，包括式I的化合物和共-除草剂的合并除草剂还可以包括其它组份，如，肥料、诸如表面活性剂、乳化剂、去沫剂、染料、增量剂之类的惰性辅剂。
为了更清楚地理解本发明，下面列出特定的实施例。所述的本发明及权利要求书并不只被这些实施例的范围所限定。确实，本技术领域的技术熟练者可从下列实施例和前面的叙述中作出除前所例举和叙述以外的本发明的种种改进。这类改进仍属本发明的权利要求范围内。1H、13C、19FNMR依次指质子、碳和氟核磁共振谱、IR是指红外光谱，HPLC指高效液相色谱。
                      实施例12-羟基-3-甲氧基乙酰苯
Figure A9510759200191
在氮气下以保持回流温度的速度向3-甲氧基水杨酸(4.0g，24毫摩尔)在四氢呋喃中的混合物滴加甲基锂(56ml1.4M醚溶液，78.4毫摩尔)。将反应混合物在回流温度下搅拌17小时，冷却至室温，倒入盐水、冰和6NHCl的混合物上。所得的混合物用乙酸乙酯萃取。合并有机萃取物，用盐水洗涤，用Na2SO4干燥并过滤。真空浓缩滤液，得到暗橙色残留物，用1∶2乙酸乙酯∶己烷收拾残留物，用硅胶塞过滤，再蒸发，得到残留物。该残留物用己烷结晶得到黄色针状的标题产物，2.08g(53％得率)，熔点49～51℃。用HPLC、1HNMR和质谱分析加以鉴定。
                      实施例28-甲氧基香豆素的制备
Figure A9510759200201
在N2下将2-羟基-3-甲氧基乙酰萃(0.80g，4.8毫摩尔)在氯仿中的溶液滴加至搅拌着的NaH(0.58g，60％NaH、14.5毫摩尔)和碳酸乙酯(2.84g，24毫摩尔)在氯仿中的混合物中，在回流温度下加热处理40小时。冷却至室温，用约45mlIN NaOH处理并剧烈搅拌24小时。分离各相，水相用6NHCl酸化。过滤所得的沉淀，用水洗涤，干燥，得到白色固体的标题产物0.88g(96％)得率，用1HNMR分析加以鉴定。
                        实施例34-氯-6-甲氧基香豆素的制备
Figure A9510759200202
在25℃用三正丁胺(250ml，1.73摩尔)滴加至搅拌着的4-羟基-6-甲氧基香豆素(116g，0.603摩尔)和POCl3(462.29g，3.015摩尔)在甲苯中的混合物，在100～110℃下加热，用HPLC分析监测、当反应完成后。使混合物冷却至室温，倒入冰中，机械搅拌约2小时，过滤。滤饼用水和甲苯清洗，溶于二氯甲烷中，用硅藻土过滤。浓缩二氯甲烷滤液，用二甲基甲酰胺和乙腈的混合物处理，得到结晶。将混合物过滤得到标题产物81.7g(64％得率)，用HPLC分析加以鉴定。
                        实施例44-(2，6-二氯苯氧基)-6-甲氧基香豆素的制备
Figure A9510759200211
通N2下将搅拌着的4-氯-6-甲氧基香豆素(1.0g，4.75毫摩尔)、2，6-二氯苯酚(0.85g，5.22毫摩尔)和K2CO3(0.98g，7.12毫摩尔)在乙腈中的混合物在回流温度下加热16小时。冷却至室温并倒入冰水中。该混合物用醚萃取数次。合并萃取物，真空浓缩，得到综褐色固体残留物。残留物用乙酸乙酯/己烷结晶，得到褐色晶状的标题产物1.17g(73％得率)，熔点170～171℃，用IR、1HNMR、13CN-MR和质谱加以鉴定。
                        实施例54-(2，6-二氯苯氧基)-6-羟基香豆素的制备
通N2下，于-70℃用BBr3在二氯甲烷中的1.0M溶液296ml滴加处理4-(2，6-二氯苯氧基)-6-甲氧基香豆素(25g，0.074摩尔)在二氯甲烷中的溶液。加料完成后，除去干冰/丙酮冷却浴，让反应在16小时里回复至室温。再加入二氯甲烷稀释反应混合物，机械搅拌下倒入冰水中，过滤得到淡黄色固体滤饼。让固体进行空气干燥，用二甲基甲酰胺/乙腈/水(1∶1∶0.1)结晶，得到白色晶状的标题产物，19.7g(86％得率)，熔点＞250℃，用1HNMR分析加以鉴定。
                      实施例64-(2，6-二氯苯氧基)-6-(二氟甲氧基)香豆素的制备
在室温和通N2下向搅拌着的4-(2，6-二氯苯氧基)-6-羟基香豆素(1.3g，3.71毫摩尔)在丙酮中的悬浮液中吹入氯代二氟甲烷持续约30～45分钟，冷却到5～10℃，用50％NaOH溶液(2.4g，1.2gNaOH，29.7毫摩尔NaOH)处理，在室温下搅拌2小时，过滤。固体滤饼用二氯甲烷洗涤，用乙腈/甲醇/水结晶，得到白色固体的标题产物，0.95g(69％得率)，熔点145～148℃，用IR，1HNMR，19FN-MR，13CNMR和质谱加以鉴定。
                     实施例74-羟基-8-硝基香豆素的制备
用于冰/丙酮冷却浴冷却NaH(6.94g，0.291摩尔)在二甲氧基乙烷中的溶液，用丙二酸二乙酯(46.6g，0.29摩尔)滴加处理，任其温热至9℃，用3-硝基水杨酰氯(19.5g，0.10摩尔)在二甲氧基乙烷中的溶液滴加处理，任其温热至室温，在室温下搅拌3小时，在60℃下加热至HPLC分析表示反应已完成为止。冷却到室温，倒入冰水和二氯甲烷的混合物中，搅拌约0.5小时。分离各相，水相用18％HCl酸化至pH5，过滤，将滤饼分散在乙酸中，加热并过滤。让滤饼空气干燥，将8.6g分散在二甲亚砜中，在100℃加热约2小时，冷却至室温，倒入冰水中，过滤。固体用乙腈收拾之，热过滤，冷却并过滤，得到标题产物，熔点242～245℃，用IR、1HNMR和质谱分析加以鉴定。
                    实施例84-(2，6-二氯苯氧基)-6-甲氧基硫代香豆素的制备
Figure A9510759200232
将4-(2，6-二氯苯氧基)-6-甲氧基香豆素(0.40g，1.2毫摩尔)和Lawesson试剂1(0.53g，1.3毫摩尔)在二噁烷中的混合物在回流温度下加热，搅拌约4小时，冷却至室温，在室温下搅拌16小时，过滤。滤饼用石油醚洗涤，空气干燥，得黄色固体的标题产物，0.28g(57％得率)，熔点231°～232℃，用1HNMR、13CNMR和质谱分析加以鉴定。①
                实施例9～15和96～984-苯氧基硫代香豆素衍生物的制备
Figure A9510759200241
用基本上与实施例8所述的相同的操作，并替代适当的4-苯氧基香豆素，得到下列化合物。
                表1
Figure A9510759200242
甲氧基苯基硫羰基膦化硫二聚物实施例序号    X   X′  R     W    R1          熔点℃  9    Cl    Cl   H     O    5-OH             --10    Br    Br   H     O    7-OCH3          --11    Cl    Cl   H     O    7-OCH3          --12    Cl    Cl   H     O    6，7-di-OCH3 219-22213    Cl    Cl   H     O    7-NO2           --14    Cl    Cl   H     O    5-OC2H5        --15    Cl    Cl   H     O    5-OCHF2         --96    Cl    Cl   H     O    6-OCHF2      177-18097    Cl    Cl   H     O    8-OCH3       156-15898    Cl    Cl   H     O    5-CF3        209-211
                   实施例164-(2，6-二氯苯氧基)-6-(N-甲基氨基甲酰基)香豆素的制备
Figure A9510759200251
在氮气和室温下用三乙胺(0.7ml，5毫摩尔)处理4-(2，6-二氯苯氧基)-6-羟基香豆素(0.5g，1.55毫摩尔)在二甲基甲酰胺中的溶液，然后用CH3NCO(0.5ml，5，5毫摩尔)处理，让它在室温下搅拌约1小时。当由HPLC分析指出反应已完成时，将反应混合物倒入水中，并用二氯甲烷萃取。真空浓缩萃取物，得到残留物。残留物用二氯甲烷/己烷结晶，得到白色晶状标题产物0.38g(71％得率)，熔点292℃～299℃，用1HNMR，13CNMR和IR分析加以鉴定。
                   实施例174-(2，6-二氯苯氧基)-6-(甲氧基甲基氧基)香豆素的制备
使4-(2，6-二氯苯氧基)-6-羟基香豆素(1.2g，3.2毫摩尔)、二甲氧基甲烷(0.565g、7.4毫摩尔)、POCl3(0.74g，4.8毫摩尔)和二甲基甲酰胺(0.43克，5.94毫摩尔)在甲苯中的混合物在90～100℃下加热4小时，冷却到室温，倒入冰水中，过滤，干燥滤饼，用乙腈/水重结晶，得到标题产物，0.45g(38％得率)，熔点302～305℃(分解)，用1HNMR、13CNMR和IR分析加以鉴定。
                       实施例182-羟基-4，5-二甲氧基乙酰苯的制备
Figure A9510759200262
在25℃下用三氟化硼醚合物1.20ml，9.72毫摩尔处理3，4-二甲氧基苯酚(0.50g，3.24毫摩尔)在乙酸中的溶液，在回流温度下加热至薄层层析表明反应完成为止，冷却到室温，倒入冰水中。过滤所得的混合物，滤饼用水和醚洗涤，真空干燥，给出橙色粉未状标题产物，0.64g(100％得率)，用1HNMR加以鉴定。
                      实施例192-[4-(三氟甲氧基)苯氧基]富马酸的制备
在室温和氮气氛下用苄基三甲基氢氧化铵(0.15ml，40％水溶液)处理4-(三氟甲氧基)苯酚(2.75g，12.5毫摩尔)和乙炔三羧酸二甲酯(1.69ml，13.7毫摩尔)在二噁烷中的混合物，加热至90～95℃(由薄层层析表明缩合完成)，冷却至40℃，用氢氧化钠处理(10ml，20％水溶液)，在90℃下加热1小时，冷却至室温。反应混合物用10％HCl水溶液处理至pH7，过滤，滤液用HCl酸化至约pH1，得到黄色沉淀。过滤固体，干燥，得到标题产物，2.56g(70％得率)，熔点208～210℃，用1H、13C和19FNMR、质谱和元素分析加以鉴定。
                      实施例206-(三氟甲氧基)色酮-2-羧酸的制备
Figure A9510759200272
用2-[4-(三氟甲氧基)苯氧基]富马酸(2.00g，6.85毫摩尔)处理五氧化磷(1.17g，8.21毫摩尔)在甲磺酸(14.38g)中的溶液，在氛围温度下搅拌16～18小时，在70℃下搅拌7小时，冷却至室温，并倒入冰中。过滤所得的混合物，干燥滤饼，得到标题产物，1.75g(93％得率)，熔点192～194℃，用1H和13CNMR、IR、质谱和元素分析加以鉴定。
