CN87106917A - 新型卤代环丙基化合物,其制备方法及其作为除草剂的应用 - Google Patents
新型卤代环丙基化合物,其制备方法及其作为除草剂的应用 Download PDFInfo
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- CN87106917A CN87106917A CN198787106917A CN87106917A CN87106917A CN 87106917 A CN87106917 A CN 87106917A CN 198787106917 A CN198787106917 A CN 198787106917A CN 87106917 A CN87106917 A CN 87106917A CN 87106917 A CN87106917 A CN 87106917A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/32—Cyclic imides of polybasic carboxylic acids or thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
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- A—HUMAN NECESSITIES
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
- C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Indole Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
本发明公开式I新型卤代环丙基化合物,其中R1、R2、R3、X、Y、n、U、V和W如说明书所述。
Description
本发明涉及新型囟代环丙基化合物,按已知方法的制备方法以及其作为除草剂的应用。
已知某些四氢吲唑和四氢邻苯二甲酰亚胺具有除草特性(EP61741和105721)。这些物质芽前芽后应用活性均很好但其缺点是与某些作物如棉花,大豆和谷物的相容性不够。
现已出乎意料地发现,式Ⅰ囟代环丙基化合物与水稻,小麦,大豆,玉米,棉花和大麦的相容性很好,同时又具有显著的除草活性。
其中
R1、R2和R3分别为氢或1-4碳烷基,
X为氢或囟素,
Y为囟素,
n为0,1,2或3
U和V为氢或囟素,和
W为以下杂环基
其中
T为囟素,1-4碳烷基,1-4碳囟代烷基,CN或OR9,
Q为CH或N,
Z为O或S,
R4,R5,R6,R7和R8分别为直链,支化或环状1-7碳烷基,必要时还可由1-6个囟原子取代,或
R4和R5也可一起形成饱和或非饱和4-7圆环,其中可含O,S或N等杂原子,必要时还可由1-3个甲基或1-6个囟原子取代,和
R9为氢,1-4碳烷基或1-4碳囟代烷基。
“囟素”为F,Cl,Br或I,而“囟代烷基”意为烷基中已有一或多个氢原子由囟素取代了。
杂环具体例子包括:吡咯,噁唑,噻唑,咪唑,吡啶,噁嗪,噻嗪,嘧啶,吡嗪,三嗪,噁二嗪和噻二嗪以及其二,四或优选为六氢衍生物。
本发明化合物可按已知方式依据下述方案制得:
a)将式Ⅱ囟化物与式Ⅲ酚反应
其中R1,R2,R3X,Y和n同式Ⅰ定义,A为Cl,Br或L,
其中U,V和W同式Ⅰ定义,
或
b)为制得W为4,5,6,7-四氢吲唑-2-基的式Ⅰ化合物,将式Ⅳ化合物与式Ⅴ化合物反应
其中R1,R2,R3X,Y,n,U,V同式Ⅰ定义,
其中R10为1-4碳烷基,1-4碳囟代烷基或1-4碳烷氧基,
必要时可将这样制得的T为羟基的式Ⅰ化合物改性如与硫酸二烷基酯反应得T为烷氧基的对应化合物或与磷酰氯反应得T为囟素的对应化合物且必要时还可用Na CN处理而转化成T为CN的对应化合物,
或
c)为制得W为2H-1,2,4-三唑啉-3-酮-2-基的式Ⅰ化合物,将上述式Ⅳ化合物与式Ⅵ化合物反应
其中R4和R5同式Ⅰ定义,R11为1-4碳烷基,
或
将式上述Ⅳ化合物与式Ⅻ酮酸反应
其中R8同式Ⅰ定义,
从而制得式Ⅺ化合物
其中R1,R2,R3,R8,X,Y,n,U和V同式Ⅰ定义,再用磷酸酯叠氮化物进行环化处理而制成式ⅩⅩⅢ化合物
其中R1,R2,R3,R5,X,Y,n,U和V同式Ⅰ定义,必要时可还将其与式Ⅹ化合物反应
其中R4同式Ⅰ定义,A为Cl,Br或I,
或
d)为制得W为3H-1,3,4-二唑-2-酮-3-基的式Ⅰ化合物,将上述式Ⅳ化合物与式Ⅷ酸衍生物反应
其中R6同式Ⅰ定义,R12为囟素或1-4碳烷氧基,从而制得式Ⅶ中间产物
