CN1061776A - 具有除草作用的甲酰胺类衍生物 - Google Patents

具有除草作用的甲酰胺类衍生物 Download PDF

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CN1061776A
CN1061776A CN91111100A CN91111100A CN1061776A CN 1061776 A CN1061776 A CN 1061776A CN 91111100 A CN91111100 A CN 91111100A CN 91111100 A CN91111100 A CN 91111100A CN 1061776 A CN1061776 A CN 1061776A
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C·J·福斯特
T·吉尔科森
R·斯托克
I·J·吉尔摩
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Abstract

下式化合物是除草剂，

Description

本发明是关于具有除草作用的甲酰胺类衍生物、它们的制备、含有该类衍生物的除草剂组合物以及在抑制不需要的植物生长中它们的应用。
2-苯氧基-3-吡啶甲酰胺类化合物的除草作用是熟知的。在1981和1982年公布了三篇美国专利说明书（4251263，4270946和4327218），它们是关于A.D.Gutman的工作-2-苯氧基烟酰胺类除草剂。后来Gutman的综述（“Synthesis  and  Chemistry  of  Agrochem-icals”，第5章，1987，由美国化学会出版）表明，他的研究是由2-苯氧基烟酸类化合物（该类化合物被发现是无效的）开始，发展到研究N-烷基酰胺类衍生物（该类化合物被发现有弱的除草作用），然后集中研究N-苯基和N-苄基酰胺类化合物，它们是最有效的化合物类型。吡氟草胺〔N-（2，4-二氟苯基）-2-（3-三氟甲基苯氧基）-3-吡啶甲酰胺〕后来确定由不同的研究部门开发为商业除草剂用于抗冬季谷物（如冬小麦和大麦）的阔叶杂草。
美国专利说明书4251263涉及Gutman的N-烷基酰胺类，以及N-链烯基和N-炔基酰胺类。制得的并经试验证实最有效的脂肪族酰胺类化合物是N-（1，1-二甲基丙-2-炔-2-（3-三氟甲基苯氧基）-3-吡啶甲酰胺，对于特定的窄叶和阔叶杂草，芽前施药它具有85%的控制作用，芽后施药它仅有57%的控制作用。
现已惊奇地发现，酰胺氮原子带有脂肪族（直链和脂环族的）和其他取代基的2-苯氧基-6-吡啶甲酰胺类化合物，在芽前和/或芽后施药时对于典型的窄叶或阔叶杂草具有意想不到的好的除草作用;某些实例在芽前和芽后施药的情况下对试验种类的杂草具有90-100%的效果。
因此，本发明提供了具有下述通式Ⅰ的化合物
Figure 91111100X_IMG6
（Ⅰ）
其中n为整数1-5，并且各个X独立地代表氢或卤原子、，由1个或多个相同或不同的选自卤原子和氰基、羟基或烷氧基的取代基任意取代的烷基或烷氧基，或者为氰基、硝基、链烯氧基、炔氧基、烷硫基、卤代烷硫基、烯硫基或炔硫基;
m为零或1-3的整数，并且各个Y独立地代表卤原子或烷基或卤代烷基;
Z代表氧原子或硫原子;并且
