CN85106974A - 醚类除草剂 - Google Patents

醚类除草剂 Download PDF

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CN85106974A
CN85106974A CN198585106974A CN85106974A CN85106974A CN 85106974 A CN85106974 A CN 85106974A CN 198585106974 A CN198585106974 A CN 198585106974A CN 85106974 A CN85106974 A CN 85106974A CN 85106974 A CN85106974 A CN 85106974A
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截维·蒙罗
里诺·安东尼奥·比特
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Shell Internationale Research Maatschappij BV
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Abstract

本发明涉及通式为I的二苯醚环亚胺衍生物及其制备方法，这些化合物及含有这些化合物的组合物用作除草剂的使用方法。
通式中R1代表卤原子或卤烷基：；R2和R3可以相同也可以不同，各自代表氢或卤原子或者硝基、氰基或卤烷基。A代表氰基、烷基、芳基、烷氧基、芳氧基、烷硫基或芳硫基或者它们的S-氧合衍生物、酰基、酰氧基或烷氧羰基；B代表氢原子或A规定的某一基团。

Description

本发明涉及某些二苯醚亚胺衍生物，这些化合物的制备方法，含有这些化合物的除草组合物，以及在抑制有害植物生长方面它们的应用。
已知，某些二苯醚类化合物是有效的除草剂，例如英国专利申请2049695所述，二苯醚链烷酸类化合物及其作为除草剂的应用。业已发现，有效的除草活性存在于带有环亚胺取代基的二苯醚类化合物中。
本发明提供的二苯醚环亚胺类衍生物具有如下通式：
Figure 85106974_IMG4
其中R1代表卤素（最好是氯）或者卤烷基;R2和R3可以相同或不同，各自代表氢或卤素（最好是氯）或者是硝基、氰基或卤烷基;
A代表氰基、烷基、芳基、烷氧基、芳氧基、烷硫基或芳硫基或者它们的S-氧合衍生物，最好是砜、酰基、酸基或烷氧羰基;B代表氢或A所给定的某一基团。
当上述任何取代基是或者含有烷基或卤烷基时，这些取代基最多含6个碳原子较合适，最好最含4个碳原子，在卤烷基中的卤原子是氟或氯较合适，三氟甲基是最合适的卤烷基。当任何取代基是或者含有芳基时，这一取代基最好是可以被任意取代的苯基。当上述基团被任意取代时，合适的取代基包括卤原子（特别是氯原子）和氰基。当A或B任何一个代表硫衍生物时，烷基磺酰基、芳硫基或芳基磺酰基最合适，特别是苯硫基或苯磺酰基。当A或B代表酰基时，可以是任何有机酸，如羧酸、磺酸、膦酸或氨基甲酸的酰基。选定的化合物是R1代表卤烷基特别是三氟甲基;R2代表卤原子特别是氯原子和R3代表氢原子的那些化合物。
B最好是氢原子或烷基部分至多有6个碳原子的烷氧羰基，特别是甲氧羰基。A最好是氰基、苯基、芳硫基或芳基磺酰基，特别是苯硫基或苯磺酰基、烷氧基特别是甲氧基、氨基、甲酰基、膦酸烷基酯特别是膦酸甲酯或乙酯、烷基部分最多含6个碳原子的烷基羰基、烷基羰氧基或烷氧羰基，特别是乙酰基、乙酸基或甲氧羰基。
本发明还提供了如上限定的环亚胺的制备方法，即通式为Ⅱ的卤代醛肟与通式为B-CH＝CH-A的稀属衍生物在碱的存在下反应。
Figure 85106974_IMG5
其中R1、R2、R3、A和B如上所规定，HaI是卤素。适合的碱是三烷基胺，如三乙胺。反应最好在有机溶剂（如乙醚）中进行。此反应可以在环境温度下顺利地进行。
已经发现通式为Ⅰ的一类化合物用作除草剂时，显示出很大的活性。因此，本发明又提供了一类由通式为Ⅰ的化合物与至少一种载体组成的除草组合物，并提供了这类组合物的制造方法，即，通式为Ⅰ的化合物与至少一种载体的组合方法。
本发明还提供了这类化合物或组合物用作除草剂的使用方法。更有体地说，提供了一种将本发明的化合物或组合物用于某场所，从而，抑制该场所有害植物生长的方法。使用方法可分为预处理和后处理两种。活性成份用量为0.05-5kg/ha。