其中R1,R2,R3,R6,X,Y,n,U和V同式Ⅰ定义,
再将其与光气或其带活性官能团的衍生物反应,
或
e)为制得W为2H,4H-1,2,4-三嗪-3,5-二酮-2-基的式Ⅰ化合物,将上述式Ⅳ化合物与式Ⅻ酮酸反应
其中R8同式Ⅰ定义,
从而制得式Ⅺ化合物
其中R1,R2,R3,R8,X,Y,n,U和V同式Ⅰ定义,然后将其用亚硫酰(二)氯或磷酰氯并在其后用氨基甲酸酯进行环化而制成式Ⅸ化合物
其中R1,R2,R3,R8,X,Y,n,U和V同式Ⅰ定义,再将其与式Ⅹ化合物反应
其中R7同式Ⅰ定义,A为Cl,Br或I,
或
f)为制得W为4,5,6,7-四氢-2H-1,2,3-三唑并[3,4-a]吡啶-8-鎓-3-羟桥合-2-基的式Ⅰ化合物,将式ⅩⅤ化合物用亚硝酸重氮化后与哌啶-2-羧酸反应并在其后用乙酸酐环化
其中R1,R2,R3,X,Y,n,U和V同式Ⅰ定义,
g)为制得W为1,3,4,5,6,7-六氢-2H-异吲哚-1,3-二酮-2-基的式Ⅰ化合物,将上述式ⅩⅤ与式ⅩⅥ反应
其中Z为O或S,
或
h)为制得W为2,3,5,6,7,8-六氢-1H-咪唑并[1,5-a]-吡啶-1,3-二酮-2-基或2,3,5,6,7,8-六氢-1H-1,3,4-三唑并[1,2-a]-哒嗪-1,3-二酮-2-基的式Ⅰ化合物,将上述式ⅩⅤ化合物与式ⅩⅦ或ⅩⅧ化合物反应
其中Z为O或S,Q为CH或N,R15为1-4碳烷基,
或
将上述式ⅩⅤ化合物与光气或硫光气反应可制得式ⅩⅨ化合物,
其中R1,R2,R3,X,Y,n,U,V和Z同式Ⅰ定义,
然后再将式ⅩⅨ化合物与式ⅩⅩ化合物反应
其中Q为CH或N,Z为O或S,R15为1-4碳烷基,
或
i)将式ⅩⅩⅠ化合物与式ⅩⅩⅡ囟代甲烷衍生物反应
其中R1,R2,R3,U,V,W和n同式Ⅰ定义,
按照制备方案a),反应可适当地借助酸性接受体于0-150℃特别是室温至反应混合物回流温度下进行。适宜酸性接受体包括常用碱特别是脂肪胺如三乙胺或二异丙胺以及碱金属碳酸盐及其水溶液等等。
醚化反应也可用催化剂于两相系统中且必要时在溶剂中进行。适宜碱包括固态或水溶液态碱金属氢氧化物和碳酸盐等等。适宜溶剂包括反应物本身(如为液态)等等。此外,可用不与水相混并对碱成惰性的物质如脂肪或芳族烃如己烷,苯或甲苯等等。优选催化剂为冠醚如1,4,7,10,13,16-六氧环十八烷和季铵盐(见于Dehmlow和Dehmlow,Phase Transfer Catalysts,Weinhem 1980)等等。
一般采用化学计算的起始物料,但某些情况下也可使某种起始物料过量。
按照制备方案b)和c),反应一般在适宜溶剂中于催化剂存在下进行。反应温度一般为室温-150℃特别是反应混合物的回流温度。适宜溶剂包括二甲亚砜,囟代烃如二氯甲烷和氯仿,芳烃如苯,甲苯,二甲苯,氯苯和二氯苯以及其它对反应物成惰性的溶剂如乙醚,四氢呋喃成二甲基甲酰胺等等。
催化剂具体例子包括酸如乙酸或硫酸以及酸性离子交换树脂。
按照制备方案d),反应一般在有或没有适宜惰性溶剂下进行。适宜溶剂包括二甲亚砜,囟代烃如二氯甲烷和氯仿,芳烃如苯,甲苯,二甲苯,氯苯和二氯苯以及其它对反应物成惰性的溶剂如乙醚,四氢呋喃或二甲基甲酰胺等等。
按照制备方法e),式Ⅸ化合物与式Ⅹ化合物的反应可适当地借助酸性接受体于0-150℃特别是室温至反应混合物回流温度下进行。适宜酸性接受包括常用碱特别是脂肪胺如三乙胺或二异丙胺以及碱金属碳酸盐及其水溶液等等。
烷基化反应可用催化剂于两相系统中且必要时在溶剂中进行。适宜碱包括固态或水溶液态碱金属氢氧化物和碳酸盐等等。适宜溶剂包括反应物本身(如为液态)等等。此外,可用不与水相混并对碱成惰性的物质如脂肪或芳族烃如己烷,苯或甲苯等等。适宜催化剂包括冠醚和季铵盐等等。
一般采用化学计量的起始物料,但某些情况下也可使某种或某些起始物料过量。
按照制备方案f),反应一般分三阶段进行且其间并不提纯中间产物。除水而外还可用任何惰性有机溶剂。反应温度为-20-100℃特别是-10℃至室温。
按照制备方案g)和h),反应一般在20℃以上的温度如100℃或反应混合物的回流温度下进行。当反应物之一为酸酐如式ⅩⅥ或ⅩⅦ化合物时,反应可适当地在酸如乙酸存在下进行,其中乙酸又可作为溶剂。但反应也可在有或没有惰性溶剂如二氯甲烷过二甲亚砜存在下进行并可用酸酐如乙酸酐将中间交叉产物环化。
按照用式ⅩⅨ和ⅩⅩ化合物进行的制备方案h),反应一般在惰性溶剂中于20-150℃特别是溶剂沸点下进行。适宜溶剂包括必要时可氯化的脂肪烃和芳烃如石油醚,苯,甲苯,二甲苯,二氯甲烷,氯仿,四氯甲烷,1,2-二氯乙烷和氯苯以及醚如乙醚和正丁醚,甲基叔丁基醚,四氢呋喃和二噁烷,酮如丙酮,甲乙酮和甲基异丙基酮以及腈如乙腈和丙腈和亚砜如二甲亚砜或环丁砜等等。