R1和R2各自独立地代表氢原子、由1个或多个相同或不同的选自卤原子或羟基、氰基、烷氧基、烷硫基、烷氧基羰基、或者一或二烷氨基取代基任意取代的烷基，或者为链烯基、炔基、环烷基、或任意取代的环烷基烷基，或者为羟基、烷氧基、烯氧基、炔氧基、烷氧基羰基、氨基、一或二烷氨基、烷氧基羰基氨基、由卤原子任意取代的芳氨基、或二烷基氨基甲酰基;或者
R1和R2一起代表由氧或硫原子或由基团-NR-任意断开的亚烷基链，其中R代表氢原子或烷基。
如果任一取代基X、Y、R1和R2代表或含有一烷基、链烯基或炔基取代基，那么它可以是直链或支链的，并且有直到12个碳原子是合适的，有直到8个碳原子较好，有直到5个碳原子尤其好。因此，例如烷基R2可以是丁基，如异丁基、正丁基、仲丁基或叔丁基。如果有环烷基取代基，那么有3-8个碳原子环是合适的，有3-6个碳原子环较好。合适的芳基是苯基。亚烷基链有3-6个链节是合适的，有4或5个链节较好。合适的卤原子指氟、氯、溴或碘原子;较好的卤代烷基是三氟甲基、三氟乙基和氟乙基。
取代基Xn可以在苯氧环上任何自由的位置，或者结合在苯氧环上的一组位置。
1个苯氧基取代基X希望是位于3-（或间-）位，并且是氢、氟、氯或溴原子、或为硝基、乙基、甲氧基较好，以三氟甲基为最好。如果有另外的取代基X，那么它们在4-和/或5-位是合适的，并且可以与间位的取代基相同，或者最好不相同。该另外的取代基X选择氯原子较好，选择氟原子最好。
当然，取代基Xn可以在其他位置，并且可以是例如2，3-或2，5-二甲基。
仅有1个或2个取代基X是较好的，并且最好是X之一或唯一的一个X代表取代基3-三氟甲基。
m为零较好。
Z代表氧原子较好。
基团R1和R2在各自存在时可以是相同的或不同的。R1代表氢原子或C1-4烷基或C2-4链烯基较好，代表烯丙基是合适的，代表氢或C1-4烷基最好，而R2代表未取代的C1-8烷基，特别是C1-6烷基;由氟、羟基、氰基、C1-2烷氧基、（C1-2烷氧基）羰基或者一或二（C1-2烷基）氨基取代的C1-4烷基，如氟乙基、三氟乙基、氰基丙基、羟乙基、甲氧基乙基、乙氧羰基甲基或二甲氨基乙基;C3-8环烷基，特别是环丙基、环丁基、环戊基或环己基;C2-4链烯基，如烯丙基或甲代烯丙基;C2-4炔基，如丙炔基;C1-4烷氧基，例如乙氧基;（C1-4烷基）氨基，例如甲氨基;C2-4链烯氧基，如丙烯氧基;（C1-2烷氧基）羰基，如乙氧基羰基;（C1-2烷氧基）羰基氨基，如乙氧基羰基氨基;二（C1-2烷基）氨基甲酰基，如二甲基氨基甲酰基;芳氨基，如苯氨基或对氯苯氨基;卤素取代的（C3-6环烷基）C1-4烷基，如氯取代的环丙基甲基。
特别好的是R1代表氢原子，而R2代表未取代的C1-5烷基、由氟或甲氧基取代的C1-2烷基、C3-6环烷基、C3链烯基、C3炔基、C1-2烷氧基、C3链烯氧基或氯取代的环丙基甲基，或者R1代表C1-3烷基，而R2代表相同的C1-3烷基或氯取代的环丙基甲基。
特别好的化合物是其中R1代表氢原子，R2代表乙基、丙基、环丙基或环丁基的化合物。
当R1和R2一起代表亚烷基链时，合适的链是由4或5个链原子组成的，例如-（CH2）4-、（CH2）2O（CH2）2-或-（CH2）2NR（CH2）2-，这里R是C1-2烷基，甲基是合适的。R1和R2为-（CH2）4-较好。