                      实施例214-氯-6-(三氟甲氧基)香豆素的制备
Figure A9510759200281
用1滴二甲基甲酰胺(DMF)处理搅拌着的6-(三氟甲氧基)色酮-2-羧酸(1.50g，5.47毫摩尔)在亚硫酰氯(6.0ml)中的混合物，在回流温度下加热6小时，冷至室温，真空浓缩。将残留物分散于甲苯中，用饱和NaHCO3溶液处理，搅拌直至被中和。分离各相，真空浓缩甲苯相。将所得残留物在乙腈和二氯甲烷中纯化，得到标题产物，1.04g(72％得率)，熔点85～87℃，用1H、13C和19FNMR、IR、质谱和元素分析来加以鉴定。
                     实施例22～1924-(2，6-二取代苯氧基)香豆素衍生物的制备
使用基本上与实施例1～21中所述的相同的操作，得到表II所示的下列4-(2，6-二取代苯氧基)香豆素衍生物。
                            表I
Figure A9510759200291
实施例序号    X    X′   R    W    Y          R1             熔点℃
22       Cl    Cl    H    O    O          H                 159
23        F    F     H    O    O          H                195.6
24       Br    Br    H    O    O          H               162-170
25      CH3   CH3  H    O    O          H               163-164
26        F    OCH3 H    O    O          H               145-146
27        F    NO2  H    O    O          H               203-205
28     OCH3   OCH3 H    O    O          H                 175
29       Cl    Cl    H    O    O 6-(2Cl，4CF3，6F-C6H2)155-157
                     表I实施例序号   X    X′   R    W    Y     R1            熔点℃30       Cl   Cl     H    O    O    6-CH3         191-19231       Br   Br     H    O    O    6-OCH3       174-17532       Br   Br     H    O    O    6-OH3        182-18333       Cl   Cl     H    O    O 6-(O-CONHC2H5) 220-22134      OCH3 OCH3  H    O    O    6-OCH3       206-20835       Cl   Cl     H    O    O    7-OCH3        165-16836      OCH3 OCH3  H    O    O    7-OCH3       205.5-20737      OCH3 OCH3  H    O    O    5-OCH3       186.5-188.5
                          表I实施例序号    X    X′   R    W    Y         R1           熔点℃38        Cl    Cl    H    O    O    7-(OCH2CH＝CH2)  18 5.5-18239        Cl    Cl    H    O    O    5-(OCH2CH＝CH2)  156.5-158.540        Cl    Cl    H    O    O     5-(OCH2COOCH)    161.2-162.641        Cl    Cl    H    O    O     6-(OCH2COOCH)      135-13642        Cl    Cl    H    O    O    6-(OCH2CH＝CH2)    145-14643        Cl    Cl    H    O    O     6-(OCH2C≡CH)        15344        Cl    Cl    H    O    O    6-(OCH2CH2CF＝CF2)  14645        Cl    Cl    H    O    O       6-OCH(CH3)2       141
                          表I实施例序号    X    X′   R    W    Y          R1         熔点℃
46       Cl    Cl    H    O    O    6-OCH(CH3)C2H5 138
47       Cl    Cl    H    S    O        6-OCH3       216-217
48       Cl    Cl    H    O    O       6-OSO2CF3    137
49       Br    Br    H    O    O          6-F          165
50       Cl    Cl    H    O    O        6-C2H5      184
51       Cl    Cl    H    O    O          6-F          183
52       Cl    Cl    H    S    O          6-F          168
53       Cl    Cl    H    S    O        6-C2H5      182
                        表I
Figure A9510759200331
实施例序号    X    X′    R     W    Y         R1      熔点℃
54       Cl    Cl    4-Cl   O    O    6，7-di-CH3   264
55       Br    Br     H     O    O    6，7-di-OCH3  191
56       Cl    Cl    4-F    O    O       6-OCH3     217
57       Cl    Cl     H     O    O        6-Cl       204
58       Br    Br     H     O    O        6-Cl       188
59       Cl    Cl     H     S    O        6-Cl       214
60       Cl    Cl    4-Cl   O    O       6-OCH3     196
61       Cl    Cl    4-F    O    O    6，7-di-CH3   255
                         表I实施例序号    X    X′   R    W    Y        R1       熔点℃62        Cl    Cl    H    O    O    6-OCH2CHF2   16763        Cl    Cl    H    O    O    6，7-di-CH3   21264        Cl    Cl    H    S    O    6，7-di-CH3   24665        Cl    Cl    H    O    O    6，7-di-OCH3  19166        Cl    Cl    H    S    O    6，7-di-OCH3  17267        Cl    Cl    H    O    O    6，8-di-Cl     20668        Cl    Cl    H    S    O          H        21269        Br    Br    H    O    O       6-C2H5    159
                        表I实施例序号    X    X′    R    W    Y        R1       熔点℃
70       Br    Br     H    O    O    6，7-di-CH3   210
71       Br    Br     H    O    O    6，8-di-Cl     218
72       Cl    Cl    4-F   O    O        6-F        187
73       Cl    Cl    4-Cl  O    O        6-F        208
74       Cl    Cl    4-F   O    O    6，7-di-OCH3  205
75       Cl    Cl    4-Cl  O    O        6-Cl       221
76       Cl    Cl    4-F   O    O        6-Cl       200
77       Cl    Cl     H    O    O      6-OC2H5    162
                                  表I
Figure A9510759200361
实施例序号    X    X′       R           W    Y        R1            熔点℃
78        F    F    3，4，5-tri-F    O    O        6-F            173
79       Br    Br       4-CH3       O    O    6，7-di-OCH3      154
80       Cl    Cl        H           O    O 6-OCH2C6H4OCF3-p 129
81       Br    Br       4-F          O    O       6-OCH3         200
82       Br    Br       4-Br         O    O       6-OCH3        195-197