按照制备方案i),反应一般在对反应物成惰性的溶剂如氯仿,醚如二烷或二乙二醇二烷基醚,脂肪烃如环己烷或癸烷中于室温至200℃特别是在溶剂沸点下并在必要时还借助强碱如碱金属醇化物或氢氧化物的影响且优选是以两相系统采用相转化催化剂如Dehmlow和Dehmlow在“Phase Transfer Catalysts,Weinhem 1980”中所述催化剂来进行。
按照上述方法制得的本发明化合物可以常规方式如采用常压或减压蒸馏溶剂或萃取法进行分离。
一般还可采用柱色谱法以及分馏法来提高纯度。
本发明化合物一般成晶体或粘性物质,一部分在囟代烃如氯仿,亚砜如二甲亚砜或酯如乙酸乙酯中极易溶解。
本发明化合物还可含一个或多个非对称碳原子。本发明还包括必要时的旋光体及其混合物。在实施例中。除另有说明而外,得到的是外消旋物。
式Ⅳ和ⅩⅤ起始物质可按已知方法制得,可行的合成途径示于以下反应流程:
其它起始物料的制备在这里就不再说明,因为这些起始物料是已知的或可按已知方法的相似方法制得。
本发明化合物对经济作物影响重大的单子叶和双子叶杂草具有显著的除草活性,而且在播种前,芽前或芽后喷洒均可。
还出乎意料地发现本发明化合物与水稻,小麦,大豆,玉米,棉花和大麦的相容性很好。
本发明化合物可用于清除以下杂草:
以下双子叶杂草:茼麻属,菊属,芸苔属,向日葵属,薄荷属,芥属,独行菜属,猪殃殃属,狼毒属,春黄菊属,藜属,滨藜属,千里光属,马齿苋属,番薯属,母菊属,牛膝菊属,荨麻属,苋属,蓼属,田菁属,豚草属,苦苣菜属,茄属,野芝麻属,婆婆纳属,曼陀罗属,堇菜属,矢车菊属和鼬瓣花属;
以下单子叶杂草:燕麦属,看麦娘属,稗属,狗毛草属,黍属,马唐属,早熟禾属,蟋蟀草属,臂形草属,毒麦属,雀麦属,荷草属,冰草属,慈姑属,狗芽根属,雨久花属,飘拂草属,荸荠属,lschaemum和Apera。
本发明化合物并不仅限于上述杂草和作物,而是可类似地用于其它植物。
本发明还适于以大用量用来对工厂周围和铁路沿线以及道路两旁和空地上的杂草进行总控制,也可用来清除长期培植地带如森林,观赏植物园,果园,葡萄园,柑桔园,坚果园,香蕉园,咖啡园,茶场,橡胶园,油棕园,椰子林,桨果园以及忽布花园中的杂草。
活性物质用量可在很宽范围内变化,主要视需达到的效果而定,一般用量为0.01-5kg活性物质/ha,而除草优选用量为0.1-0.5kg活性物质/ha。
如想扩大活性谱,还可混用其它除草剂。这方面适用的混用除草活性组分包括Wees Abstracts,Vol.35,No.3,1986中以题为“Lists of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstracts”的文章中所列的活性除草剂等等。
所说活性物质或其混合物可适当地以可湿性粉,撒粉,粒,溶液,乳液或悬浮液等制剂形式得到应用,其中添加液态和/或固态载体和/或稀释剂且必要时还添加粘合剂,润湿剂,乳化剂和/或分散剂。
适宜液体载体包括脂肪烃和芳烃如甲苯,二甲苯和环己酮,异佛尔酮,二甲亚砜,二甲基甲酰胺以及其它矿物油组分和植物油等等。
适宜固体载体包括矿物成分如石膏,Tonsil,膨润土,硅胶,滑石,高岭土,硅镁土,石灰石,硅酸以及植物产品如面粉等等。
表面活性剂可用木素磺酸钙,聚乙烯烷基苯基醚,聚环氧乙烷-山梨糖醇酯,聚环氧乙烷-聚环氧丙烷高聚物,萘磺酸及其盐,带部分可由聚乙氧基取代的叔胺的阳离子表面活性剂,苯酚磺酸及其盐,甲醛缩合产物,脂肪醇硫酸盐以及取代苯磺酸及其盐。
各种制剂中活性成分百分比可在很宽的范围内变化如其中可含约10-90%w/w活性成分和约90-10%w/w液态或固态载体以及必要时可含高达20%w/w表面活性剂。
制剂可按常规方法施用如用水作载体以约100-3000 l/ha v/v的用量喷洒制剂混合物,也可采用所谓的低体积或超低体积技术以所谓的微粒形式进行施用。
这些制剂可采用常规方法如研磨或混合工艺制得。必要时也可在施用前夕才将各成分混合起来如采用所谓的常用罐混方法进行混合。
作为本发明举例,采用下列成分制成以下制剂(含量以重量计):
a1)可湿性粉
80%活性物质
10%高岭土
2%N-甲基-N-油酰牛磺酸钠
8%木素磺酸钙
a2)可湿性粉
20%活性物质
35%膨润土
8%木素磺酸钙
2%N-甲基-N-油酰牛磺酸钠
35%硅酸
b)糊
45%活性物质
5%硅酸铝钠
15%鲸蜡基聚乙二醇醚与8摩尔环氧乙烷的混聚产物
2%锭子油
10%聚乙二醇
23%水
c)乳油
20%活性物质
75%异佛尔酮
2%十二(烷)基苯磺酸钙
3%脂肪醇聚乙二醇醚
下述为本发明化合物制备例。
制备例1
N-[4-氯-5-(2,2-二氯环丙基甲氧基)-2-氟苯基]-3,4,5,6-四氢邻苯二甲酰亚胺(化合物No.1.1)