通式Ⅰ的化合物可以通过合适的苯氧基吡啶甲酸衍生物与合适的胺反应制备（方法A），或者通过合适的2-卤素-6-吡啶甲酰胺衍生物与合适的碱金属酚盐反应制备（方法B）。上述方法构成了本发明的又一方面。
按照方法A，其中Z为氧的通式Ⅰ化合物可按下法制备;使通式Ⅱ的化合物（其中Xn和Ym的定义同前，L代表离去基团）与通式NHR1R2（其中R1和R2的定义同前）的胺反应，
Figure 91111100X_IMG7
（Ⅱ）
离去基团是在反应条件下从起始物质中分解的基团，结果促进了在一特定位置的反应。
离去基团可以合适地为卤素原子，例如溴或者特别是氯原子、或烷氧基（合适地为C1-4烷氧基，特别是甲氧基）。
方法A在惰性有机溶剂，例如二甲基甲酰胺，或芳香族烃类（如苯或甲苯），或卤代烃类（如二氯甲烷）或醚（如***），或酯（如乙酸乙酯）存在下进行均是合适的，在0-100℃范围内进行是合适的。
用大体上等摩尔量的反应物进行反应是合适的。但是一种反应物（通常是胺）过量是有利的，例如苯氧基吡啶甲酸衍生物与胺的摩尔比在1∶1-1∶1.1的范围内。
当L代表卤素原子时，上述反应在0-50℃范围内进行是合适的，最好在环境温度下进行，并且上述反应在碱（如碳酸钾）存在下进行是合适的，最好在胺碱（如三乙胺或过量的胺起始物质）存在下进行。
当L代表烷氧基时，上述反应在0-100℃范围内进行是合适的，最好在室温（或20℃）和在没有附加碱的情况下进行。
按照方法B，其中Z为氧的通式Ⅰ化合物可以按下法制备：使通式Ⅲ化合物与通式Ⅳ化合物反应，
Figure 91111100X_IMG8
（Ⅲ）
式Ⅲ中Ym、R1和R2的定义同上，Hal代表卤素原子，
Figure 91111100X_IMG9
（Ⅳ）
式Ⅳ中Zn的定义同上，M代表碱金属原子。
Hal代表溴原子是合适的，或者代表氯原子是特别合适的。R代表钾原子是合适的，或者代表钠原子是特别合适的。
反应B可以按下述方法进行：用碱金属醇盐（如甲醇钠）与酚制得碱金属酚盐，然后在吡啶中于芳香族烃（如二甲苯）存在下，使该酚盐与大体上等摩尔量的反应物Ⅲ及铜催化剂（如氯化亚铜）一起反应，反应在适当高的温度（如回流）下进行。该方法已在英国专利说明书2050168A中叙述。
另外，方法B也可以在碱金属氢化物如氢化钠存在下，于无水溶剂如二甲基甲酰胺中，在高温（如在50℃-125℃）下进行，或者在碱金属碳酸盐如碳酸钠或碳酸钾存在下，在有机溶剂如二甲基甲酰胺或喹啉中，于20℃-150℃范围（在反应混合物的回流温度下进行反应是方便的）与氧化亚铜和/或铜粉反应。
其中Z代表硫原子的通式Ⅰ化合物按下法制备：使其中Z代表氧原子的通式Ⅰ化合物与五硫化二磷在一般条件，例如于惰性芳香族溶剂如苯、甲苯、吡啶或喹啉存在下，在加热（在回流下是合适的）下进行。
本发明的化合物可以用一般的技术，例如溶剂萃取、蒸发、然后重结晶，或经硅胶层析进行分离和纯化。
可以从相应的苯氧基-取代的吡啶甲酸按一般的方法制备通式Ⅱ化合物，例如可以用醇和酸催化剂制得酯，用亚硫酰氯或亚硫酰溴制得酰基氯或酰基溴。苯氧基取代的吡啶甲酸本身可以按一般的方法从氯吡啶甲酸或其酯制得。氯吡啶甲酸或其酯可以按J.Pharm.Belg.（1980），35，1，5-11所述的方法制备。
式Ⅲ化合物可以按方法A类似的方法进行制备，即使命名式NHR1R2取代胺与2-卤素-6-吡啶甲酸衍生物（式Ⅴ）进行反应，
Figure 91111100X_IMG10
Ⅴ
