CN87108192A - 二唑酮衍生物,其制备方法,及含有该衍生物的除草剂 - Google Patents
二唑酮衍生物,其制备方法,及含有该衍生物的除草剂 Download PDFInfo
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- CN87108192A CN87108192A CN198787108192A CN87108192A CN87108192A CN 87108192 A CN87108192 A CN 87108192A CN 198787108192 A CN198787108192 A CN 198787108192A CN 87108192 A CN87108192 A CN 87108192A CN 87108192 A CN87108192 A CN 87108192A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
- C07D271/113—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明揭示了一种新的化合物,5-叔丁基-3-(4-氯-2-氟-5-炔丙氧基苯基)-1,3,4-二唑-2-酮,作为一种除草剂的活性成分,及其制备方法。
Description
本发明涉及一种新的化合物,5-叔丁基-3-(4-氯-2-氟-5-炔丙氧基苯基)-1,3,4-噁二唑-2-酮,其一种制备方法,及含有该化合物作为一种活性成分的一种除草剂。
上面所述的化合物是新的且具有以前从来没有在文献中描述过或在一个专利中揭示过的优良的除草活性。尽管具有一种相似结构的化合物是众所周知的。例如,具有下列结构式的一种化合物物在美国专利3385862中被揭示,
其中苯环基未被取代或被1至4个选自卤素原子和具有1至4个碳原子的烷基和烷氧基取代基所取代。
同样,具有下列结构式的一种化合物在美国专利3818026中被揭示,
其中R表示一种直链或带支链的C1-C4烷基或C2-C4链烯基。
在已有技术中所揭示的化合物中包括具有较好的除草活性的化合物,且其中某些化合物已处于实际应用。目前,除草剂必须具有较高的活性,保证安全性及由于经济性的原因,因此除草剂的新一代的出现是所希望的。因而,上面所述的在已有技术中所揭示的化合物未必具有令人满意的除草活性,因而对一种具有较高活性的化合物有更高的需求。
为了发展一种具有高除草活性的化合物,本发明人合成并测试了大量化合物以确定这种化合物作为一种除草剂是否有用。结果,出乎意料之外地发现上面所述的化合物具有已有技术中未预见到的高除草活性,本发明即在此发现基础上完成。
因此,本发明的一个目的在于提供一种通过下列结构式表示的化合物5-叔丁基-3-(4-氯-2-氟-5-炔丙氧基苯基)-1,3,4-噁二唑-2-酮,及一种含有该化合物作为一种活性成分的除草剂。
根据本发明通过上面的结构式,其中苯环被一个氟原子取代表示的化合物不仅是新的而且其除草活性是未知的。本发明人通过在苯环上导入一个氟原子而研究提高除草活性的方法,结果,意想不到地发现通过下列结构式表示的化合物显示出特别高的除草活性,
其中X1为一个氟原子,X2为一个氯原子,且R为一种C1-C6烷基或一种C3-C4链烯基或炔基。即,当X1=F,X2=H;X=Cl,X2=F;或X1=H,X2=F时该化合物具有微弱或几乎无除草作用,而且只有上述化合物中当X1=F和X2=Cl时,才能得到极高的活性。同时还发现,当R为一种通过-CH2C-CH表示的炔丙基时,获得最高的除草效果。已发现该化合物比在上面所述的已有技术中所指出的化合物(D),其结构式如下所示具有高得多的除草活性。
这是一种不能从上面所述的已有技术中预见到的惊人的效果,且因此本发明使用低剂量控制有害的杂草是可能的,而且提供了一种非常经济的除草方法。另外,本发明的化合物对温血动物是极安全的。
本发明的化合物可通过下列反应来制备,
其中X表示一种氯原子或溴原子。换句话讲,本发明的化合物可通过5-叔丁基-3-(4-氯-2-氟-5-羟基苯基)-1,3,4-噁二唑-2-酮与炔丙基氯或炔丙基溴反应来制备。