本发明的组合物中所用的载体是与活性成分配制后有利于用于被处理场所（如植物、种子或土壤）的任何材料，同时，有利于贮存、运输和操作。载体可以是固体或液体，包括常态是气体但已经压缩成液体的物质，在配方除草组合物中常用的任何载体可以使用。本发明的最佳除草组合物含有0.5-95%（重）的活性成份。
适宜的固体包括天然的和合成的粘土和硅酸盐，例如硅藻土那样的天然硅石;硅酸镁;如滑石;硅酸铝镁，如硅镁土和蛭石;硅酸铝，如高岭石、蒙脱石和云母;碳酸钙;硫酸钙;硫酸铵;合成的水玻璃和合成的硅酸钙或硅酸铝;碳、硫等元素;天然的和合成的树脂，如苯并呋喃树脂，聚氯乙烯，苯乙烯聚合物和共聚物;固体聚氯苯酚;沥青、石蜡;和固体肥料如过磷酸盐。
适宜的液体载体包括水;醇类如异丙醇和二元醇类;酮类如丙酮、丁酮、甲基、异丁基酮和环己基酮;醚类;芳香烃或芳脂烃如苯、甲苯和二甲苯;石油馏份和煤油和轻质矿物油;氯化烃如四氯化碳、全氯乙烯和三氯乙烷。不同液体的混合物通常是合适的。
农用组合物通常以浓缩物配制和运输，使用前由使用者稀释。少量表面活性剂载体的存在有利于此稀释过程。因此，本发明的组合物中最好至少一种载体是表面活性剂。例如，该组合物至少有两种载体，其中至少一种是表面活性剂。
表面活性剂可以是非离子型的或离子型的乳化剂、分散剂或润湿剂。合适的表面活性剂包括聚丙稀酸的和木质素磺酸的钠盐或钙盐;至少含12个碳原子的脂肪酸或脂肪胺或酰胺与环氧乙烷和/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;这些化合物与环氧乙烷和/或环氧丙烷的缩合物;脂肪族醇或烷基酚如对-辛基苯酚或对-辛基甲苯酚与环氧乙烷和/或环氧丙烷的缩合产物;这些缩合产物的硫酸酯或磺酸酯;每分子至少含10个碳原子的硫酸酯的或磺酸酯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、磺化篦麻油的钠盐和烷基芳基磺酸钠如十二烷基苯磺酸盐;环氧乙烷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是可湿性粉末、粉剂、颗粒、溶液、可乳化的浓缩物、乳化液、悬浮浓缩物和气溶剂。可湿性粉末通常含有25、50或75%（重量）的活性成份，除了固体惰性载体外通常含有3-10%（重量）分散剂，必要时含有0-10%（重量）的稳定剂和/或渗透剂或粘合剂等其它添加剂。粉剂通常配制成组成类似于可湿粉末，但没有分散剂的粉状浓缩物，在田间用其他固体载体稀释成通常含1/2-10%（重量）活性成份的组合物。颗粒通常制成10-100目（1.676-0.152mm）大小，可以通过凝聚或浸渍技术制造。一般来说，这种颗粒含有1/2-75%（重量）活性成份和0-10%（重量）的稳定剂、表面活性剂、聚释调节剂和粘合剂等添加剂。所谓“干燥可流动粉末”是由含活性成份较高的较小颗粒组成。乳化浓缩液除溶剂和必要时含有共溶剂之处，通常含有10-50%（w/v）活性成分，2-20%（w/v）乳化剂和0-20%（w/v）稳定剂、渗透剂和缓蚀剂等其他添加剂。悬浮浓缩液通常配制成稳定的、非沉降的可流动产物，通常含有10-75%（重量）的活性成份，0.5-15%（重量）的分散剂，0.1-10%（重量）的悬浮剂和保护胶体和触变剂0-10%（重量）消泡剂、缓蚀剂、稳定剂、渗透剂和粘合剂等其他添加剂，水或活性成分大体不溶解的有机液体;在配方中，溶解某些有机固体或无机盐，有助于防沉降或作水的抗冻剂。
按明本发明用水稀释可湿性粉末或浓缩液所得的水分散液和乳化液也属于本发明的范围。所说的乳化液可以是从油包水型或水包油型，可以有象浓的蛋黄酱一样的粘稠度。
本发明的组合物也可以含有其他组份，例如有具除草、杀虫或杀菌活性的其他化合物。以下实例进一步阐明本发明。
例1
3-（2-氯-4-三氟甲基苯氧基）-苯甲酸的硝化
a）30g3-（2-氯-4-三氟甲基苯氧基）-苯甲酸与40ml二氯甲烷和80ml浓硫酸混合，冷却至0℃并维持此温度，于30分钟加入6.5g硝酸钾。将反应混合物倾入冰水中，以氯仿提取除去溶剂得到浅黄色油状物，经重晶后得到无色结晶，m.p.149-155℃。
b）9g    a）产物溶解于50ml苯中，在干燥氮气氛下搅拌回流，于1小时中滴加3.3g氯化硫酰。除去溶剂得到无色油状物，直接用于下一步反应。
c）9.5g    b）产物溶解于50ml丙酮中，室温搅拌下，与13g三苯基膦和15.5g双（三苯基膦）氢硼化铜反应1小时。过滤反应混合物，除去溶剂得到一种橙色油。将其溶解于氯仿并与氯化亚铜搅拌1小时，过滤，除去溶剂。所得油状物经色层提纯和重结晶，得到3-（2-氯-4-三氟甲基苯氧基）-6-硝基苯甲醛，为无色结晶，m.p.95-96℃。