将8.9g(0.031mol)4-氯-2-氟-5-(2,2-二氯环丙基甲氧基)苯胺溶于12.5ml乙酸并加入3.85g 3,4,5,6-四氢邻苯二甲酸酐。混合物回流加热3小时后倒入冰水中用乙醚萃取。醚相用碳酸氢钠水溶液中和,用饱和盐水洗涤后用硫酸镁干燥并除去溶剂。残余物用9份己烷加1份乙酸乙酯的混合物作洗脱液进行硅胶色谱分析。
得到褐色晶体7.8克(理论值的75%,m.p.121-122℃)。
以类似方法可制得以下化合物:
化合物 R1R2R3n X Y U V 物理常数
No
1.2 H H H 1 F F Cl F n=1.5375
1.3 H H H 2 F F Cl F n=1.5280
1.4 H H H 2 Cl Cl Cl F n=1.5555
制备例2
2-[4-氯-5-(2,2-二氟环丙基甲氧基)-2-氟苯基]-4,5,6,7-四氢-(2H)-1,2,3-三唑并[3,4-a]吡啶-8-鎓-3-羟桥合物(化合物No.2.1)
将4.6g 4-氯-5-(2,2-二氯环丙基甲氧基)-2-氟苯胺溶于9.7ml浓盐酸和41.5ml水的混合物中并将混合物冷至-10℃。然后滴加入1.38g亚硝酸钠的4.2ml水溶液,其添加速度应使反应混合物的温度不致于上升到-5℃以上。之后再于-5℃搅拌1小时并用尿素消耗掉过量的亚硝酸直至碘试淀粉纸试验成负性为止。所得溶液加热至0℃后滴加入2.3g哌可酸和8.3ml三乙胺于27.7ml水中的冰冷却溶液中。之后再于0℃搅拌1小时并用二氯甲烷萃取反应混合物几次。将有机相组合起来用硫酸镁干燥并蒸出溶剂。残余物于40ml乙醚中进行提取并加入4.14ml乙酸酐和2.07ml吡啶进行处理。混合物于室温下搅拌过夜后倒入冰水中并用乙酸乙酯萃取。有机相用硫酸镁干燥并蒸出溶剂。残余物用95份乙酸乙酯加5份甲醇的混合物作洗脱液进行硅胶色谱分析。
得到晶体0.9克(理论值的13.4%,m.p.125-127℃)。
制备例3
3-氯-2-[4-氯-5-(2,2-二氟环丙基乙氧基)-2-氟苯基]-4,5,6,7-四氢-2H-吲唑(化合物No.3.1)
将5g4-氯-5-(2,2-二氟环丙基乙氧基)-2-氟苯基肼溶于18ml乙酸中,再加入2.85ml环己酮-2-羧酸乙酯并将混合物回流加热8小时。然后将混合物倒入水中用二氯甲烷萃取。有机相用碳酸氢钾水溶液中和并用饱和盐水洗涤后用硫酸镁干燥。蒸出溶剂得8.4g(理论值的100%)粗产物。该产物用3.6ml磷酰氯处理后将混合物回流加热。4小时后将其冷却并于二氯甲烷中进行提取,用水并在其后用饱和苏打溶液洗涤后用硫酸镁干燥并蒸出溶剂、残余物用95份二氯甲烷加5份甲醇的混合物作洗脱液进行硅胶色谱分析。
得到棕色油状物2.6g(理论值的35.6%,n25 D=1.5345)。
化合物 R1R2R3n X Y U V 物理常数
No
3.2 H H H 1 F F Cl F n=1.538
3.3 H H H 1 Cl Cl Cl F n=1.5713
3.4 H H H 2 Cl Cl Cl F n=1.5615
制备例4
2-[4-氯-5-(2,2-二氟环丙基甲氧基)-2-氟苯基]-2,3,5,6,7,8-六氢-1,2,4-三唑并[4,3-a]吡啶-3-酮(化合物No.4.1)
将3g4-氯-5-(2,2-二氟环丙基甲氧基)-2-氟苯基肼溶于40ml二甲苯中并加入2.4g 1-乙氧基羰基-2-哌啶酮和1g五氧化二磷。混合物回流加热3小时后倒入100ml水中并分离出有机相。该有机相用碳酸氢钾水溶液中和后用硫酸镁干燥并除去溶剂。残余物甲乙酸乙酯作洗脱液进行硅胶色谱分析。
得到油状物1.2g(理论值的23%,n20 D=1.5438)。
化合物 R1R2R3n X Y U V 物理常数
No
4.2 H H H 1 Cl Cl Cl F n=1.5655
4.3 H H H 2 Cl Cl Cl F n=1.5620
4.4 H H H 2 F F Cl F n=1.5332
制备例5
2-[4-氯-5-(2,2-二氟环丙基乙氧基)-2-氟苯基]-3-硫代-2,3,5,6,7,8-六氢-1H-咪唑并[1,5-a]吡啶-1-酮(化合物No.5.1)
将2.9g4-氯-5-(2,2-二氟环丙基乙氧基)-2-氟苯基异硫氰酸酯溶于20ml己烷并将混合物滴加入1.5ml哌啶-2-羧酸乙酯的10ml己烷溶液。混合物回流加热2小时。除去溶剂后残余物用3份己烷加1份乙酸乙酯的混合物作洗脱液进行硅胶色谱分析。
得到粘性油状物3.2g(理论值的82%,n40 D=1.54)。
制备例6
2-[4-氯-5-(2,2-二氟环丙基甲氧基)-2-氟苯基]-2,3,5,6,7,8-六氢-1H-咪唑并[1,5-a]吡啶-1,3-二酮(化合物No.6.1)