此反应可在一种非质子传递溶剂如乙腈,二甲基甲酰胺,二甲基亚砜,丙酮,甲基乙基酮,氯仿和二氯甲烷或一种能传递质子溶剂如甲醇,乙醇,丙醇,异丙醇和丁醇,或它们的一种混合溶剂中进行。较好的是,该反应在一种碱性物质存在下进行。该碱性物质的实例包括碱金属碳酸盐如碳酸钾,碳酸钠和碳酸氢钠;碱金属氢氧化物如氢氧化钠和氢氧化钾;及碱金属醇盐如甲醇钠和乙醇钠。该反应的温度为10至150℃,最好为40至110℃。
在上面的反应中的起始物料,即是:5-叔丁基-3-(4-氯-2-氟-5-羟基苯基)-1,3,4-噁二唑-2-酮可通过5-叔丁基-3-(4-氯-2-氟-5-异丙氧基苯基)-1,3,4-噁二唑-2-酮与氯化铝反应而得到。该5-叔丁基-3-(4-氯-2-氟-5-异丙氧基苯基)-1,3,4-噁二唑-2-酮可通过将下列结构式的苯肼衍生物用碳酰气(光气)环合制得。
该苯肼衍生物可通过用新戊酸酰氯酰化具有下列结构式所表示的苯肼而得到。
该苯肼可通过下列方法而得到。首先,在乙腈中,在碳酸钾存在下,用异丙基溴或异丙基氯烷基化2-氯-4-氟-5-硝基苯酚(它由,例如,日本经审查的专利申请(Kokoku)10661/1974揭示)而给出4-氯-2-氟-5-异丙氧基硝基苯。在该化合物中的硝基被还原为一个氨基且该氨基被重氮化。因此所产生的化合物最后用新产生的硫酸氢钠还原,如在有机化学杂志(Jounral of Organic Chemistry)30,3946(1965)中所揭示的,或用氯化亚锡还原,如在美国化学协会杂志70,1381(1948)中所揭示的。
当在高地田中通过施用于叶子或施用于土壤时,本发明的化合物显示很强的除草活性;对这种杂草是高效的,如Mehishiba(马唐属睫状肌),Inubiyu(稗属胫-鸡亚目),Shiroza(藜属album),Nagabagishigishi(酸模属皱叶),Aobiyu(苋属翠绿色),Marubaasagao(番薯属coccinea),Himejion(飞逢属一年逢),Inugarashi(焊莱indica),Enokorogusa(狗尾草属翠绿色)和Oonamomi(加拿大苍耳属);且对有用的庄稼作物和谷物,小麦,高地田稻,大豆,棉花和向日葵不会产生化学损伤。
另外,当用于水稻田时,本发明的化合物对一年生杂草如稗子(稗属oryzicola),多叶水苋菜(水苋菜属多花)和雨久花属(雨久花属vaginalis)及多年生杂草如蔗草(蔗草属juncoides),慈姑(慈姑属pygmaea)和莎草(莎草属serotinus)同样有效,但对稻不会产生化学损伤。
本发明的化合物也可为一种用于草地和非作物土地的除草剂的活性成分。
当本发明的化合物用作为一种除草剂的活性成分时,通过与辅剂如固态载体,液态载体和表面活性剂混合,它可配成颗粒,可湿性粉末,一种乳液或一种液体等。作为一种活性成分,本发明的化合物的含量,根据配方的形式,可分布在0.05至80%范围内。
固态载体的实例包括粘土,高岭土,滑石,硅藻土,膨润土,酸性粘土,碳酸钙和植物粉。液态载体包括甲苯,二甲苯,甲基萘,丁醇,异丙醇,1,2-亚乙基二醇,环己酮,甲基乙基酮和动物油及植物油。
本发明的化合物还可与不仅其它除草剂而且其它农业杀虫剂和杀菌剂,植物生长调节剂及肥料混合应用。
作为一种除草剂的剂量根据杂草类,应用时间,应用方法,土壤条件等而变化,用量在0.05至50克每公顷范围内,最好为0.1至50克每公顷。
现在,将通过叙述实施例,比较实施例和参考实施例进一步详细描述本发明,但本发明的范围,当然,不仅仅限于这些实施例。用于比较的化合物如表1中所示,对于并不公知的化合物如参考实施例1至3中所述制备。
表1
化合物 化学结构式 注意
表示
制备方法及性质
制备方法及性质
C
参见参考实施例3
制备方法及性质
中揭示
参考实施例1(制备化合物A的方法)
用于根据本发明的化合物的制备基本相同的方法,从以对氯苯酚作为一种起始物料中得到一种化合物5-叔丁基-3-(4-氯-2-氟-5-异丙氧基苯基)-1,3,4-噁二唑-2-酮,以具有熔点67-68.5℃的结晶形式存在。在无水氯化铝存在下,在二氯甲烷中搅拌所产生的化合物而给出5-叔丁基-3-(2-氯-5-羟基苯基)-1,3,4-噁二唑-2-酮。该化合物用炔丙基溴烷基化而给出熔点为80-81℃的5-叔丁基-3-(2-氟-5-炔丙氧基苯基)-1,3,4-噁二唑-2-酮。其结构已由核磁共振谱,质谱和红外光谱所确证。
参考实施例2(制备化合物B的方法)