83       Cl    Cl       3-Cl         O    O       6-OCH3        218-220
84        F    F         H           O    O       6-OCH3        213-214
85       Cl    Cl        H           O    O        6-CN          249-250
                           表I实施例序号    X    X′   R    W    Y           R1          熔点℃
86       Cl    Cl    H    O    O    5，6，7-tri-OCH3  169-170
87       Cl    Cl    H    O    O         5-OCH3      203.6-207.5
88       Cl    Cl    H    O    O          7-OH         263-264.5
89       Cl    Cl    H    O    O          5-OH         250-256
90       Cl    Cl    H    S    O         5-OCH3       204-205
91       Br    Br    H    O    O         5-OCH3       201-203
92       Cl    Cl    H    S    O         8-OCH3       183-185
93       Br    Br    H    O    O         8-OCH3         157
                           表I实施例序号    X    X′   R    W    Y           R1          熔点℃
94       Cl    Cl    H    O    O          8-OCH3     142-144
95       Br    Br    H    O    O    5，6，7-tri-OCH3 179-181
99       Br    Br    H    O    O           6-OH         210
100      Cl    Cl    H    O    O           6-I        266-267
101      Br    Br    H    O    O         6-OCHF2     151-152
102      Cl    Cl    H    O    O         8-OCHF2     198-201
103      Br    Br    H    O    O         8-OCHF2     181-183
104      Cl    Cl    H    O    O        6-CH2OCH3     158
                          表I
Figure A9510759200391
实施例序号    Y        X′       R    W    Y      R1      熔点℃
105      Br        Br        H    O    O     8-OH      227
106      Cl        Cl        H    O    O     8-OH      252
107     CH3   CH2CH＝CH2 H    O    O    6-OCH3   88-90
108  CH(CH3)2 CH(CH3)2  H    O    O    6-OCH3  129-131
109     CH3     CH3       H    O    O    6-OCH3   192-193
110     Cl        Cl         H    O    O    6-OCF3   172-175
111     Cl        Cl         H    O    O     6-CF3   181-183
112     Br        Br         H    O    O    6-CH2Br    220
                       表I
Figure A9510759200401
实施例序号    X    X′      R    W    Y         R1           熔点℃
113      Cl    Cl       H    O    O        6-CHO           200
114     CH3 C(CH3)3 H    O    O       6-OCH3        148-151
115      Cl    Cl       H    O    O       6-C6H5       146-152
116      Cl    Cl       H    O    O       6-COOH           305
117      Br    Br       H    O    O        6-CHO         185-197
118      Cl    Cl       H    O    O    6-OCH2CH2OC2H5 89-91
119      Cl    Cl       H    O    O       6-SCH3        168-170
120      Cl    CH3     H    O    O       6-OCH3          192
                        表I
Figure A9510759200411
实施例序号    X     X′      R    W    Y         R1        熔点℃121       Cl    CH3      H    O    O    6，7-di-OCH3   141122       Cl    CH3      H    O    O    6，7-di-OCH3  172-173123       Cl    CH3      H    O    O      6-CH3        186124       Cl    CH3      H    O    O      6-C2H5     165-166125       Cl    CH3      H    O    O      8-OCH3      157-158126      CH3   CH3      H    O    O      8-OCH3      142-143127       Cl     Cl       H    O    O    6，7-di-OH      ＞300128      CH3   n-C3H7 H    O    O      6-OCH3        --
                           表I实施例序号    X    X′     R        W      Y          R1         熔点℃
129     CH3  CH3     H        O      O        6-CF3       193-194
130     CH3  CH3     H        O      O        6-OCF3      162-164
131     Cl    CH3     H        O      O        8-CF3       205-206
132     Br     Br 3，5-di-OCH3 O      O        6-OCH3      233-234
133     Cl    CH3     H        O      O   5，6，7-tri-OCH3 143-144
134     I      I      4-I       O      O         6-OCH3     202-203
135     Cl    Cl       H        O      O         8-CF3      217-218
136     Cl    CH3     H        O      O         5-OCH3     172-173
                         表I
Figure A9510759200431
实施例序号    X    X′    R    W    Y        R1       熔点℃
137      Cl    Cl     H    O    O       5-CF3    159-160
138      Br    Br     H    O    O       5-CF3    179-189
139      Cl    CH3   H    O    O       5-CF3    157-159
140      Cl    CH3   H    O    O   6-Cl，7-OCH3 167-168
141      Br    CH3   H    O    O      6-OCH3    180-181
142      Cl    Cl     H    O    O      6-C≡CH    220-224
143      Cl    CH3   H    O    O       8-CH3    174-175
144      Cl    Cl     H    O    O      7-OCHF2   158-160
                      表I实施例序号    X     X′    R     W    Y        R1         熔点℃145         Cl    CH3    H     O    O      6-OCHF2    158-161146         Cl    Cl      H     O    O       7-CF3     180-181147         Cl    CH3    H     O    O       7-CF3     146-148148         Cl    CH3    H     O    O    7，8-di-OCH3 179-181.5149         Cl    Cl      H     O    O    5-OCH(CH3)2 158.5-162150         Cl    Cl      H     O    O      5-OC2H5   152.5-155151         Cl    Cl      H     O    O      5-OCHF2    178.3-180152         Cl    Cl      H     O    O    5-OCH3，6-Cl  176-178