以类似于制备例5的方法将8.33g4-氯-2-氟-5-(2,2-二氟环丙基甲氧基)苯基异硫氰酸酯与4.69ml哌啶-2-羧酸乙酯于100ml己烷中反应即可得到半晶体油状产物7.7g(理论值的6%),其NMR谱如下:
δ=1,1-2,4ppm(m)9H,δ=2.7-3.15ppm(m)1H,
δ=3.85-4.4ppm(m)4H,δ=6.87(d 6Hz)1H,
δ=7.3(d 9Hz)1H
制备例7
3-[4-氯-5-(2,2-二氟环丙基甲氧基)-2-氟苯基]-5-叔丁基-1,3,4-噁二唑啉-2-(3H)-酮(化合物No.7.1)
将3g4-氯-5-(2,2-二氟环丙基甲氧基)-2-氟苯基肼氢氯化物悬浮于18.5ml甲苯中,用3.6ml三乙胺处理并将混合物搅拌至氢氯化物溶解。然后不经冷却而缓慢加入1.6ml新戊酰氯并将混合物于室温下搅拌2小时。反应混合物用水,然后用饱和碳酸氢钾水溶液,之后再用水洗涤,此后用硫酸镁干燥并除去溶剂。作为残余物得到的3.7g红色油状产物中除杂质而外含N′-[4-氯-5-(2,2-二氟环丙基甲氧基)-2-氟苯基]新戊酰肼。将此粗产物溶于22ml 20%光气的甲苯溶液,缓慢加热至100℃后保温3小时。然后将其冷却并用20ml甲醇处理后进行浓缩。残余物于二氯甲烷中进行提取,用碳酸氢钾洗两次并用水洗涤一次后用硫酸镁干燥并进行浓缩。所得粗产物用己烷/乙酸乙酯混合物(4∶1)作洗脱液进行硅胶色谱分析以进行提纯。
得到产物1.2g(理论值的24.5%,n20 D=1.5082)。
制备例8
N-[4-氯-5-(2,2-二氟环丙基丙氧基)-2-氟苯基]-5,6,7,8-四氢邻苯二甲酰亚胺(化合物No.8.1)
将1.2g N-[4-氯-2-氟-5-乙烯基氧苯基)-5,6,7,8-四氢邻苯二甲酰亚胺溶于5ml二乙二醇二甲醚中,混合物加热回流后缓慢加入2.8g氯二氟乙酸钠的20ml二乙二醇二甲醚溶液。再将混合物回流加热5小时后从生成的氯化钠中分离出来并除去溶剂。残余物用己烷/乙醚混合物(1∶1)作洗脱液进行硅胶色谱分析。
得到晶体物质0.6g(理论值的43%,m.p.105-107℃)。
制备例9
1-[4-氯-5-(2,2-二氟环丙基甲氧基)-2-氟苯基]-4-二氟甲基-3-甲基-1,2,4-二唑啉-5-(4H)-酮(化合物No.9.1)
将8.2g4-氯-5-(2,2-二氟环丙基甲氧基)-2-氟苯基肼氢氯化物溶于163ml水中,先用81ml乙醇处理之后再滴入2.75ml丙酮酸的81ml水溶液。混合物搅拌1小时后滤出沉淀产物并进行干燥。得到仍有些不纯的腙7.9g,可就这样得到应用。
将腙溶于130ml甲苯中,用3.3ml三乙胺处理并加热直至溶液变得清澈。将其冷却至约35℃并滴加入磷酸二苯基酯叠氮化物,再将混合物缓慢加热至75℃。在此温度下保温直至无氮气生成为止,然后加热回流。12小时后将其冷却,用10%烧碱溶液洗涤3次,水相再用甲苯洗涤两次并加以酸化。产物用甲苯萃取后将有机相干燥。除去溶剂后产物用乙酸乙酯作洗脱液进行硅胶色谱分析。得到1-[4-氯-5-(2,2-二氟环丙基甲氧基)-2-氟苯基]-3-甲基-1,2,4-三唑啉-5-(4H)-酮3.7g(理论值的35%)。
将上述所得产物溶于300ml环己烷中,用2.7g氢氧化钾和2g溴化四丁胺处理,将混合物加热回流后通入氯二氟甲烷。反应完全(由薄层色谱示出)后将溶液倾出,各用1N盐酸和10%烧碱水溶液洗涤两次,用硫酸镁干燥后进行浓缩。残余物用乙酸乙酯并在其后用二氯甲烷作洗脱液进行硅胶色谱分析。
得到产物80mg(理论值的2%,n40 D=1.535)。
制备某些起始物料
制备4-氯-5-(2,2-二氟环丙基甲氧基)-2-氟硝基苯
将3.6 2-氯-4-氟-5-硝基酚溶于二甲基甲酰胺中并用碳酸钾处理。混合物于室温下搅拌1小时,然后加入3.3g 2,2-二氟环丙基甲基溴。将其于80℃下加热2小时后倒入水中。混合物用二氯甲烷萃取后有机相用饱和盐水洗涤,用硫酸镁干燥并进行浓缩。残余物用3份己烷加1份乙酸乙酯的混合物作洗脱液进行硅胶色谱分析。得到黄色晶体5g(理论值的93%),其NMR谱如下:
δ=1,1-2,4ppm(m)3H,δ=4,15ppm(d 7Hz,tr 1.5Hz)2H,
δ=7.35ppm(d 10Hz)1H,δ=7.5ppm(d 7Hz)1H
以类似方法可制得以下化合物:
R1R2R3X Y n U V
H H H F F 2 Cl F
H H H Cl Cl 1 Cl F
H H H Cl Cl 2 Cl F
制备4-氯-2-氟-5-(2,2-二氟环丙基甲氧基)苯胺
