CN85106961A - 醚类除草剂 - Google Patents

醚类除草剂 Download PDF

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CN85106961A
CN85106961A CN198585106961A CN85106961A CN85106961A CN 85106961 A CN85106961 A CN 85106961A CN 198585106961 A CN198585106961 A CN 198585106961A CN 85106961 A CN85106961 A CN 85106961A CN 85106961 A CN85106961 A CN 85106961A
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戴维·蒙罗
迈克尔·索马斯·克拉克
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Shell Internationale Research Maatschappij BV
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Abstract

本发明涉及通式为I的肟基二苯醚衍生物及其制备方法和含有这些化合物的除草组合物及其使用方法，其中，R1为卤原子或卤烷基；R2和R3可相同也可不同，各自为氢、卤原子、硝基、氰基或卤烷基；X为氰基、三唑基、SR4或NR5R6，这里R4为任一取代的烷基、芳基、芳烷基、烷氧羰基烷基或酰基，R5为任一取代的烷基或芳烷基；R6为任一取代的烷基、芳烷基或烷氧基，或者R5和R6连在一起为烷撑基；Z为氢原子或任一取代的烷基、环烷基、链烯基、芳烷基、烷氧羰基烷基或酰基。

Description

本发明涉及某些肟基二苯醚衍生物及其制备方法，含这类化合物的除草剂组合物及其在抑制有害植物的生长方面的使用。
已知，二苯醚类化合物是有效的除草剂。例如，英国专利申请2049695记述了二苯醚链烷酸及其作除草剂的应用。现已发现，有效的除草活性存在于带有肟基的二苯醚类化合物中。
本发明提供的肟基二苯醚类衍生物具有通式Ⅰ的结构：
其中R1为卤素（最好是氯原子）或卤烷基;R2和R3可相同也可不同，它们各自代表氢、卤素（最好是氯原子）、硝基、氰基或卤烷基;X代表氰基、三唑基、SR4或NR5R6，其中R4为任一取代的烷基、芳基、芳烷基、烷氧羰基烷基或酰基，R5为任一取代的烷基或芳烷基，R6为任一取代的烷基、芳烷基或烷氧基或者R5，R6是连在一起的烷撑基;Z为氢或任一取代的烷基、环烷基、链烯基、烷氧羰基烷基或酰基。
当上面的任何取代基代表或含有烷基或卤烷基时，这些取代基至多含六个碳原子为宜，最好含四个以下碳原子，卤烷基中的卤原子最好是氟和氯，以三氟甲基最合适。当取代基是芳基或含有芳基时，最好是含任意取代基的苯基。前面提到的任意取代基，最好是卤素（特别是氯原子）和氰基。当R5和R6是连在一起的烷撑基时，则可以是直链的，也可以是支链的，最好含三个至八个碳原子，特别是含四个或五个碳原子更合适。当X或Z中任一个是酰基时，可以是任何有机酸，例如：羧酸、磺酸、膦酸或氨基甲酸的酰基。
最合适的化合物是：R1为卤烷基，特别是三氟甲基;R2为卤素，特别是氯原子;R3为氢原子。X最好是氰基、三唑基、SR4或NR5R6，其中R4为至多含四个碳原子的烷基（最好是甲基）、苯基、或至多含八个碳原子的烷酰基或烷氧羰基烷基，其中以乙酰基或乙氧羰基甲基为最好;R5和R6各为至多含四个碳原子的烷基，最好是甲基;R5，R6也可连在一起为含三个至八个碳原子的烷撑基，特别是四个或五个亚甲基。Z最好代表：氢原子、氰基或苯基取代的至多四个碳原子的烷基，最好是甲基、至多含六个碳原子的烷酰基、烷基氨基甲酰基或烷基磺酰基，其中最好是乙酰基、甲基氨基甲酰基或甲基磺酰基或至多含八个碳原子的烷氧羰基烷基，最好是甲氧羰基甲基。
本发明还提供了上面限定的醚类的制备方法，即是，在碱的存在下使通式为Ⅱ的卤代醛肟与化合物XH反应。
Figure 85106961_IMG5
其中R1、R2、R3、X和Z如上规定，HaL是卤素。合适的碱是三烷基胺（如三乙胺），反应在有机溶剂（如醚）中进行较适宜。该反应能在常温（25℃）下顺利进行。当X是SR4或NR5R6时，那么，Z最好是氢原子。反应产物是通式Ⅰ的肟类化合物，这里Z是氢原子;若要得到通式Ⅰ的其它衍生物，那么，在碱金属氢化物如氢化钠的存在下，使得到的肟与HaL Z（这里，Z不是氢原子）进一步进行反应。该反应在极性有机溶剂如四氢呋喃中进行较适宜，反应在回流条件下顺利进行。
通式Ⅰ的化合物显示出有效的除草活性，因此，本发明进一步提供了通式Ⅰ限定的化合物与至少一种载体组成的除草组合物并提供了制作这种组合物的方法。