                        表I
Figure A9510759200451
实施例序号     X     X′    R     W    Y       R1         熔点℃153          Cl    Cl      H     O    O      8-Cl       206-208154          Cl    Cl      H     O    O    5-OCOCH3    130-133155          Cl    CH3    H     O    O      5-Cl       135-136156          Br    Br      H     O    O      5-Cl       155-156157          Cl    Cl      H     O    O      5-Cl       157-158158          Cl    Cl      H     O    O  5-OCH3，8-Cl 213-215.5159          Cl    CH3    H     O    O   5-CH3，8-Cl  175-176160          Cl    Cl      H     O    O   5-CH3，8-Cl  166-167
                        表I
Figure A9510759200461
实施例序号    X    X′   R    W    Y         R1         熔点℃
161      Cl    Cl    H    O    O    5-OCOC(CH3)3 139-141
162      Br    Br    H    O    O      5-OCOCH3    220-223
163      Br    Br    H    O    O    5-OCOC(CH3)3 218.3-220
164      Cl    Cl    H    O    O      7-OCOCH3    182-183.5
165      Cl    Cl    H    O    O    7-OCOC(CH3)3 135-137
166      Cl    Cl    H    O    O      8-OCOCH3    161-163
167      Cl    Cl    H    O    O    8-OCOC(CH3)3 144-146
168      Cl    Cl    H    O    O         5-F       146-147
                        表I实施例序号    X     X′    R    W    Y       R1         熔点℃169        Cl    CH3    H    O    O       5-F        137-138170        Cl    Cl      H    O    O      5-CH3      129-130171        Cl    CH3    H    O    O      5-CH3      118-119172        Cl    Cl      H    O    O    5，7-di-Cl    205-207173        Br    Br      H    O    O    5，7-di-Cl    208-209174        Cl    CH3    H    O    O    5，7-di-Cl    158-160175        Cl    Cl      H    O    O    6，7-di-Cl    195-196176        Cl    Cl      H    O    O    5，6-di-Cl    193-195
                            表I
Figure A9510759200481
实施例序号    X    X′    R    W    Y            R1          熔点℃
177      Cl    CH3   H    O    O       6，7-di-Cl       210-212
178      Br    Br     H    O    O      6，7-di-CH3      155-156
179      Br    Br     H    O    O        5，6-di-Cl      209-211
180      Br    Br     H    O    O        6，7-di-Cl      206-208
181      Cl    Cl     H    O    O    5，7-di-CH3，6-Cl  210-212
182      Br    Br     H    O    O    5，7-di-CH3，6-Cl  219-221
183      Cl    CH3   H    O    O    5，7-di-CH3，6-Cl  187-188
184      Cl    Cl     H    O    O        7，8-di-Cl       212-214
                             表I实施例序号   X    X′    R    W    Y            R1        熔点℃185      Br    Br     H    O    O       7，8-di-Cl      211-212186      Cl    CH3   H    O    O       7，8-di-Cl      234-236187      Cl    Cl     H    O    O    5，7-di-Br，6-CH3 217-218188      Cl    CH3   H    O    O    5，7-di-Br，6-CH3 201-203189      Cl    Cl     H    O    O       5，8-di-Cl      190-191190      Br    Br     H    O    O       5，8-di-Cl      203-205191      Cl    CH3   H    O    O       5，8-di-Cl      181-183192      Cl    Cl     H    O    O         5-NO2        211-212
                      实施例1934-羟基-5-(三氟甲基)二硫代香豆素的制备
Figure A9510759200501
在15～25℃下用60％氢化钠在矿物油(1.15g，28.8毫摩尔NaH)中的分散体于1.5小时内分批处理2’-氟-6’(三氟甲基)乙酰苯(3.0g，14.5毫摩尔)、二硫化碳(1.5ml，26.7毫摩尔)和二甲基甲酰胺(DMF)(12.5ml)在苯中的混合物，搅拌0.5小时，在125℃下加热1小时，冷却到室温，用水稀释。所得的混合物用乙酸处理，用醚萃取。水相用HCl酸化至pH3，并用乙酸乙酯萃取。合并乙酸乙酯萃取物，依次用水和盐水洗涤，用MgSO4干燥，真空浓缩，得到橙色油状残留物。残留物用乙醚/己烷结晶，得到白色固体的标题产物，3.0g(79％得率，熔点142～144℃，用IR、1HNMR、19FNMR和质谱分析加以鉴定。
                      实施例1944-(2，6-二氯苯氧基)-5-(三氟甲基)二硫代香豆素的制备
用基本上与上述实施例3和4所述的相同的操作，得到标题产物，用IR、1HNMR、19FNMR和质谱分析加以鉴定。
                     实施例1954-(2，6-二氯苯氧基)-6-氯二硫代香豆素的制备
用基本上与上述实施例3、4和193所述的相同的操作，得到标题化合物，熔点208～210℃，用IR、1HNMR和质谱分析加以鉴定。
                     实施例196在灌水的稻由中，在有移植稻存在下对试验化合物的芽前除草评估
按下列方法测定在移植后施药条件下的芽前除草活性和对稻作物的毒性，将杂草种子或块茎种在无排水孔的塑料容器内，它被种于淤泥沃土下的0.5cm处，4～6株两叶状态的稻禾(CV.Tebonnet)被移植入相同的容器内。塑料容器可以是32盎司，直径10.5cm或13cm×13cm占方，8cm深。在播种和移植后，将容器放在温室台上，使土壤保持3天浸透状态。在第3天，在容器中放水灌至土壤表面上的2～3cm处。灌水的土壤表面然后用选择好的丙酮水溶液(20/80V/V水/丙酮)混合物和足量的能达到约4.0Kg/公顷至0.50Kg/公顷活性组份的试验化合物进行处理。处理后，将容器放在温室台上，加水使其水平面保持在土壤表面2～3cm以上。
处理后的3～4周对植物作评估，并根据肉眼观察到的生长疏密度、大小、生气、颜色、生长变形及所有外观给除草作用分等级，等级系统如下所示。若再进行试验，则将数据平均，结果如表III所示。
            所用等级系统等级           含义          控制％
                           比较核对
0            无作用           0
1            痕量作用        1～5
2            稍有作用        6～15
3            中等作用       16～29
4            损伤           30～44
5            明显损伤       45～64
6            除草作用       65～79
7            良好的除草作用 80～90
8            接近完全杀除   91～99
9            完全杀除        100
－           未试验
           所用植物种类缩写名    一般名         学科名ECHCG        稗草    Echinochloa crus-galli
                 (L.)Beauv.ECHORE       水草    Echinochloa oryzoides
                 (ARD.)FritschORYSAT    Tebonnet稻 Oryaz sativa，L.