常温常压下通过添加以活性炭作载体的5g10%金属Pd将36.9g 4-氯-2-氟-5-(2,2-二氟环丙基甲氧基)硝基苯于600ml乙醇中加氢。加氢完成后滤出催化剂并蒸出溶剂,得到油状产物29.3g(理论值的89%),其NMR谱如下:
δ=1,1-2,2ppm(m)3H,δ=4,0ppm(d 10Hz breit)2H,
δ=5ppm(s breit)2H,δ=6.5ppm(d 7Hz)1H,
δ=7.0ppm(d 10Hz)1H
以类似方法可制得以下化合物:
R1R2R3X Y n U V
H H H F F 2 Cl F
H H H Cl Cl 1 Cl F
H H H Cl Cl 2 Cl F
制备4-氯-2-氟-5-(2,2-二氟环丙基甲氧基)苯基肼
取29.3g 4-氯-2-氟-5-(2,2-二氟环丙基甲氧基)苯胺,首先用45ml半浓盐酸,然后用273ml浓盐酸处理。之后将其冷却到-10℃,滴加入8.3g亚硝酸钠的17ml水溶液进行处理,其添加速度应使反应混合物的温度不致于上升到-5℃以上。将其于-5℃,然后于-15℃搅拌3小时后滴加入57.3g氯化锡(Ⅱ)二水合物的34ml浓盐酸溶液,其添加速度应使反应混合物的温度不致于超过-10℃。之后室温加热过夜。再将其冷却到0℃并用430ml 32%烧碱溶液缓慢中和以进行后处理。用Celite过滤分离出沉淀出的氢氧化锡浆料,而滤饼用乙醚洗涤并将母液水溶液用乙醚萃取。将有机相组合起来后用硫酸镁干燥并除去溶剂。
得到油状产物26g(理论值的100%),其NMR谱如下:
δ=1,1-2,3ppm(m)3H,δ=4,0ppm(d 8Hz breit)2H,
δ=6,85ppm(d 7Hz)1H,δ=7.0ppm(d 10Hz)1H
以类似方法可制得以下化合物:
R1R2R3n X Y U V
H H H 2 F F Cl F
H H H 1 Cl Cl Cl F
H H H 2 Cl Cl Cl F
下述实施例表明本发明化合物的活性。
应用例A
在温室中将本发明化合物以1kg活性物质的500升水乳液/ha的用量于芽前和芽后喷洒于母菊属和堇菜属试验植物上。处理3星期后评价结果。以0=无活性和4=完全根除的标准评价制备例1-9化合物的除草效果。
应用例B
在温室中用下列化合物以0.1kg活性物质/ha的用量芽前处理下列植物,其中化合物以500升水乳液/ha的形态均匀喷洒于植物上。处理3星期后进行评价,与已知物质比较起来,本发明化合物除具有显著的除草活性而外,还具有很高的选择性。
化合物 Br So Go Gl St Ab Ma Vi Av Al Ec Se Cy
No 4.1 4 4 0 0 4 4 4 4 4 4 4 4 4
对比制剂
EP61 741
No 1 2 3 1 1 3 3 4 4 2 2 2 4 1
EP105 721
No 1 3 4 2 1 3 4 4 4 2 3 4 4 0
噁二唑酮 0 3 0 0 2 3 2 4 0 2 1 3 0
评价标准
0=无活性
1=轻微损坏
2=中等损坏
3=严重损坏
4=完全根除
植物名
Br=Brassica ssp.
So=Solanumn ssp.
Go=Gossypium hirsutum
Gl=Glycine max.
St=Stellaria media
Ab=Abutilon hybridum
Ma=Matricaria chamomilla
Vi=Viola tricolor
Av=Avena fatua
Al=Alopecurus myosuroides
Ec=Echinochloa crus-galli
Se=Setaria italica
Cy=Cyperus esculentus
应用例C
在温室中用下列化合物以0.3kg活性物质/ha的用量芽后处理下列植物,其中化合物以500升水乳液/ha的形态均匀喷洒于植物上。处理3星期后进行评价,与已知物质比较起来,本发明化合物除具有显著的除草活性而外,还具有很高的选择性。
化合物Br So Gl He St Ab Ma Vi Ch Ip Ze Tr Ho Or SrSe
No1.14 4 0 4 4 4 4 4 4 4 0 0 0 0 0 3
No3.14 4 0 4 2 2 4 3 4 3 0 0 0 0 0 4
No3.24 4 0 3 4 3 4 4 4 4 0 0 0 0 0 4
No3.42 3 0 3 1 1 2 3 3 2 0 0 0 0 0 1
No4.33 4 0 3 3 4 4 3 4 4 0 0 0 0 0 3
对比制剂
噁二唑酮4 4 4 2 2 3 3 4 3 4 2 2 2 2 2 4
评价标准
0=无活性
1=轻微损坏
2=中等损坏
3=严重损坏
4=完全根除
植物名
Br=Brassica ssp.
So=Solanumn ssp.
Gl=Glycine max.