其中Ym、Hal和L的定义同上。式Ⅴ化合物可以按一般的方法从吡啶甲酸制得。
取代的胺NHR1R2和式Ⅳ的酚盐或者是已知的，或者可以用一般的方法制得。
在芽前和芽后施用时，已经发现本发明化合物对杂草，特别是对阔叶杂草，包括鼠尾看麦娘、野燕麦、大狗尾草、狗尾草、园叶牵牛、猪殃殃、龙葵、婆婆纳和繁缕具有十分好的广谱除草作用。试验实例表示本发明化合物对于小粒谷类作物如玉米、小麦、大麦和稻子，以及对于阔叶作物如大豆、向日葵和棉花具有选择性，这表明本发明化合物可以用于抑制上述作物田中的杂草生长。
此外，本发明还提供了含有上述定义的式Ⅰ化合物以及载体的除草组合物，以及制备该组合物的方法，该方法包括使式Ⅰ化合物与载体相混合。
本发明还提供了本发明的化合物或组合物作为除草剂的应用。另外，本发明也提供了抑制某场所不需要的植物生长的方法，该方法包括用本发明的化合物或组合物处理该场所。给该场所施药可以是芽前施药或芽后施药。应用的有效成分的剂量可以是例如在0.01-10kg/ha的范围，0.05-4kg/ha是合适的。该场所可以是例如土壤或作物区的植物，具有代表性的作物是禾谷类，如小麦、大麦，以及阔叶作物，如大豆、向日葵和棉花。
本发明组合物中的载体是与有效成分一起配制的、以便容易向需要处理的场所（例如植物、种子或土壤）施药，或者便于贮存、运输和使用的任何物质。载体可以是固体或液体，并包括通常为气体但已被压缩成液体的物质，通常用于配制除草剂组合物的任何载体均可以应用。本发明的组合物含有0.5-95%重量的有效成分较好。
合适的固体载体包括天然的和合成的粘土及硅酸盐，例如天然的硅石，如硅藻土;硅酸镁，如滑石;硅酸铝镁，如绿坡缕石和蛭石;硅酸铝，如高岭土、蒙脱土和云母;碳酸钙;硫酸钙;硫酸铵;合成的水合氧化硅和合成的硅酸钙或硅酸铝。元素，如碳和硫;天然的和合成的树脂，如苯并呋喃树脂、聚氯乙烯、以及苯乙烯聚合物和共聚物;固体多氯酚;沥清;石蜡;以及固体肥料，如过磷酸钙。
合适的液体载体包括水;醇，如异丙醇和二元醇;酮，如丙酮、甲乙酮、甲基异丁基酮和环己酮;醚;芳香族或脂肪族烃类，如苯、甲苯和二甲苯、石油馏分，如煤油和轻元机油;氯代烃类，如四氯化碳、全氯乙烯和三氯乙烷。各种不同的液体混合物通常是合适的。
配制和运输的农用组合物通常为浓的形式，然后在施药前由使用者进行稀释。存在少量的表面活性剂有利于稀释过程。因此，最好在本发明的组合物中，至少有一种载体是表面活性剂。例如组合物可以含有至少二种载体，其中至少一种是表面活性剂。
表面活性剂可以是乳化剂、分散剂或湿润剂;它可以是非离子型的或离子型的。合适的表面活性剂其实例有聚丙烯酸和木素磺酸的钠盐和钙盐;在分子中含有至少12个碳原子的脂肪酸或脂肪族胺或酰胺与环氧乙烷和/或氧化丙烯的缩合产物;丙三醇、山梨糖醇、蔗糖或季戊四醇的脂肪酸酯;上述物质与环氧乙烷和/或氧化丙烯的缩合物;脂肪醇或烷基酚例如对辛基酚或对辛基甲酚与环氧乙烷和/或氧化丙烯的缩合产物;上述缩合产物的硫酸盐或磺酸盐;碱金属或碱土金属的盐，最好是在分子中含有至少10个碳原子的硫酸或磺酸酯的钠盐，如十二烷基硫酸钠、仲烷基硫酸钠、磺化的蓖麻油的钠盐和烷基芳基磺酸钠，如十二烷基苯磺酸钠;以及环氧乙烷的聚合物和环氧乙烷与氧化丙烯的共聚物。