                 CV.Tehonnet
               表III
           芽前/移植后评估实施例   用量序号    kg/ha    ECHCG    ECHORC    ORYSAT8       2.0      9.0       -         0.0
     1.0      9.0      9.0        0.3
     0.5      9.0      9.0        0.39       1.0      9.0       -         1.5
     0.5      9.0       -         1.510      1.0      9.0      9.0        0.0
     0.5      9.0      9.0        0.012      1.0       -       9.0        0.0
     0.5       -       8.0        0.021      1.0       -       8.0        0.0
     0.5      7.0       -         0.022      1.0      9.0       -         0.5
     0.5      9.0       -         0.523      1.0      0.0       -         0.0
     0.5      0.0       -         0.024      1.0      9.0       -         2.0
     0.5      9.0       -         2.025      1.0       -       6.0        0.0
     0.5       -       2.0        0.029      1.0       -       7.0        3.0
     0.5      7.0       -         2.0
              表III
         芽前/移植后评估实施例    用量序号      kg/ha    ECHCG    ECHORC    ORYSAT30       1.0      9.0        -        0.5
      0.5      9.0        -        0.331       1.0      9.0        -        0.0
      0.5      9.0        -        0.032       1.0      9.0        -        0.0
      0.5      9.0        -        0.033       1.0      0.0        -        0.0
      0.5      0.0        -        0.034       4.0      9.0        -        0.0
      1.0      9.0       9.0       0.0
      0.5      9.0       7.0       0.038       1.0      8.0        -        0.0
      0.5      7.0        -        0.039       1.0      7.0        -        0.0
      0.5      7.0        -        0.040       1.0      9.0        -        0.0
      0.5      6.0        -        0.041       1.0      9.0        -        0.0
      0.5      9.0        -        0.042       1.0      0.0        -        0.0
      0.5      0.0        -        0.0
              表III
        芽前/移植后评估实施例    用量序号    kg/ha     ECHCG    ECHORC    ORYSAT43       1.0      8.0        -       1.0
      0.5      7.0        -       0.044       1.0      9.0        -       0.0
      0.5      7.0        -       0.045       1.0      9.0        -       0.0
      0.5      9.0        -       0.046       1.0      1.0        -       0.0
      0.5      0.0        -       0.047       1.0      0.0        -       0.0
      0.5      0.0        -       0.048       1.0      0.0        -       0.0
      0.5      0.0        -       0.049       1.0      9.0        -       0.0
      0.5      9.0        -       0.050       1.0       -        9.0      0.0
      0.5       -        9.0      0.051       1.0       -        9.0      0.0
      0.5       -        9.0      0.052       4.0      3.0        -       0.0
      1.0      7.0       0.0      0.0
      0.5      2.0       0.0      0.053       4.0      0.0        -       0.0
              表III
        芽前/移植后评估实施例    用量序号     kg/ha    ECHCG    ECHORC    ORYSAT
      1.0      2.0       -        0.0
      0.5      1.0       -        0.054       1.0      0.0       -        0.0
      0.5      0.0       -        0.055       1.0      9.0      9.0       0.0
      0.5      9.0      9.0       0.056       1.0      9.0       -        0.0
      0.5      8.0       -        0.057       1.0      9.0       -        0.0
      0.5      9.0       -        0.058       1.0      9.0       -        0.0
      0.5      9.0       -        0.059       1.0      0.0       -        0.0
      0.5      0.0       -        0.060       1.0      9.0       -        0.0
      0.5      9.0       -        0.061       1.0      2.0       -        0.0
      0.5      1.0       -        0.062       1.0      0.0       -        0.0
      0.5      0.0       -        0.063       1.0      9.0       -        0.0
               表III
         芽前/移植后评估实施例    用量序号     kg/ha    ECHCG    ECHORC    ORYSAT
      0.5      9.0       -         0.064       1.0      0.0       -         0.0
      0.5      0.0       -         0.065       1.0      9.0      9.0        0.0
      0.5      9.0      9.0        0.066       1.0      7.0       -         0.0
      0.5      1.0       -         0.067       1.0      9.0       -         0.0
      0.5      6.0       -         0.068       1.0      0.0       -         0.0
      0.5      0.0       -         0.069       1.0      9.0       -         0.0
      0.5      9.0       -         0.070       1.0      9.0       -         0.0
      0.5      9.0       -         0.071       1.0      0.0       -         0.0
      0.5      0.0       -         0.072       1.0      9.0       -         0.0
      0.5      9.0       -         0.073       1.0      0.0       -         0.0
             表III
         芽前/移植后评估实施例    用量序号     kg/ha    ECHCG    ECHORC    ORYSA
     0.5       0.0       -        0.074      1.0       9.0       -        0.0
     0.5       9.0       -        0.075      1.0       0.0       -        0.0
     0.5       0.0       -        0.076      1.0       4.0       -        0.0
     0.5       2.0       -        0.077      1.0       0.0       -        0.0
     0.5       0.0       -        0.078      1.0        -       0.0       0.0
     0.5        -       0.0       0.079      1.0        -       9.0       0.0
     0.5        -       9.0       0.080      1.0        -       0.0       0.0
     0.5        -       0.0       0.081      1.0        -       0.0       0.0
     0.5        -       0.0       0.082      1.0        -       9.0       0.0
     0.5        -       8.0       0.083      1.0        -       0.0       0.0
             表III
       芽前/移植后评估实施例    用量序号     kg/ha    ECHCG    ECHORC    ORYSAT
      0.5       -       0.0        0.084       1.0       -       6.0        0.0
      0.5       -       1.0        0.085       1.0      9.0       -         0.0
      0.5      9.0       -         0.086       1.0      9.0      9.0        0.0
      0.5      9.0      9.0        0.087       4.0      9.0       -         0.0
      1.0      9.0      9.0        0.0
      0.5      9.0      9.0        0.088       1.0      7.0       -         0.0
      0.5      6.0       -         0.089       1.0      6.0       -         0.0
      0.5      6.0       -         0.090       1.0      4.5       -         0.0
      0.5      3.5       -         0.091       1.0      9.0       -         0.0
      0.5      9.0       -         0.092       1.0      2.0       -         0.0