元素分析结果，实验值：C＝48.9，H＝1.9，N＝3.9%理论值（C19H7NClF3O4）：C＝48.6，H＝0.05，N＝4.05%。
d）8.2g盐酸羟胺溶解于30ml水中，加入9.8g醋酸钠，接着加入5g    c）产物和乙醇。在氮气氛下回流搅拌反应混合物，直至得到清液，继续回流30分钟。加入800ml二氯甲烷和水（50/50）分离得到有机层，洗涤、干燥，除去溶剂得到一种黄色油，色层提纯和重结晶得到无色结晶m.p.120℃。
e）3g    d）产物溶解于10ml二甲基酰胺中，于25℃搅拌下加入1.1gN-氯琥珀酰亚胺，加热此混合物至50-60℃使其反应。通过另外4.4gN-氯琥珀酰亚胺的加入速度和加热/冷却来维持反应温度在50℃左右。将产物倾入冰水中，以乙醚提取二次，洗涤有机层并干燥。除去溶剂得到a-氯苯甲醛肟，为无色油状物。
f）将2g    e）产物a-氯苯甲醛溶解于10ml乙醚与0.55g丙烯酸酯中，于氮气氛和室温搅拌下滴加0.7g三乙胺与5ml乙醚溶液，立即得到盐酸三乙胺的沉淀。滤得沉淀，真空除去溶剂，得到一种浅黄色油，色层提纯得到一种几乎无色的油，此化合物的结构如通式1，其中，R1＝CF3，R2＝Cl，R3＝H，B＝H和A＝COOCH3。
此结构为NMR所证实：
δ    3.55    d（J＝9Hz）    2H
3.9    S    3H
5.25 t（J＝9H2） 1H
7.0-8.3    m    6H
元素分析，实验值：C＝47.7    H＝2.7    N＝5.9%
理论值（C13H12N2ClF8O6）：C＝48.6 H＝2.7 N＝6.3%
例2-10
下述制备方法类似于例1的方法，只是以另选的烯属衍生物代替f）步骤的丙烯酸甲酯，是制备本发明的化合物的又一些实例，其结构由NMR所证实，其化学分析结果及物理性列于表1中。
表中同时给出通式中的取代基A。
Figure 85106974_IMG6
Figure 85106974_IMG7
例11
（A）2g3-（2-氯-4-三氯甲基苯氧基）-6-硝基-a-氯苯甲醛肟（制法如例1e）溶解于20ml乙醚并加入1g富马酸二甲酯与5ml干燥四氢呋喃的溶液，然后，于室温激烈搅拌下1分钟滴加1g三乙胺。立即生成盐酸三乙胺沉淀。加入200ml乙醚/水（50/50），分离出有机层，洗涤、干燥，得到一种橙色油。色层提纯并重结晶，得通式1的结晶化合物，其中R1＝CF3，R2＝Cl，R3＝H，A＝COOCH3和B＝COOCH3。结构为反式构型，并已由NMR证实。m.p.125℃。
元素分析：理论值：C47.75，H2.8，N5.55%
测定值：C47.75，H2.8，N5.55%
（B）同一化合物的顺式构型也已制备，为结晶化合物，m.p.122℃，元素分析结果：
测定值：C47.9，H2.7，N5.5%
例12    除草活性
为了评价本发明有关化合物的除草活性所应用的代表性植物是：玉米（Zea    mayz）;水稻（Oryza    sativa）;稗子（（Echinochloa    crusgall）;燕麦（Avena    sativa）;亚麻（Linum    usitatissimum）;芥菜（SinaPsis    alba）;甜菜（Beta    Vulgaris）和大豆（Glyeine    max）。
试验分为予处理和后处理两种类型。予处理是喷洒液体除草剂配方于刚刚播种上述植物种子的土壤上。后处理试验又分成两类，即土壤浸湿和叶丛喷洒。土壤浸湿试验是指用含本发明化合物的液体配方浸湿正在生长上述播种植物的土壤;叶丛喷洒试验是指用这样的配方喷洒播种的植物。
试验用的土壤是加工过的园林沃土。
试验用的除草剂配方是含0.4%（重量）烷基酚/环氧乙烷缩合物（商标为TRITONX-155）的供试化合物的丙酮溶液。用水稀释丙酮溶液得到试验用配方，在土壤喷洒和叶丛喷洒情况下，按每公顷5kg活性物质，相当于每公顷600升使用;在土壤浸湿试验中，按每公顷10kg活性物质，相当于每公顷3000升使用。
在预处理试验中，以未处理的已播种土壤做对照，在后处理试验中，以长着播种植物的未处理土壤做对照。
这些化合物的除草效果，在喷洒叶丛和土壤后十二天和浸湿土壤后十三天目视评定，并分0-9等级记录。0级表示未处理对照组的生长情况，9级代表杂草死亡。每增加一级表示效果大约增加10%。
试验结果见表Ⅱ。
Figure 85106974_IMG8
Figure 85106974_IMG9
Figure 85106974_IMG10