可以将本发明的组合物配制成例如可湿性粉剂、粉剂、颗粒剂、溶液剂、乳油、乳剂、浓混悬液剂和气雾剂。可湿性粉剂通常含有25、50或75%重量的有效成分，除了固体惰性载体之外通常含3-10%重量的分散剂，并且如果需要，可以含有0-10%重量的稳定剂和/或其他添加剂，如渗透剂或粘着剂。粉剂通常配制成与可湿性粉剂具有相同组份但没有分散剂的浓粉剂，并且在现场用另外的固体载体进行稀释，得到通常含有1/2-10%重量的有效成分的组合物。通常将颗粒剂制成具有10-100英国标准筛号（1.676-0.152mm）的大小，并可以通过附聚作用或浸渍技术进行制备。一般来说，颗粒剂含有1/2-75%重量的有效成分和0-10%重量的添加剂如稳定剂、表面活性剂、缓释调节剂及粘合剂。所谓“干的可流动的粉剂”是由具有较高浓度有效成分的较小颗粒所组成。乳油通常含有溶剂、10-50%w/v的有效成分、2-20%乳化剂和0-20%w/v的其他添加剂，如稳定剂、渗透剂和腐蚀抑制剂，如果需要，乳油除含溶剂之外还含有共溶剂。通常配制浓混悬液剂，以便得到稳定的、无沉淀物的可流动的产物，并通常含有10-75%重量的有效成分、0.5-15%重量的分散剂、0.1-10%重量的悬浮剂，如保护胶体和摇溶剂，和0-10%重量的其他添加剂，如去泡剂、腐蚀抑制剂、稳定剂、渗透剂和粘着剂，以及水或有效成分实质上不溶的有机液体，某些有机固体或无机盐可以溶解在上述组合物中，以便有助于防止沉淀或作为水的抗冻剂。
例如通过用水稀释本发明的可湿性粉剂或浓乳油得到的水分散剂和乳剂也在本发明的范围内。所述乳剂可以是水包油型的，或为油包水型的，并且可以有像“蛋黄酱”一样浓稠的稠度。
本发明的组合物还可以含有其他成分，例如具有杀虫或杀菌作用的化合物或其他的除草剂。
下述实例详细地叙述本发明。实例1叙述了通式Ⅱ酯的制备方法，实例2-63是关于通式Ⅰ化合物的制备方法;实例2-61是用方法A，实例62是用方法B，实例63是将其中Z为氧的通式Ⅰ化合物转变为其中Z为硫的通式Ⅰ化合物。所有的结构均经质谱和/或3001H核磁共振谱确证。
实例1
制备6-（3-α，α，α-三氟甲基苯氧基）吡啶甲酸甲酯
向3-α，α，α-三氟甲基苯酚（8.9g）的二甲苯（50ml）溶液中加入甲醇钠（由1.3g金属钠置于20ml甲醇中制得）溶液。真空下蒸除溶剂得到干燥的酚钠盐。加入吡啶（25ml）和二甲苯（50ml），随后加入氯化亚铜（1.5g），并将混合物加热回流。滴加6-氯吡啶甲酸甲酯（8.5g）的二甲苯（50ml）溶液。混合物再回流14小时。冷却后将混合物倒入水（500ml）中，并用稀硫酸酸化。分出二甲苯层，水层再用***萃取。合并的萃取液用盐水洗涤、用无水硫酸镁干燥并蒸发。残余物经硅胶柱纯化，用5%（v/v）***/二氯甲烷作为洗脱剂，得到标题化合物（7.4g），为黄色固体，mp.43-44℃。
元素分析（%）：
C14H10O3NF3：计算值：C56.6 H3.4 N4.7
实测值：C55.6  H3.4  N4.8
m/e：理论值：297
实测值：297
实施例2
N-正丙基-2-（3-α，α，α-三氟甲基苯氧基）-6-吡啶甲酰胺
（a）制备6-（3-α，α，α-三氟甲基苯氧基）吡啶甲酸
将甲基6-（3-α，α，α-三氟甲基苯氧基）吡啶甲酸酯（8g）于含氢氧化钠（2.5g）的50%稀甲醇（45ml）中的溶液回流3小时。蒸除甲醇，再向残余物中另外加入水，水溶液用***萃取。然后水相用稀盐酸酸化，折出6-（3-α，α，α-三氟甲基苯氧基）吡啶甲酸（7.1g），为白色固体，mp.92-93℃。