He=Helianthus annus
St=Stellaria media
Ab=Abutilon hybridum
Ma=Matricaria chamomilla
Vi=Viola tricolor
Ch=Chrusanthemum segetum
Ip=Ipomoea purpurea
Ze=Aea mays
Tr=Triticum aestivum
Ho=Hordeum vulgare
Or=Oryza sativa
Sr=Sorghum sativum
Se=Setaria italica
应用例D
在温室中用下列化合物以0.3kg活性物质/ha的用量芽后处理下列植物,其中化合物以500升水乳液/ha的形态均匀喷洒于植物上。处理3星期后进行评价,本发明化合物具有很高的除草性。
化合物 Ec Ce Cd Fi
No 1.1 1 1 2 3
No 1.2 4 2 4 4
No 3.2 4 1 3 4
No 4.3 3 1 3 4
No 4.4 4 3 4 4
No 5.1 1 1 3 3
No 6.1 4 4 4 4
评价标准
0=无活性
1=轻微损坏
2=中等损坏
3=严重损坏
4=完全根除
植物名
Ec=Echinochloa crus-galli
Cy=Cyperus esculentus
Cy=Cyperus difformis
Fi=Fimbristylis miliacea
应用例E
在温室中以下表给出用量应用下列化合物,其中将化合物放在装有1500水的容器中(水中用药)。植物是在2-5叶期进行处理的。用药3星期后评价对植物的损坏效果。
如表中所示,本发明化合物对重要水稻杂草具有很高的除草活性。
水中用药
化合物 ppm Ec Ce Cd Fi Sa El
No 3.2 10 4 1 3 3 - -
No 4.3 10 4 1 4 4 - -
No 4.4 1 4 3 4 4 - -
3 4 3 4 4 - -
No 5.1 1 4 2 2 2 - -
3 4 4 3 4 - -
No 6.1 1 4 4 4 4 - -
3 4 4 4 4 - -
No 7.1 3 4 - 4 - 3 4
No 8.1 3 4 - 4 - 3 4
No 9.1 3 4 - 4 - 3 4
评价标准
0=无活性
1=轻微损坏
2=中等损坏
3=严重损坏
4=完全根除
-=未试验
植物名
Ee=Echinochloa crus-galli
Cy=Cyperus esculentus
Cy=Cyperus difformis
Fi=Fimbristylis miliacea
Sa=Sagittaria pusilla
El=Eleocharis acicularis
Claims (5)
2、式Ⅰ囟代环丙基化合物的制备方法
其中
R1、R2和R3分别为氢或1-4碳烷基,
X为氢或囟素,
Y为囟素,
n为0,1,2或3
U和V为氢或囟素,和
W为以下杂环基
其中
T为囟素,1-4碳烷基,1-4碳囟代烷基,CN或OR9,
Q为CH或N,
Z为O或S,
R4,R5,R6,R7和R8分别为直链,支化或环状1-7碳烷基,必要时还可由1-6个囟原子取代,或
R4和R5也可一起形成饱和或非饱和4-7圆环,其中可含O,S或N等杂原子,必要时还可由1-3个甲基或1-6个囟原子取代,和
R9为氢,1-4碳烷基或1-4碳囟代烷基,
其特征在于
a)将式Ⅱ囟化物与式Ⅲ酚反应
其中R1,R2,R3X,Y和n同式Ⅰ定义,A为Cl,Br或L,
其中U,V和W同式Ⅰ定义,
或
b)为制得W为4,5,6,7-四氢吲唑-2-基的式Ⅰ化合物,将式Ⅳ化合物与式Ⅴ化合物反应
其中R1,R2,R3X,Y,n,U,V同式Ⅰ定义,
其中R10为1-4碳烷基,1-4碳囟代烷基或1-4碳烷氧基,且必要时可将这样制得的T为烃基的式Ⅰ化合物改性如与硫酸二烷基酯反应得T为烷氧基的对应化合物或与磷酰氯反应得T为囟素的对应化合物且必要时还可用Na CN处理而转化成T为CN的对应化合物,
或
c)为制得W为2H-1,2,4-三唑啉-3-酮-2-基的式Ⅰ化合物,将上述式Ⅳ化合物与式Ⅵ化合物反应
其中R4和R5同式Ⅰ定义,R11为1-4碳烷基,
或
将式上述Ⅳ化合物与式Ⅻ酮酸反应
其中R8同式Ⅰ定义,
从而制得式Ⅺ化合物
其中R1,R2,R3,R8,X,Y,n,U和V同式Ⅰ定义,再用磷酸酯叠氮化物进行环化处理而制成式ⅩⅩⅢ化合物
其中R1,R2,R3,R5,X,Y,n,U和V同式Ⅰ定义,必要时可还将其与式Ⅹ化合物反应
其中R4同式Ⅰ定义,A为Cl Br或I,
或
d)为制得W为3H-1,3,4-噁二唑-2-酮-3-基的式Ⅰ化合物,将上述式Ⅳ化合物与式Ⅷ酸衍生物反应
其中R6同式Ⅰ定义,R12为囟素或1-4碳烷氧基,从而制得式Ⅶ中间产物
其中R1,R2,R3,R6,X,Y,n,U和V同式Ⅰ定义,再将其与光气或其带反应官能团的衍生物反应,
或
e)为制得W为2H,4H-1,2,4-三嗪-3,5-二酮-2-基的式Ⅰ化合物,将上述式Ⅻ化合物与式Ⅶ酮酸反应
其中R8同式Ⅰ定义,
从而制得式Ⅺ化合物
其中R1,R2,R3,R8,X,Y,n,U和V同式Ⅰ定义,然后将其用亚硫酰(二)氯或磷酰氯并在其后用氨基甲酸酯进行环化而制成式Ⅸ化合物
其中R1,R2,R3,R8,X,Y,n,U和V同式Ⅰ定义,再将其与式Ⅹ化合物反应
其中R7同式Ⅰ定义,A为Cl,Br或Ⅰ,
或
f)为制得W为4,5,6,7-四氢-2H-1,2,3-三唑并[3,4-a]吡啶-8-鎓-3-羟桥合-2-基的式Ⅰ化合物,将式ⅩⅤ化合物用亚硝酸重氮化后与哌啶-2-羧酸反应并在其后用乙酸酐环化
其中R1,R2,R3,X,Y,n,U和V同式Ⅰ定义,
g)为制得W为1,3,4,5,6,7-六氢-2H-异吲哚-1,3-二酮-2-基的式Ⅰ化合物,将上述式ⅩⅤ与式ⅩⅥ反应
其中Z为O或S,
或
h)为制得W为2,3,5,6,7,8-六氢-1H-咪唑并[1,5-a]-吡啶-1,3-二酮-2-基或2,3,5,6,7,8-六氢-1H-1,3,4-三唑并[1,2-a]-哒嗪-1,3-二酮-2-基的式Ⅰ化合物,将上述式ⅩⅤ化合物与式ⅩⅦ或ⅩⅧ化合物反应
其中Z为O或S,Q为CH或N,R15为1-4碳烷基,
或
将上述式ⅩⅤ化合物与光气或硫光气反应可制得式ⅩⅨ化合物,
其中R1,R2,R3,X,Y,n,U,V和Z同式Ⅰ定义,然后再将式ⅩⅨ化合物与式ⅩⅩ化合物反应
其中Q为CH或N,Z为O或S,R15为1-4碳烷基,
或
i)将式ⅩⅩⅠ化合物与式ⅩⅩⅡ囟代甲烷衍生物反应
其中R1,R2,R3,U,V,W和n同式Ⅰ定义,
3、除草制剂,其特征在于其中含至少一种权利要求1化合物或至少一种权利要求2方法制得的化合物。
4、权利要求3的除草制剂,其特征在于其中混用载体和/或助剂。
5、应用权利要求1或权利要求2方法制得的化合物除掉有用植物中的双子叶和单子叶植物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP3635309.4 | 1986-10-14 | ||
DE19863635309 DE3635309A1 (de) | 1986-10-14 | 1986-10-14 | Halogencyclopropyl-verbindungen, ihre herstellung und verwendung als herbizide mittel |
Publications (1)
Publication Number | Publication Date |
---|---|
CN87106917A true CN87106917A (zh) | 1988-07-13 |
Family
ID=6311886
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN198787106917A Pending CN87106917A (zh) | 1986-10-14 | 1987-10-13 | 新型卤代环丙基化合物,其制备方法及其作为除草剂的应用 |