Claims (11)

1、通式为(I)的二苯醚环亚胺类衍生物的制备方法，
Figure 85106974_IMG2
其中R1代表囟原子或囟烷基，R2和R3可以相同或不同，各自代表氢或囟原子或硝基、氰基或者囟烷基，A代表氰基、烷基、芳基、烷氧基、芳氧基、烷硫基或芳硫基或者它们的S-氧合衍生物、酰基、酰氧基或烷氧羰基，B代表氢原子或A所代表的某一基团。
该方法的特征是通式为(Ⅱ)的囟代醛肟与通式为
B-CH=CH-A的烯属衍生物在碱的存在下反应，
Figure 85106974_IMG3
其中R1、R2、R3、A和B与上述相同，Hal代表囟素。
2、按照权利要求1规定的方法，通式（Ⅰ）中R1代表三氟甲基，R2代表氯原子和R3代表氢原子。
3、按照权利要求1或2规定的方法，通式（Ⅰ）中B代表氢原子或烷基部分最多含6个碳原子的烷氧羰基。
4、按照权利要求1或2规定的方法，通式（Ⅰ）中A代表氰基、苯基芳硫基或芳基磺酰基、烷氧基、氨基甲酰基、膦酸烷酯、或烷基部分最多含6个碳原子的烷羰基、烷羰氧基或烷氧羰基。
5、按照权利要求3规定的方法，通式（Ⅰ）中A代表氰基、苯基、芳硫基或芳基磺酰基、烷氧基、氨基甲酰基、膦酸烷酯、或烷基部分最多含6个碳原子的烷羰基、烷羰氧基或烷氧羰基。
6、按照权利要求3规定的方法，通式（Ⅰ）中B代表氢原子、或甲氧羰基，A代表氰基、苯基、苯硫基、苯磺酰基、甲氧基、氨基甲酰基、膦酸二乙酯、乙酰基、乙酰氧基或甲氧羰基。
7、按照权利要求4规定的方法，通式（Ⅰ）中B代表氢原子、或甲氧羰基，A代表氰基、苯基、苯硫基、苯磺酰基、甲氧基、氨基甲酰基、膦酸二乙酯、乙酰基、乙酰氧基或甲氧羰基。
8、按照权利要求5规定的方法，通式（Ⅰ）中B代表氢原子或甲氧羰基，A代表氰基、苯基、苯硫基、苯磺酰基、甲氧基、氨基甲酰基、膦酸二乙酯、乙酰基、乙酰氧基或甲氧羰基。
9、本发明的除草组合物由权利要求1～8任一项规定的化合物和载体组成。
10、抑制某些场所有害植物生长的方法，是用权利要求1～8任一项规定的化合物或权利要求9规定的组合物处理这些场所。
11、按照权利要求1～8任一项规定的化合物作为除草剂的应用。
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