用与用于参考实施例1基本相同的方法,从以邻氟苯酚作为一种起始物料中得到作为一种中间体的化合物5-叔丁基-3-(4-氯-3-异丙氧基苯基)-1,3,4-噁二唑-2-酮(熔点72.5-74℃)。随后将该化合物制成所需的具有熔点87-90℃的产物5-叔丁基-3-(4-氟-3-炔丙氧基苯基)-1,3,4-噁二唑-2-酮。其结构已由核磁共振谱和红外光谱所确证。
参考实施例3(制备化合物C的方法)
在作为一种溶剂的二氯甲烷中,该在参考实施例2中所得到的中间体5-叔丁基-3-(4-氟-3-异丙氧基苯基)-1,3,4-噁二唑-2-酮与硫酰氯反应,给出具有熔点67-69℃的5-叔丁基-3-(2-氯-4-氟-5-异丙氧基苯基)-1,3,4-噁二唑-2-酮。随后,将该化合物制成所需的具有熔点114.5-117℃的产物5-叔丁基-3-(2-氯-4-氟-5-炔丙氧基苯基)-1,3,4-噁二唑-2-酮。其结构已由核磁共振谱和红外光谱所确证
实施例1
在80℃下,1.2克5-叔丁基-3-(4-氯-2-氟-5-羟基苯基)-1,3,4-噁二唑-2-酮,0.76克3-溴丙炔,40毫升乙腈和0.3克碳酸钾搅拌反应6小时。冷却后,过滤该反应产物,且将滤液真空蒸馏以除去溶剂。向该剩余物中加入30毫升二氯甲烷,并用5%氢氧化钠水溶液及水洗涤。再经蒸馏除去溶剂,得到1.31克5-叔丁基-3-(4-氯-2-氟-5-炔丙氧基苯基)-1,3,4-噁二唑-2-酮。从正己烷中重结晶,得到具有熔点72-73℃的一种化合物。
核磁共振(200兆赫氘代氯仿(CDCl3)δ
百万分率2.60(1H,t,J=2.44赫)
4.78(2H,d,J=2.44赫)
7.25(1H,d,J=6.35赫)
4.30(1H,d,J=6.35赫)
红外(溴化钾片)厘米-13277,1772
5-叔丁基-3-(4-氯-2-氟-5-羟基苯基)-1,3,4-噁二唑-2-酮的制备:将5克5-叔丁基-3-(4-氯-2-氟-5-异丙氧基苯基)-1,3,4-噁二唑-2-酮溶解在二氯甲烷中,并向该溶液中加入10克细碎的无水氯化铝,然后在25-30℃下搅拌2小时。将冰加入该反应混合物中,用水洗涤该有机层,蒸去此溶剂,并得到4.7克所需要的产物。将一部份产物从正己烷中重结晶得到具有熔点117-119℃的一种产物。
5-叔丁基-3-(4-氯-2-氟-5-异丙氧基苯基)-1,3,4-噁二唑-2-酮的制备:将8.5克4-氯-2-氟-5-异丙氧基苯肼溶解在80毫升甲苯中,并在搅拌下向该溶液中加入19毫升10%的氢氧化钠水溶液。然后在5分钟内将5.4克三甲基乙酰氯滴加至该溶液中并在室温下继续搅拌3小时。分离出该有机层并用一种5%的氢氧化钠水溶液及水洗涤,将因此得到的有机层移至一个烧瓶中,并在40-80℃下将气态碳酰氯(光气)导入该烧瓶3小时。
冷却后,用碱性水及水洗涤该反应液体,蒸去溶剂,并得到12克所需的产物。从水-乙醇混合溶剂中重结晶,得到具有熔点83-85.5℃的一种化合物。
根据在下列实施例2至6中所示的配方,将如上面所述的产生的本发明的化合物配制成除草剂,其中“份”是指“以重量计的份”。
实施例2
通过粉碎及混合50份本发明的化合物,2份十二烷基硫酸钠,2份聚氧乙烯烷基硫酸盐,2份木素硫酸钙,5份白碳和39份高岭土制备一种可湿性粉末。
实施例3
通过粉碎及混合0.1份本发明的化合物,1份聚氧乙烯壬基苯基醚,30份膨润土和68.9份滑石粉,且再用水捏和该混合物,然后成粒和干燥制备一种颗粒。
实施例4
通过混合2份本发明的化合物,5份Solpol 2680-H(Toho Kagaku股份有限公司的一种产品),10份甲基萘和83份二甲苯制备一种乳液。
制备5
通过一种湿法粉碎2份本发明的化合物,2份二辛基硫代琥珀酸钠,3份聚氧乙烯-聚氧丙烯共聚物,4.5份丙二醇,1.5份羧甲基纤维素,2份膨润土和86.5份水制备一种液体配方,直至该活性成份的平均颗粒尺寸小于5微米。
实施例6
通过一种湿法粉碎20份本发明的化合物,3份二辛基硫代琥珀酸钠,3份聚氧乙烯-聚氧丙烯共聚物,4.5份丙二醇,0.5份羧甲基纤维素和69份水制备一种液体配方,直至该活性成份的平均颗粒尺寸小于5微米。
在实施例7至9中测定本发明的化合物和参考化合物的除草效果和化学损伤。在该测定中,用目测观察到测试植物的发芽和生长,该结果用六个等级(0,1,2,3,4和5)来表示。当测试植物正常生长时,样品化合物的除草效果或化学损伤为“0”级,而且当测试植物死亡或一点也不生长时,样品化合物的除草效果或化学损伤为“5”级。