      0.5      2.0       -         0.093       1.0      9.0       -         0.0
              表III
         芽前/移植后评估实施例    用量序号     kg/ha    ECHCG    ECHORC    ORYSAT
      0.5      9.0      9.0       0.094       1.0      9.0       -        0.0
      0.5      9.0      9.0       0.095       1.0       -       9.0       0.0
      0.5       -       9.0       0.0101       1.0       -       9.0       0.0
      0.5       -       9.0       0.0110       1.0       -       8.5       0.0
      0.5       -       8.0       0.0111       1.0       -       9.0       0.0
      0.5       -       9.0       0.0114       2.0       -       0.0       0.0
      1.0       -       0.0       0.0
      0.5       -       0.0       0.0116       1.0       -       5.5       0.0
      0.5       -       1.5       0.0117       2.0       -       7.0       4.0
      1.0       -       7.0       3.0
      0.5       -       3.0       0.5121       1.0       -       9.0       2.0
      0.5       -       9.0       1.0
              表III
         芽前/移植后评估实施例    用量序号    kg/ha    ECHCG    ECHORC    ORYSAT122     1.0        -       9.0       0.0
     0.5        -       9.0       0.0127     1.0        -       0.0       0.0
     0.5        -       0.0       0.0133     1.0        -       9.0       0.0
     0.5        -       9.0       0.0136     1.0        -       9.0       0.0
     0.5        -       9.0       0.5137     1.0        -       9.0       0.0
     0.5        -       9.0       0.2138     2.0        -       9.0       4.0
     1.0        -       9.0       0.0
     0.5        -       9.0       0.0139     1.0        -       9.0       0.0
     0.5        -       9.0       0.0148     1.0        -       0.0       0.0
     0.5        -       0.0       0.0155     1.0        -       9.0       0.0
     0.5        -       9.0       0.0156     1.0        -       9.0       0.0
     0.5        -       9.0       0.0
             表III
       芽前/移植后评估实施例    用量序号    kg/ha     ECHCG     ECHORC   ORYSAT157    1.0         -        9.0      0.0
    0.5         -        9.0      0.0172    1.0         -        9.0      0.0
    0.5         -        8.5      0.0173    1.0         -        8.0      0.0
    0.5         -        8.0      0.0174    1.0         -        9.0      0.0
    0.5         -        9.0      0.0175    1.0         -        9.0      0.0
    0.5         -        9.0      0.0176    1.0         -        9.0      0.0
    0.5         -        9.0      0.0177    1.0         -        7.0      0.0
    0.5         -        5.5      0.0192    1.0         -        9.0      0.0
    0.5         -        9.0      0.0
                     实施例197在灌水的稻田条件下，在有移植稻存在时的试验化合物的芽前除草的评估。
在此实施例中，将Deluvian淤土(Toyokawa淤泥)放在100cm2×9cm(深)的塑料罐中。向罐中加水至土壤表面的水平处，并将混合物拌3cm深处。
然后将单子杂草和块茎种入罐中土壤0～2cm深处，移入2.5叶片状态的稻植物，将犁植物种在约3cm土壤深处。然后向所有罐中加水至3cm深，并在试验期间保持3cm深。在移植入稻植物和播入杂草种子和块茎后按实施例196所述的方法施加试验化合物。然后将罐子放在温室台上，按常规方法护理。处理后于20和30天时评估试验。处理后30天评估的结果如表IV所示。所用的等级系统与实施例196所述的相同。
                  所用的植物
缩写    一般名                    学科名
ECHCG    稗草                Echinochloa crus-galli
SAGPY    慈菇                Sagittaria pygmaea
CYPSE    平莎草，多年生      Cyperus serotinus
MOOVA    雨久花              Monochoria Vaginalis
CYPDI    平莎草，小花        Cyperus difformis
SCPJU    纸莎草              Scirpus juncoides
ORYSAK    稻，Koshihikari    Oryaz sativa，L.
                             CV.Koshihikari
                            表IV
                     芽前/移植后评估实施例   用量序号     kg/ha   ECHCG   SAGPY   CYPSE   MOOVA   CYPDI   SCPJU   ORYSAK8       1.0      9       2       2       9       9       8       0
     0.5      9       1       0       9       9       7       09       1.0      7       0       0       1       2       0       0
     0.5      6       0       0       0       0       0       010      1.0      9       2       0       9       9       5       0
     0.5      9       0       0       8       9       4       012      1.0      9       0       0       7       3       0       0
     0.5      9       0       0       6       2       0       021      1.0      8       0       7       3       5       0       0
     0.5      7       0       2       0       3       0       022      1.0      9       1       1       9       8       7       0
     0.5      9       0       0       8       7       5       023      2.0      9       0       0       3       2       2       0
     1.0      6       0       0       0       0       0       0
     0.5      4       0       0       0       0       0       025      1.0      9       0       0       9       6       3       0
     0.5      9       0       0       8       3       0       031      1.0      9       0       4       7       7       3       0
     0.5      9       0       0       7       6       0       032      1.0      9       0       2       8       8       2       0
     0.5      9       0       1       7       7       0       033      2.0      6       9       9       9       9       7       8
     1.0      4       8       9       9       9       6       8
     0.5      2       7       9       9       8       5       535      2.0      8       2       0       0       1       0       0
     1.0      8       0       0       0       0       0       0
     0.5      7       0       0       0       0       0       038      1.0      8       0       0       0       0       0       0
     0.5      6       0       0       0       0       0       039      1.0      7       0       0       0       0       0       0
     0.5      5       0       0       0       0       0       0
                             表IV
                       芽前/移植后评估实施例   用量序号     kg/ha   ECHCG   SAGPY   CYPSE   MOOVA   CYPDI   SCPJU   ORYSAK40      1.0       9       0       0       0       0       0       0
     0.5       9       0       0       0       0       0       041      1.0       9       1       7       8       9       2       1
     0.5       9       0       3       7       7       1       042      2.0       2       0       0       0       0       0       0
     1.0       0       0       0       0       0       0       0
     0.5       0       0       0       0       0       0       043      1.0       8       0       0       0       0       0       0
     0.5       6       0       0       0       0       0       044      1.0       8       0       0       0       0       0       0