本发明还提供了按本发明规定的化合物或组合物，作为除草剂的应用;还提供了上述化合物或组合物处理某些点位从而抑制有害植物生长的方法。对于这些点位的应用可以是预处理或后处理。除草活性组分用量可以是0.04-4公斤/公顷。本发明的除草组合物中的载体可以是任何一种材料，只要这些材料与活性成份配制后，便于应用到被处理的点位如植物、种子或土壤，并便于贮存、运输和操作。载体可以是固体或液体，也可以是常态为液体，而已经压缩成液体的物质，通常用于配制除草组合物的任何载体都可以应用。本发明的最佳组合物含有0.5-95%（重量）活性成份。
合适的固体载体包括天然或合成的粘土和硅酸盐例如硅藻土那样的天然硅石;滑石那样的硅酸镁;硅酸铝镁如硅镁土和蛭石;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、硅酸钙和硅酸铝;各种单质如碳和硫;天然的和合成的树脂如苯并呋喃树脂、聚氯乙烯、各种苯乙烯聚合物和共聚物;各种固体聚氯苯酚;沥青;石腊或各种固体的肥料如过磷酸盐。
合适的液体载体包括水;醇类如异丙醇和二元醇类;酮类如丙酮、丁酮、甲基、异丁基酮和环己酮;醚类;芳香烃或芳脂烃如苯、甲苯和二甲苯;石油镏份如煤油和轻质矿物油;氯代烃如四氯化碳、全氯乙烯和三氯乙烷;另外还经常采用不同液体的混合物。
农用的除草组合物经常配制成便于运输的浓缩物，使用前再由使用者稀释。少量表面活性剂载体的存在有利于稀释过程。因此，按本发明配制的组合物至少有一种载体是表面活性剂。例如：该组合物中至少有两种载体，其中至少有一种是表面活性剂。
表面活性剂可以是离子型或非离子型的乳化剂、分散剂或湿润剂。合适的表面活性包括：聚丙烯酸和木质素磺酸的钠盐或钙盐;至少含十二个碳原子的脂肪酸、脂肪胺或脂肪酰胺与环氧乙烷和/或环氧丙烷的缩合物;甘油、脱水山梨醇、蔗糖或季戊四醇的脂肪酸酯;上述化合物与环氧乙烷和/或环氧丙烷的缩合物;脂肪族醇或烷基苯酚如对-辛基苯酚或对-辛基甲酚与环氧乙烷和/或环氧丙烷的缩合物;上述缩合产物的硫酸盐或磺酸盐;分子中至少含十个碳原子的硫酸或磺酸的碱金属或碱土金属盐，最好是钠盐例如十二烷基硫酸钠、仲烷基硫酸钠、磺化蓖麻油的钠盐和烷基芳基磺酸钠如十二烷基苯磺酸盐以及环氧乙烷的聚合物和环氧乙烷与环氧丙烷的共聚物。
本发明的组合物可以配制成可湿润性粉末、粉剂、颗粒、溶液、可乳化的浓缩液、乳化液、悬浮浓缩液及气溶胶。可湿润性粉末的活性成分含量通常为25%、50%或75%（重），除含固体惰性载体以外，通常还含有3-10%的分散剂，必要时还含有0-10%（重）的稳定剂和/或其它的添加剂如渗透剂或粘合剂。粉剂通常配制成组成类似于可湿润粉末，但不加分散剂的粉状浓缩物，在田间再进一步用固体载体稀释，得到活性成分含量通常为1/2-10%（重）的组合物。颗粒通常为10-100英国标准目（1.676-0.152毫米），这种颗粒可用凝聚或浸渍技术制造。颗粒中活性成分含量通常为1/2-75%（重），添加剂如稳定剂、表面活性剂、缓释调节剂及粘合剂的含量为0-10%（重）。所谓“干燥可流动粉末”，是由活性浓度较高的较小颗粒组成。可乳化浓缩物除含溶剂外，必要时含有共溶剂，活性成分的含量通常为10-50%（w/v），乳化剂为2-20%（w/v），其它添加剂如稳定剂、渗透剂和防腐剂为0-20%（w/v）。悬浮浓缩液通常是稳定的不沉积的可流动产品，通常含有活性成分10-75%（重），分散剂0.5-15%（重），其它添加剂如去沫剂、防腐剂、稳定剂、渗透剂和粘合剂以及水或基本上不溶解活性成分的有机液体共占0-10%（重）。在配方中，溶解某些有机固体或无机盐有助于防止沉积或作为水的抗冻剂。
将本发明的可湿润性粉末或浓缩液用水冲稀，得到的水分散体或水乳化液也属于本发明的范围。上述乳化液可以是油包水型，也可以是水包油型，并且可以有象蛋黄酱那样的粘稠度。
本发明的组合物也可以含有其它成分，如具有除草、杀虫或杀菌活性的其它化合物。
用下述实例对本发明作进一步阐明
例1α-甲硫基-3-（2-氯-4-三氟甲基苯氧基）-6-硝基-苯甲醛肟的制备
a）3-（2-氯-4-三氟甲基苯氧基）-苯甲酸的硝化
在保持0℃条件下，将3-（2-氯-4-三氟甲基苯氧基）-苯甲酸（20克）与二氯甲烷（40毫升），浓硫酸（80毫升）混合，冷却至0℃并保持三十分钟，加入硝酸钾（6.5克）。将反应混合物倾入冰水中，用氯仿萃取，然后除去溶剂，得到淡黄色油，重结晶得无色结晶，熔点：149-155℃。
b）在搅拌、回流和通干燥氮气的条件下，将亚硫酰氯（3.3克）滴加到a）产物（9克）的苯（50毫升）溶液中，反应需一小时，除去溶剂得无色的油，该油可直接用于下一步。