实施例7
在水稻田中测试除草效果和化学损伤,在装满在一个150平方厘米的塑料罐中的水稻田土壤中种上宽叶杂草的种子(例如多叶水苋菜和雨久花属)和蔗草,然后与约1厘米深的表面层混合。接着将慈姑和莎草的块茎埋在该表面层中并向此罐中灌满水。随后,移植在二叶期水稻籽苗。在一个温室中生长一天之后,施用根据实施例2所制得的可湿性粉末。用8毫升水稀释所述量的可湿性粉末且用一根移液管向该溶液中注入水。该测试植物在一个温室中生长19天并测试除草效果和化学损伤。结果如表2所示。
在表2中可以看出,当施用于水稻田时,本发明的化合物比比较化合物A至E具有好得多的除草效果,且不仅对稗子(主要的水稻田杂草)和宽叶杂草而且对蔗草,慈姑和莎草,这些是强壮的多年生且难以控制的杂草,是有效的。这是已有技所未预见到的惊人效果。对(水)稻的化学损伤实际上是微不足道的
实施例8
通过在高地田芽前的土壤中的施用测试除草效果和化学损伤。
在装满在一个325平方厘米的塑料罐中的高地田土壤里种上杂草和庄稼的种子,然后用约5毫米深的土覆盖。施用根据实施例2所制得的可湿性粉末。用5毫升水稀释所述量的可湿性粉末并用一个小喷雾器喷洒在该土壤表面。该测试植物在一个温室中生长15天并测试除草效果和化学损伤。结果如表3所示。在表3中注意,本发明的化合物比比较化合物对强壮的高地田杂草如Shiroza(藜科藜属album),Nagbagishigishi(蓼科酸模属皱叶),Aobiyu(苋科,苋属翠绿色)和Oonamomi(菊科,加拿大苍耳属)有效得多。
实施例9
通过在高地田中的叶子施用测试除草效果和化学损伤。
在装满在一个325平方厘米的塑料罐中的高田地土壤里种上杂草和庄稼的种子,然后用约5毫米深的土覆盖。该测试植物在一个温室中生长10天。对该幼小的测试植物施用根据实施例2所制得的可湿性粉末。用5毫升水稀释所述量的可湿性粉末并用一个小喷雾器喷洒在该测试植物上。该测试植物在一个温室中生长20天并测试除草效果和化学损伤。结果如表4所示。从表4中可以看出本发明的化合物比比较化合物A至E对Mehishiba(禾本科,马唐属睫状肌),Inubiyu(苋属,稗属胫-鸡亚目),Hakobe(石竹科,繁缕属中翅脉),Shiroza(藜科,藜属album),Nagabagishigishi(蓼科,酸模属皱叶),Aobiyu(苋科,苋属翠绿色),Oonamomi(菊科,加拿大苍耳属和Inugarashi(十字花科,焊菜indica)有效得多。
Claims (5)
1、一种化合物5-叔丁基-3-(4-氯-2-氟-5-炔丙氧基苯基)-1,3,4-噁二唑-2-酮。
2、一种制备化合物5-叔丁基-3-(4-氯-2-氟-5-炔丙氧基苯基)-1,3,4-噁二唑-2-酮的方法,包括步骤:在一种溶剂中,5-叔丁基-3-(4-氯-2-氟-5-羟基苯基)-1,3,4-噁二唑-2-酮与炔丙基氯或炔丙基溴反应。
3、根据权利要求2所述的一种方法,其特征在于所述的反应在一种碱性物质存在下进行。
4、根据权利要求2所述的一种方法,其特征在于所述的反应在10℃至150℃温度下进行。
5、一种含有5-叔丁基-3-(4-氯-2-氟-5-炔丙氧基苯基)-1,3,4-噁二唑-2-酮作为一种活性成分的除草剂。
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AU (1) | AU598887B2 (zh) |
BR (1) | BR8706848A (zh) |
CS (1) | CS268694B2 (zh) |
DD (1) | DD264843A5 (zh) |
DK (1) | DK657587A (zh) |
FI (1) | FI875509A (zh) |
HU (1) | HUT48223A (zh) |
IE (1) | IE873400L (zh) |
IL (1) | IL84732A0 (zh) |
MA (1) | MA21132A1 (zh) |
MY (1) | MY101530A (zh) |
NZ (1) | NZ222928A (zh) |
OA (1) | OA08700A (zh) |