元素分析（%）：
C13H18NO3F3：计算值：C55.1 H2.8 N4.9
实测值：C53.3  H3.0  N5.0
m/e：理论值：283
实测值：283
（b）制备N-正丙基-2-（3-α，α，α-三氟甲基苯氧基）-6-吡啶甲酰胺
将6-（3-α，α，α-三氟甲基苯氧基）吡啶甲酸（1.5g）置于亚硫酰氯（20ml）中并回流1小时。在真空下蒸除过量的亚硫酰氯，向残余的吡啶甲酰氯中加入二氯甲烷（20ml）。在环境温度下滴加正丙胺（0.6g）和三乙胺（1.0g）的二氯甲烷（20ml）溶液。再进一步搅拌1/2小时后，反应混合物用水洗涤，用无水硫酸镁干燥，并蒸除二氯甲烷。残余物经硅胶柱纯化，用5%（v/v）***/二氯甲烷作为洗脱剂，得到N-正丙基-2-（3-α，α，α-三氟甲基苯氧基）-6-吡啶甲酰胺（1.5g），为油状物。
元素分析（%）：
C16H15O2N2F3：计算值：C59.3 H4.6 N8.6
实测值：C60.0  H5.0  N8.7
m/e：理论值324
实测值324
实例2A
制备N-正丙基-2-（3-α，α，α-三氟甲基苯氧基）-6-吡啶甲酰胺
将6-（3-α，α，α-三氟甲基苯氧基）吡啶甲酸甲酯（0.8g）和正丙胺（1.4g，过量）于室温下放置1小时。蒸除过量的正丙胺，留下标题化合物（0.7g），为无色油状物。
元素分析（%）：
C16H15O2N2F3：计算值：C59.2 H4.6 N8.6
实测值：C58.6  H4.9  N8.8
m/e：理论值：324
实测值：324
实例3-61
按上面实例2的方法，用适当选择的起始物质制备通式Ⅰ所示的其他化合物。制得的通式Ⅰ所示化合物的详情列于下面表1，起始酸的详情列于表2。
Figure 91111100X_IMG12
Figure 91111100X_IMG13
Figure 91111100X_IMG14
Figure 91111100X_IMG15
Figure 91111100X_IMG16
Figure 91111100X_IMG17
Figure 91111100X_IMG18
Figure 91111100X_IMG19
Figure 91111100X_IMG20
Figure 91111100X_IMG21
实施例62
制备N-正丙基-2-（3-α，α，α-三氟甲基苯氧基）-6-吡啶甲酰胺
（a）将6-氯吡啶甲酸（3g）和亚硫酰氯（50ml）回流1小时。在真空下蒸除过量的亚硫酰氯，向残余的吡啶甲酰氯中加入二氯甲烷。将该溶液倒入含过量正丙胺的二氯甲烷中。然后溶液用水洗涤，经无水硫酸镁干燥并蒸除二氯甲烷，得到6-氯-2-N-正丙基吡啶甲酰胺（3g），为黄色油状物。
分析（%）
C9H11N2OCl：计算值：C54.5 H5.5 N14.1
实测值：C54.2  H5.9  N14.0
m/e：理论值：198
实测值：198
（b）向3-α，α，α-三氟甲基酚（2.6g）的二甲苯（20ml）溶液中加入甲醇钠溶液（由0.4g金属钠置于20ml甲醇中制得）。在真空下蒸除溶剂，得到干燥的酚钠盐。加入吡啶（14ml）和二甲苯（30ml），随后加入氯化亚铜（0.4g）并将混合物加热回流。滴加6-氯-2-N-正丙基吡啶甲酰胺（3g）的二甲苯（20ml）溶液，得到的混合物再回流18小时。冷却后将混合物倒入水中，并用稀盐酸酸化。整个溶液用***萃取。合并的萃取液经无水硫酸镁干燥并蒸发。残余物经硅胶柱纯化，用5%（v/v）***/二氯甲烷作为洗脱剂，得到起始物质（6-氯-2-N-正丙基吡啶甲酰胺，60%）和标题化合物（40%），为无色油状物。