c）将b）产物（9.5克）的丙酮（50毫升）溶液与三苯膦（13克）和双-（三苯膦）氢硼化铜（15.5克）在常温下搅拌反应一小时。过滤反应混合物，除去溶剂得到橙色油。将该油溶于氯仿中并与氯化亚铜一起搅拌一小时，过滤并除去溶剂。用色层法将油纯化，并重结晶得无色结晶3-（2-氯-4-三氟甲基苯氧基）-6-硝基苯甲醛，熔点：95-96℃
元素分析：
实测值    碳＝48.9%;氢＝1.9%;氮＝3.9%
计算值（C14H7NCLF3O4）碳＝48.6%;氢＝2.05%;氮＝4.05%
d）将醋酸钠（9.8克）加入盐酸羟胺（8.2克）的水（30毫升）溶液中，随后加入c）的苯甲醛产物（5克）和乙醇，在氮气中将混合物搅拌回流直至成为清液，继续回流三十分钟。加入二氯甲烷和水（800毫升;50/50），分出有机层、洗涤、干燥并除去溶剂，将得到的黄色油用色层法纯化并重结晶，得无色结晶，熔点：120℃。
e）在25℃和搅拌条件下，将N-氯琥珀酰亚胺（1.1克）加入d）的苯甲醛肟（3克）的二甲基甲酰胺（10毫升）溶液中，将此混合物加热至50-60℃使开始反应，然后掌握加入余下的N-琥珀亚胺（4.4克）的速度和加热或冷却的办法使反应温度维持在50℃左右。将反应产物倾入冰水中，用乙醚萃取两次，洗涤有机层并干燥，除去溶剂，得到α-氯代苯甲醛肟，为无色油状物。
f）在常温和氮气中，将三乙胺（1.4克）的乙醚（20毫升）溶液滴加到e）的α-氯代苯甲醛肟（4克）的乙醚（20毫升）溶液中，立即沉淀出盐酸三乙胺。在室温和搅拌条件下，将甲硫醇气通入该溶液，反应一小时，加入乙醚和水（500毫升;50/50），分出有机层、洗涤、干燥，该产物用色层法纯化得预期的最终产物，熔点：180℃。
元素分析：
实测值    碳＝44.3%;氢＝2.45%;氮＝6.9%
计算值（C15H10N2CLF3O4S） 碳＝44.3%;氢＝2.45%;氮＝6.9%
例2
将例1的α-甲硫基-苯甲醛肟（2克）溶于干燥的四氢呋喃（10毫升）中，在室温、搅拌和通氮气条件下，滴加到氢化钠（0.2克）的四氢呋喃（50毫升）悬浮液中。一小时后，加入溴代乙酸甲酯（1克），回流反应混合物一小时，然后加乙醚和水（500毫升;50/50），分出有机层、洗涤并干燥。产物用色层法纯化，得淡黄油状物，α-甲硫基-3-（2-氯-4-三氟甲基苯氧基）-6-硝基-苯甲醛-0-甲氧羰基甲肟。
元素分析：
实测值    碳＝45.7%;氢＝3.0%;氮＝5.1%
计算值（C18H14N2CLF3O6S） 碳＝45.2%;氢＝2.9%;氮＝5.8%
例3-21
操作步骤类似于例1和例2，但例1（f）的甲硫醇用选自XH的适当反应物代替和/或例2的溴代乙酸甲酯用选自HaLZ的适当反应物代替，制得本发明的另一些化合物。它们的物理性质和化学分析结果列于表1中。表Ⅰ同时列出下面通式的取代基：
Figure 85106961_IMG6
Figure 85106961_IMG7
Figure 85106961_IMG8
例22
除草活性
为了评价本发明的化合物的除草活性，所用的有代表性的植物是：玉米（Zea    mays）（Mz）;水稻（Oryza    sativa）（R）;稗子（Echinochloa    crusgalli（BG）;燕麦（Avena    sativa）（O）;亚麻子（Linum    usitatissimum（L）;芥菜（Sinapsis    alba（M）;甜菜（Beta    vulgaris（SB）和大豆（Glycinemax（S）。
试验分预处理和后处理两种情况。预处理试验是将化合物的液体配方喷洒在刚刚播种了上述植物种子的土壤上;后处理试验包括两类：土壤的湿润和对植物叶子的喷洒。土壤的湿润试验是用含有本发明的化合物的液体配方湿润正生长着上述植物的土壤;而植物叶子的喷洒试验是把这样的配方喷洒到正在生长的植物上。
试验用的土壤是一种特别处理过的园艺沃土。
试验中使用的配方由试验化合物的丙酮溶液配制，丙酮中含0.4%商标为TRITON    X-155的烷基苯酚/环氧乙烷缩合物。上述丙酮溶液用水冲稀，在对土壤喷洒和叶子喷洒试验中，每公顷需5公斤或一公斤活性物质，相当于每公顷喷洒上述配方溶液600升;在土壤湿润试验中，每公顷需10公斤活性物质，相当于每公顷用液量的3000升。
在预处理试验中，用未处理的播有种子的土壤作参比;在后处理试验中，用未处理长有上述植物的土壤作参比。
对叶丛和土壤喷洒试验，待喷洒十二天后观察评价试验化合物的除草效力;对于湿润土壤，待湿润十三天后观察评价除草效力。其结果分成0-9级记录。零级表示未处理的参照物的生长，9级表示杂草死亡。每增加一级，除草效力大约增加10%。
试验结果列于表Ⅱ，表中的化合物请参照例子。
Figure 85106961_IMG9
Figure 85106961_IMG11
Figure 85106961_IMG12
Figure 85106961_IMG13