PH (1) | PH24164A (zh) |
PL (1) | PL269465A1 (zh) |
PT (1) | PT86368B (zh) |
TR (1) | TR23141A (zh) |
WO (1) | WO1988004653A1 (zh) |
YU (1) | YU228987A (zh) |
ZA (1) | ZA879231B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111226953A (zh) * | 2020-03-08 | 2020-06-05 | 安徽喜田生物科技有限公司 | 一种含有丙炔噁草酮和西草净的除草组合物 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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KR900003140A (ko) * | 1988-08-11 | 1990-03-23 | 오노 알버어서 | 옥사디아졸론 제초제, 그 제조방법 및 그 사용 |
IT1277681B1 (it) * | 1995-12-21 | 1997-11-11 | Isagro Ricerca Srl | Ariltiadiazoloni ad attivita' erbicida |
WO2003013248A1 (en) * | 2001-08-08 | 2003-02-20 | Bayer Cropscience S.A. | Weed control |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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ES403445A1 (es) * | 1971-06-02 | 1975-05-16 | Rhone Poulenc Sa | Procedimiento para la obtencion de derivados de la oxadia- zolona. |
WO1985001939A1 (en) * | 1983-11-04 | 1985-05-09 | Fmc Corporation | Herbicidal 1-aryl-4-substituted-1,4-dihydro-5h-tetrazol-5-ones and sulfur analogs thereof |
AU566839B2 (en) * | 1984-03-29 | 1987-10-29 | Fmc Corporation | Herbicidal 1-aryl-2-1, 2, 4-triazolin-5-ones |
-
1986
- 1986-12-16 JP JP61297457A patent/JPS63150267A/ja active Pending
-
1987
- 1987-12-04 US US07/128,602 patent/US4842640A/en not_active Expired - Fee Related
- 1987-12-04 PH PH36175A patent/PH24164A/en unknown
- 1987-12-07 IL IL84732A patent/IL84732A0/xx unknown
- 1987-12-08 ZA ZA879231A patent/ZA879231B/xx unknown
- 1987-12-12 MY MYPI87003190A patent/MY101530A/en unknown
- 1987-12-14 EP EP87310973A patent/EP0274249A1/en not_active Ceased
- 1987-12-15 HU HU875668A patent/HUT48223A/hu unknown
- 1987-12-15 NZ NZ222928A patent/NZ222928A/en unknown
- 1987-12-15 DK DK657587A patent/DK657587A/da not_active Application Discontinuation