实例63
制备N-正丁基-2-（3-α，α，α-三氟甲基苯氧基）-6-吡啶硫代甲酰胺
将N-正丁基-2-（3-α，α，α-三氟甲基苯氧基）-6-吡啶甲酰胺（0.6g）和五硫化二磷（1.0g）在吡啶（50ml）中的混合物回流2小时。蒸除吡啶，向残余物中加入水。随后水溶液用二氯甲烷萃取。萃取液依次用稀盐酸和水洗涤，经无水硫酸镁干燥。蒸发二氯甲烷，残余物经硅胶柱纯化，用二氯甲烷作为洗脱剂，得到标题化合物（0.5g），为黄色固体，mp.61-62℃。
分析（%）：
C17H17N2OSF3：计算值：C57.6 H4.8 N7.9
实测值：C61.0  H4.7  N8.1
m/e：理论值：354
实测值：354
实例64
除草效果
用本发明化合物对以下具有代表性的植物进行试验。以评价它们的除草效果：玉米（Mz）;稻（R）;稗（BG）;燕麦（O）;亚麻（L）;芥菜（M）;糖用甜菜（SB）和大豆（S）。
试验分成芽前和芽后二类进行。芽前试验包括将化合物的液体组合物喷洒到最近播种了前面提到的植物种子的土壤上，芽后试验包括二种类型的试验，即土壤浸润和叶子喷洒试验。在土壤浸润试验中，用含有本发明化合物的液体组合物使长有前述植物秧苗的土壤浸润，在叶子喷洒试验中，用上述组合物喷洒植物秧苗。
用于本试验的土壤是配制的园艺沃土。
从试验化合物在含有0.4%重量的烷基酚-环氧乙烷缩合物（市售，商标为TRITON  X-155）的丙酮中的溶液制备应用于本试验的组合物。该丙酮溶液用水稀释，生成的组合物用于土壤喷洒和叶子喷洒试验，其剂量相当于每公顷5kg或1kg有效物质（以体积计相当于900升/公顷），用于土壤浸润试验，其剂量相当于每公顷10kg有效物质（以体积计相当于约3，000升/公顷）。
将芽前试验中未处理的播种土壤和芽后试验中未处理的带有植物秧苗的土壤作为对照。
在喷洒叶子和土壤之后12天和浸润土壤之后13天，用肉眼观察评价试验化合物的除草效果，并按0-9级记录。0级表示像未处理的对照组一样的生长，9级表示死亡（即100%有效）。在线性范围内每提高1个单位约增加10%的效果。
试验结果列于以下表3中，其中化合物参照前面实例进行确证。表中空白区表示0级，星号“★”表示未获得结果。
Figure 91111100X_IMG23
Figure 91111100X_IMG24
Figure 91111100X_IMG25
Figure 91111100X_IMG26
Figure 91111100X_IMG27
Figure 91111100X_IMG28
Figure 91111100X_IMG29
Figure 91111100X_IMG30
Figure 91111100X_IMG31

Claims (10)

1、通式Ⅰ化合物，
(Ⅰ)
其中n为整数1-5，并且各个X独立地代表氢或卤原子、由1个或多个相同或不同的选自卤原子和氰基、羟基或烷氧基的取代基任意取代的烷基或烷氧基，或者为氰基、硝基、链烯氧基、炔氧基、烷硫基、卤代烷硫基、烯硫基或炔硫基；