     0.5       5       0       0       0       0       0       045      1.0       7       0       0       0       0       0       0
     0.5       4       0       0       0       0       0       046      2.0       0       0       0       0       0       0       0
     1.0       0       0       0       0       0       0       047      2.0       0       0       0       0       0       0       0
     1.0       0       0       0       0       0       0       048      2.0       0       0       0       0       0       0       0
     1.0       0       0       0       0       0       0       049      1.0       9       0       5       9       9       8       0
     0.5       9       0       2       9       8       5       050      1.0       9       0       0       8       8       1       0
     0.5       9       0       0       8       7       0       051      1.0       9       0       2       8       7       0       0
     0.5       8       0       0       8       5       0       055      1.0       9       1       9       9       9       9       0
     0.5       9       0       8       9       9       8       056      1.0       8       0       0       3       2       0       0
     0.5       6       0       0       2       1       0       057      1.0       9       0       2       2       2       0       0
                             表IV
                      芽前/移植后评估实施例   用量序号     kg/ha   ECHCG   SAGPY   CYPSE   MOOVA   CYPDI   SCPJU   ORYSAK
      0.5      9       0       0       1       1       0       058       1.0      9       0       0       4       3       0       0
      0.5      9       0       0       2       1       0       059       1.0      5       0       0       1       2       2       0
      0.5      3       0       0       0       0       0       060       1.0      9       0       5       6       5       0       0
      0.5      9       0       0       5       3       0       061       1.0      4       0       0       1       1       0       0
      0.5      3       0       0       0       0       0       062       1.0      2       0       0       0       0       0       0
      0.5      0       0       0       0       0       0       063       1.0      9       0       0       2       1       1       0
      0.5      9       0       0       1       0       0       064       1.0      1       0       0       0       0       0       0
      0.5      0       0       0       0       0       0       065       1.0      9       4       5       9       9       2       1
      0.5      9       2       2       9       9       0       066       1.0      9       0       0       2       2       0       0
      0.5      8       0       0       0       0       0       067       1.0      9       0       1       2       3       0       1
      0.5      8       0       0       0       2       0       068       1.0      0       0       0       0       0       0       0
      0.5      0       0       0       0       0       0       069       1.0      9       0       2       7       7       2       1
      0.5      9       0       0       6       6       0       070       1.0      9       0       5       2       1       0       0
      0.5      9       0       0       0       0       0       071       1.0      6       0       0       0       0       0       0
      0.5      5       0       0       0       0       0       072       1.0      9       0       1       7       4       0       0
                              表IV
                         芽前/移植后评估实施例    用量序号    kg/ha    ECHCG   SAGPY    CYPSE    MOOVA    CYPDI    SCPJU    ORYSAK
     0.5       9       0        0        3        2        0        073      1.0       7       0        2        0        0        0        0
     0.5       3       0        0        0        0        0        074      1.0       9       0        0        4        6        2        0
     0.5       9       0        0        2        3        0        075      1.0       4       0        0        2        1        0        0
     0.5       2       0        0        0        0        0        076      1.0       7       0        0        2        1        1        0
     0.5       6       0        0        0        0        0        077      1.0       6       0        0        2        0        0        0
     0.5       6       0        0        1        0        0        078      1.0       2       1        4        2        0        6        0
     0.5       0       0        2        1        0        4        079      1.0       9       2        0        9        9        7        0
     0.5       9       1        0        8        7        6        085      1.0       9       0        0        4        4        2        0
     0.5       7       0        0        1        2        1        086      1.0       9       5        5        9        9        9        0
     0.5       9       2        2        9        9        8        087      1.0       9       0        4        8        8        4        0
     0.5       9       0        2        7        8        2        088      1.0       5       0        0        0        0        0        0
     0.5       4       0        0        0        0        0        089      1.0       4       0        0        0        0        0        0
     0.5       2       0        0        0        0        0        090      1.0       3       0        0        0        0        0        0
     0.5       0       0        0        0        0        0        091      1.0       9       0        0        5        8        0        0
     0.5       9       0        0        3        5        0        093      1.0       9       0        2        9        9        7        0
                               表IV
                          芽前/移植后评估实施例    用量序号    kg/ha    ECHCG    SAGPY    CYPSE    MOOVA    CYPDI    SCPJU    ORYSAK
      0.5       9        0        0        8        8        5         094       1.0       9        0        7        9        9        8         0
      0.5       9        0        3        9        9        5         0116      0.50      7        6        3        2        8        6         0
      0.25      5        4        1        0        7        5         0117      0.50      7        2        5        4        8        7         1