Claims (10)

1、通式为(Ⅰ)的肟基二苯醚衍生物的制备方法，
Figure 85106961_IMG2
其中R1代表囟原子或囟烷基，R2和R3可以相同也可不同，各自代表氢、囟原子或硝基、氰基或者囟烷基，X为氰基、三唑基、SR4或NR5R6，其中R4为任一取代的烷基、芳基、芳烷基、烷氧羰烷基或酰基，R6为任一取代的烷基或芳烷基，R6为任一取代的烷基、芳烷基或烷氧基，或者R5和R6连在一起为烷撑基，Z为氢原子或任一取代的烷基、环烷基、链烷基、芳烷基、烷氧羰烷基或酰基，
该方法的特征是，在碱的存在下化合物XH与通式为(Ⅱ)的囟代醛肟反应，
其中R1、R2、R3、X和Z的含义如上限定，Hal是囟素，当Z是氢而要求产物中Z是另外的基团之一时，应在碱金属氢化物存在下进一步与通式为Hal Z的化合物反应。
2、按照权利要求1规定的方法，通式（Ⅰ）中R1是三氟甲基，R2是氯原子，R3是氢原子。
3、按照权利要求1或2规定的方法，通式（Ⅰ）中X是氰基、三唑基、SR4或NR5R6，其中R4为至多4个碳原子的烷基、苯基或至多8个碳原子的烷酰基或烷氧羰烷基，R5和R6各自为至多4个碳原子的烷基或R5和R6连在一起为含3～8个碳原子的烷撑基。
4、按照权利要求1或2规定的方法，通式（Ⅰ）中Z为氢原子、被氰基或苯基任意取代的至多4个碳原子的烷基、至多6个碳原子的烷酰基、烷氨基甲酰基或烷磺酰基或至多8个碳原子的烷氧羰烷基。
5、按照权利要求3规定的方法，通式（Ⅰ）中Z为氢原子、被氰基或苯基任意取代的至多4个碳原子的烷基、至多6个碳原子的烷酰基、烷氨基甲酰基或烷磺酰基或至多8个碳原子的烷氧羰烷基。
6、按照权利要求1规定的方法，所说的碱是三乙胺，反应是在有机溶剂中进行。
7、按照权利要求1或6规定的方法，与Hal  Z的最后反应是在极性溶剂中进行。
8、一类除草组合物，其特征是由权利要求1～5任一项规定的化合物与载体组成。
9、抑制某些场所有害植物生长的方法，是用权利要求1～5任一项规定的化合物或权利要求8规定的组合物处理这些场所。
10、按照权利要求1～5任一项规定的化合物，作为除草剂的应用。
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