m为0或整数1-3，并且各个Y独立地代表卤原子或烷基或卤代烷基；
Z代表氧原子或硫原子；并且
R1和R2各自独立地代表氢原子、由1个或多个相同或不同的选自卤原子或羟基、氰基、烷氧基、烷硫基、烷氧基羰基、或者一或二烷氨基取代基任意取代的烷基，或者为链烯基、炔基、环烷基、或任意取代的环烷基烷基，或者为羟基、烷氧基、链烯氧基、炔氧基、烷氧基羰基、氨基、一或二烷氨基、烷氧基羰基氨基、由卤原子任意取代的芳氨基、或二烷基氨基甲酰基；或者
R1和R2一起代表由氧或硫原子或由基团-NR-任意断开的亚烷基链，其中R代表氢原子或烷基。
2、权利要求1所述化合物，其中n为1或2，并且X独立地代表氢、氟、氯或溴原子，或者代表硝基、乙基、甲氧基或三氟甲基。
3、权利要求2所述化合物，其中n为1，并且X代表3-三氟甲基或3-甲氧基或3-氯原子。
4、权利要求1-3中任何一项所述的化合物，其中R1代表氢原子或C1-4烷基或C2-4链烯基;而R2代表氢原子或未取代的C1-8烷基，由氟、羟基、氰基、C1-2烷氧基、（C1-2烷氧基）羰基或者一或二（C1-2烷基）氨基取代的C1-4烷基，或者为C3-6环烷基，C2-4链烯基，C2-4炔基，C1-4烷氧基，（C1-4烷基）氨基，C2-4链烯氧基，（C1-2烷氧基）羰基，（C1-2烷氧基）羰基氨基，二（C1-2烷基）氨基甲酰基，其中芳基由卤素任意取代的芳氨基、卤素取代的（C3-6环烷基）C1-4烷基，或者
R1和R2一起代表基团-（CH2）4-、-（CH2）2O（CH2）2-或-（CH2）2NR（CH2）2-，其中R为C1-2烷基。
5、权利要求4所述化合物，其中R1代表氢原子，而R2代表未取代的C1-5烷基、由氟或甲氧基取代的C1-2烷基、C3-6环烷基、C3链烯基、C3炔基、C1-2烷氧基、C3链烯氧基或氯取代的环丙基甲基，或者R1代表C1-3烷基，而R2代表相同的C1-3烷基或氯-取代的环丙基甲基。
6、权利要求5所述的化合物，其中R1代表氢原子，R2代表乙基、丙基、环丙基或环丁基。
7、制备权利要求1所述通式Ⅰ化合物的方法，包括制备其中Z代表氧原子的通式Ⅰ化合物的方法，
a）使通式Ⅱ化合物与通式NHR1R2（其中R1和R2的定义同权利要求1）的胺反应，
Figure 91111100X_IMG3
（Ⅱ）
其中Xn和Ym同权利要求1，L代表离去基团，或者
b）使通式Ⅲ化合物与通式Ⅳ化合物反应，
Figure 91111100X_IMG4
（Ⅲ）
其中Ym、R1和R2同权利要求1，Hal代表卤原子，
Figure 91111100X_IMG5
（Ⅳ）
其中Xn同权利要求1，M代表碱金属原子，并且可以有选择地将产物转变为其中Z代表硫原子的通式Ⅰ化合物。
8、除草剂组合物，该组合物包括权利要求1-6中任何一项所述的化合物和载体。
9、抑制在某场所不需要的植物生长的方法，该方法包括用权利要求1-6中任何一项所述的化合物，或者用权利要求8所述的组合物处理该场所。
10、应用权利要求1-7中任何一项所述化合物，或权利要求8所述组合物作为除草剂。
CN91111100A 1990-11-28 1991-11-26 含有甲酰胺类衍生物的除草剂组合物 Expired - Fee Related CN1039080C (zh)

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