      0.25      5        1        2        0        7        6         1119      0.50      9        2        0        0        2        0         0
      0.25      8        0        0        0        1        0         0120      0.50      9        0        -        6        9        8         0
      0.25      9        0        -        2        9        7         0121      0.50      9        0        3        5        9        8         0
      0.25      9        0        0        2        9        6         0122      0.50      9        4        0        0        9        5         0
      0.25      9        2        0        0        9        3         0123      0.50      9        0        0        0        9        7         0
      0.25      9        0        0        0        7        5         0124      0.50      9        2        0        0        9        7         0
      0.25      9        0        0        0        9        6         0125      0.50      9        0        2        5        9        9         0
      0.25      9        0        0        2        9        6         0126      0.50      9        2        -        3        7        6         0
      0.25      9        2        -        2        3        2         0136      0.50      9        0        0        2        7        5         0
      0.25      9        0        0        0        6        4         0137      0.50      9        0        2        7        9        9         0
      0.25      9        0        1        7        9        9         0138      0.50      9        0        0        5        9        9         0
      0.25      9        0        0        6        9        9         0139      0.50      9        0        2        8        9        9         0
                                  表IV
                            芽前/移植后评估实施例    用量序号      kg/ha   ECHCG    SAGPY    CYPSE    MOOVA    CYPDI    SCPJU    ORYSAK
      0.25      9        0        2        8        9        9         0155      0.50      9        0        2        9        9        9         0
      0.25      9        0        -        7        9        9         0

Claims (10)

1.一种用来控制单子叶年生、多年生和水生植物物种的方法，包括给含有种子或其它繁殖器官的水或土壤施加除草有效量的式I化合物：
Figure A9510759200021
(I)其中
X和X′各自是卤素、C1～C4烷基或C2～C4链烯基；
W，Y和Z各自是O或S；
R是1～3个选自H、卤素、C1～C4烷基、C3～C6环烷基、C1～C4卤代烷基或C1～C4烷氧基的任何结合形式；
R1是1～4个选自H、卤素、OH、CN、NO2、SH、任意地被一个或多个卤素或OR2取代的C1～C6的烷基、C3～C6环烷基、C1～C6烷硫基、C2～C6链烯基、C2～C6卤代链烯基、C2～C6炔基、C2～C6卤代炔基、OR2、OCH2COOR3、OCH2OR4、OCOOR5、OCONHR6、OCOR7、S(O)nR8、COR9、CH(OR10)2、任意地用一至三个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基、或任意地被一至三个卤素、CN、C1～C4烷基、C1～C4卤代烷基或C1～C4烷氧基取代的苄基的任何结合形式；
R2是H、C1～C4烷基、C1～C4卤代烷基、C2～C6链烯基。C2～C6炔基、C2～C6卤代链烯基或C2～C6卤代炔基；
R3、R4、R5、R6和R7各自是H、C1～C4烷基、C1～C4卤代烷基、C3～C6环烷基、任意地被1～3个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基、或任意地用1～3个卤素、C1～C4烷基、C1～C4卤代烷基或C1～C4卤代烷基或C1～C4烷氧基取代的苄基；R8是C1～C4烷基或任意地用1～3个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基；
R9是H、OH、C1～C4烷基、C1～C4烷氧基、任意地用1～3个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基、任意地用1～3个卤素、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苄基或是NR11R12；
R10是H、C1～C4烷基或-(CH2)m-；
R11和R12各自是H、C1～C4烷基、C2～C4链烯基或者R11和R12与其它原子连结在一起形成任意地被氧所间隔的5-元或6-元环；n是整数0、1或2；以及m是整数2或3
2.根据权利要求1所述的方法，其中式I化合物是4-(2，6-二氯苯氧基)-6-甲氧基香豆素；
4-(2，6-二溴苯氧基)-8-甲氧基香豆素；
4-(2，6-二氯苯氧基)-8-甲氧基香豆素；
4-(2，6-二氯苯氧基)-6，7-二甲氧基香豆素；
4-(2，6-二溴苯氧基)-6，7-二甲氧基香豆素；
4-(2，6-二氯苯氧基)-5，6，7-三甲氧基香豆素；
4-(2，6-二溴苯氧基)-5，6，7-三甲氧基香豆素；
4-(2，6-二氯苯氧基)-5-(三氟甲基)香豆素；
4-(2，6-二溴苯氧基)-5-(三氟甲基)香豆素；
4-[(2-氯-6-甲基)苯氧基]-5-氯香豆素；
4-(2，6-二溴苯氧基)-5-氯香豆素；
4-(2，6-二氯苯氧基)-5-氯香豆素；
4-[(2-氯-6-甲基)苯氧基]-5-氟香豆素；
4-(2，6-二氯苯氧基)-5-氟香豆素；
4-(2，6-二氯苯氧基)-5-甲基香豆素；
4-[(2-氯-6-甲基)苯氧基]-5-甲基香豆素；或
4-(2，6-二氯苯氧基)-5-硝基香豆素。
3.一种在作物存在下选择性控制杂草的方法，它包括给所述杂草的种子或繁殖器官所处的、且已种有或移植了作物的土壤或水中施加除草有效量的式I化合
              物：
Figure A9510759200041
(I)其中X、X′、W、Y、Z、R和R1的定义与权利要求1中的定义相同。
4.根据权利要求3所述的方法，其中的禾本科作物是小麦、燕麦、大麦、裸麦、稻或玉米。
5.根据权利要求4所述的方法，其中式I化合物以4.0～0.06Kg/公顷的比率施加。
6.根据权利要求5所述的方法，其中式I化合物是4-(2，6-二氯苯氧基)-6-甲氧基香豆素；
4-(2，6-二溴苯氧基)-8-甲氧基香豆素；
4-(2，6-二氯苯氧基)-8-甲氧基香豆素；
4-(2，6-二氯苯氧基)-6，7-二甲氧基香豆素；
4-(2，6-二溴苯氧基)-6，7-二甲氧基香豆素；
4-(2，6-二氯苯氧基)-5，6，7-三甲氧基香豆素；
4-(2，6-二溴苯氧基)-5，6，7-三甲氧基香豆素；
4-(2，6-二氯苯氧基)-5-(三氟甲基)香豆素；
4-(2，6-二溴苯氧基)-5-(三氟甲基)香豆素；
4-[(2-氯-6-甲基)苯氧基]-5-氯香豆素；
4-(2，6-二溴苯氧基)-5-氯香豆素；
4-(2，6-二氯苯氧基)-5-氯香豆素；
4-[(2-氯-6-甲基)苯氧基]-5-氟香豆素；
4-(2，6-二氯苯氧基)-5-氟香豆素；
4-(2，6-二氯苯氧基)-5-甲基香豆素；
4-[(2-氯-6-甲基)苯氧基]-5-甲基香豆素；或
4-(2，6-二氯苯氧基)-5-硝基香豆素。
7.一种式I化合物：
Figure A9510759200051
(I)其中
X和X′各自是卤素、C1～C4烷基或C2～C4链烯基；
W、Y和Z各自是O或S；
R是1～3个选自H、卤素、C1～C4烷基、C3～C6环烷基、C1～C4卤代烷基或C1～C4烷氧基的任何结合形式；
R1是1～4个选自H、卤素、OH、CN、NO2、SH、任意地被一个或多个卤素或OR2取代的C1～C6的烷基、C3～C6环烷基、C1～C6烷硫基、C2～C6链烯基、C2～C6卤代链烯基、C2～C6炔基、C2～C6卤代炔基、OR2、OCH2COOR3、OCH2OR4、OCOOR5、OCONHR6、OCOR7、S(O)nR8、COR9、CH(OR10)2、任意地用一至三个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基、或任意地被一至三个卤素、CN、C1～C4烷基、C1～C4卤代烷基或C1～C4烷氧基取代的苄基的任何结合形式；
R2是H、C1～C4烷基、C1～C4卤代烷基、C2～C6链烯基。C2～C6炔基、C2～C6卤代链烯基或C2～C6卤代炔基；
R3、R4、R5、R6和R7各自是H、C1～C4烷基、C1～C4卤代烷基、C3～C6环烷基、任意地被1～3个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基、或任意地用1～3个卤素、C1～C4烷基、C1～C4卤代烷基或C1～C4卤代烷基或C1～C4烷氧基取代的苄基；R8是C1～C4烷基或任意地用1～3个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基；
R9是H、OH、C1～C4烷基、C1～C4烷氧基、任意地用1～3个卤素、CN、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苯基、任意地用1～3个卤素、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基或C1～C4卤代烷氧基取代的苄基或是NR11R12；
R10是H、C1～C4烷基或-(CH2)m-；
R11和R12各自是H、C1～C4烷基、C2～C4链烯基或者R11和R12与其它原子连结在一起形成任意地被氧所间隔的5-元或6-元环；n是整数0、1或2；以及m是整数2或3
8.根据权利要求7所述的化合物，它们是4-(2，6-二氯苯氧基)-8-甲氧基香豆素：
4-(2，6-二溴苯氧基)-8-甲氧基香豆素；
4-(2，6-二氯苯氧基)-6，7-二甲氧基香豆素；
4-(2，6-二溴苯氧基)-6，7-二甲氧基香豆素；
4-(2，6-二氯苯氧基)-5，6，7-三甲氧基香豆素；
4-(2，6-二溴苯氧基)-5，6，7-三甲氧基香豆素；
4-(2，6-二氯苯氧基)-5-(三氟甲基)香豆素；
4-(2，6-二溴苯氧基)-5-(三氟甲基)香豆素；
4-[(2-氯-6-甲基)苯氧基]-5-氯香豆素；
4-(2，6-二溴苯氧基)-5-氯香豆素；
4-(2，6-二氯苯氧基)-5-氯香豆素；
4-[(2-氯-6-甲基)苯氧基]-5-氟香豆素；
4-(2，6-二氯苯氧基)-5-氟香豆素；
4-(2，6-二氯苯氧基)-5-甲基香豆素；
4-[(2-氯-6-甲基)苯氧基]-5-甲基香豆素；或
4-(2，6-二氯苯氧基)-5-硝基香豆素。
9.一种催化剂组合物，它包括农业上可接受的载体及式I化合物(I)其中X、X′、W、Y、Z、R和R1的定义与权利要求7中所述者相同。
10.一种制备式Ia化合物的方法：
Figure A9510759200081
(Ia)其中W、X、X′、R和R1的定义与权利要求7中所述者相同，它包括使式V化合物：
Figure A9510759200082
(V)与至少1摩尔当量的式VI化合物在溶剂存在下，任意地在碱的存在下，进行反应。
Figure A9510759200083
(VI)
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CN104592183A (zh) * 2015-01-15 2015-05-06 青岛农业大学 N-酰基-n-间氟苄基-8-氨基香豆素类化合物及其制备与除草用途
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CN106749144B (zh) * 2016-12-27 2019-06-28 江苏大学 7-芳氧乙酰氧基香豆素类化合物及其在农药上的应用
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