Country Status (15)
Country | Link |
---|---|
US (1) | US4859230A (zh) |
EP (1) | EP0268797A3 (zh) |
JP (1) | JPS63218662A (zh) |
CN (1) | CN87106917A (zh) |
AU (1) | AU605183B2 (zh) |
BR (1) | BR8705442A (zh) |
DD (1) | DD279394A5 (zh) |
DE (1) | DE3635309A1 (zh) |
DK (1) | DK537587A (zh) |
FI (1) | FI874514A (zh) |
HU (1) | HU201068B (zh) |
IL (1) | IL84138A0 (zh) |
PH (1) | PH23048A (zh) |
SU (1) | SU1618273A3 (zh) |
ZA (1) | ZA877732B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4430287A1 (de) * | 1994-08-26 | 1996-04-25 | Basf Ag | N-Phenyltetrahydroindazole, Verfahren zur ihrer Herstellung und ihre Verwendung als Pflanzenschutzmittel |
CA2156652A1 (en) * | 1994-08-31 | 1996-03-01 | Minoru Takano | Epoxyphenol derivatives and herbicides containing them as active ingredients |
US5852048A (en) * | 1995-03-01 | 1998-12-22 | Sumitomo Chemical Company, Limited | Ester compound and a pesticidal agent containing the same as an active ingredient |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5890570A (ja) * | 1981-11-26 | 1983-05-30 | Showa Denko Kk | オキサジアゾリン誘導体及び除草剤 |
PH18938A (en) * | 1982-09-28 | 1985-11-11 | Sumitomo Chemical Co | 2-substituted phenyl-4,5,6,7-tetrahydro-2h-indazoles and their use |
JPS59148785A (ja) * | 1983-02-15 | 1984-08-25 | Sumitomo Chem Co Ltd | ピリドトリアゾリウム誘導体、その製造法およびそれを有効成分とする除草剤 |
JPS6113175A (ja) * | 1984-06-29 | 1986-01-21 | Rhythm Watch Co Ltd | タツチスイツチ付時計 |
EP0259264A1 (de) * | 1986-09-03 | 1988-03-09 | Ciba-Geigy Ag | Neue 4-Methylphthalimide |
DE3731516A1 (de) * | 1987-09-18 | 1989-03-30 | Bayer Ag | N-aryl-stickstoffheterocyclen |
-
1986
- 1986-10-14 DE DE19863635309 patent/DE3635309A1/de not_active Withdrawn
-
1987
- 1987-10-02 AU AU79373/87A patent/AU605183B2/en not_active Expired - Fee Related
- 1987-10-09 IL IL84138A patent/IL84138A0/xx unknown
- 1987-10-09 EP EP87114775A patent/EP0268797A3/de not_active Withdrawn
- 1987-10-12 DD DD87307851A patent/DD279394A5/de unknown
- 1987-10-13 BR BR8705442A patent/BR8705442A/pt unknown
- 1987-10-13 JP JP62256444A patent/JPS63218662A/ja active Pending
- 1987-10-13 CN CN198787106917A patent/CN87106917A/zh active Pending
- 1987-10-13 FI FI874514A patent/FI874514A/fi not_active Application Discontinuation
- 1987-10-13 SU SU874203502A patent/SU1618273A3/ru active
- 1987-10-13 HU HU874613A patent/HU201068B/hu unknown
- 1987-10-14 US US07/108,380 patent/US4859230A/en not_active Expired - Fee Related
- 1987-10-14 ZA ZA877732A patent/ZA877732B/xx unknown
- 1987-10-14 PH PH35935A patent/PH23048A/en unknown
- 1987-10-14 DK DK537587A patent/DK537587A/da not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
DK537587A (da) | 1988-04-15 |
EP0268797A3 (de) | 1989-03-29 |
DE3635309A1 (de) | 1988-04-21 |
PH23048A (en) | 1989-03-10 |
SU1618273A3 (ru) | 1990-12-30 |
AU7937387A (en) | 1988-04-21 |
EP0268797A2 (de) | 1988-06-01 |
IL84138A0 (en) | 1988-03-31 |
HUT48241A (en) | 1989-05-29 |
ZA877732B (en) | 1988-06-29 |
AU605183B2 (en) | 1991-01-10 |
BR8705442A (pt) | 1988-05-24 |
HU201068B (en) | 1990-09-28 |
US4859230A (en) | 1989-08-22 |
DK537587D0 (da) | 1987-10-14 |
FI874514A (fi) | 1988-04-15 |
DD279394A5 (de) | 1990-06-06 |
JPS63218662A (ja) | 1988-09-12 |
FI874514A0 (fi) | 1987-10-13 |
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