- 1987-12-15 CN CN198787108192A patent/CN87108192A/zh active Pending
- 1987-12-15 MA MA21373A patent/MA21132A1/fr unknown
- 1987-12-15 IE IE873400A patent/IE873400L/xx unknown
- 1987-12-15 AU AU82551/87A patent/AU598887B2/en not_active Ceased
- 1987-12-15 KR KR870014335A patent/KR880007501A/ko not_active Application Discontinuation
- 1987-12-15 FI FI875509A patent/FI875509A/fi not_active IP Right Cessation
- 1987-12-15 PT PT86368A patent/PT86368B/pt not_active IP Right Cessation
- 1987-12-16 WO PCT/JP1987/000987 patent/WO1988004653A1/en unknown
- 1987-12-16 BR BR8706848A patent/BR8706848A/pt unknown
- 1987-12-16 YU YU02289/87A patent/YU228987A/xx unknown
- 1987-12-16 TR TR890/87A patent/TR23141A/xx unknown
- 1987-12-16 DD DD87310538A patent/DD264843A5/de not_active IP Right Cessation
- 1987-12-16 CS CS879303A patent/CS268694B2/cs unknown
- 1987-12-16 PL PL26946587A patent/PL269465A1/xx unknown
- 1987-12-16 OA OA59244A patent/OA08700A/xx unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111226953A (zh) * | 2020-03-08 | 2020-06-05 | 安徽喜田生物科技有限公司 | 一种含有丙炔噁草酮和西草净的除草组合物 |
Also Published As
Publication number | Publication date |
---|---|
YU228987A (en) | 1988-10-31 |
US4842640A (en) | 1989-06-27 |
DD264843A5 (de) | 1989-02-15 |
EP0274249A1 (en) | 1988-07-13 |
KR880007501A (ko) | 1988-08-27 |
CS268694B2 (en) | 1990-04-11 |
FI875509A0 (fi) | 1987-12-15 |
CS930387A2 (en) | 1989-07-12 |
MY101530A (en) | 1991-11-30 |
IL84732A0 (en) | 1988-05-31 |
ZA879231B (en) | 1988-08-31 |
HUT48223A (en) | 1989-05-29 |
DK657587D0 (da) | 1987-12-15 |
PT86368B (pt) | 1990-11-20 |
PL269465A1 (en) | 1989-08-21 |
MA21132A1 (fr) | 1988-07-01 |
BR8706848A (pt) | 1988-07-26 |
WO1988004653A1 (en) | 1988-06-30 |
AU8255187A (en) | 1988-08-04 |
DK657587A (da) | 1988-06-17 |
FI875509A (fi) | 1988-06-17 |
IE873400L (en) | 1988-06-16 |
OA08700A (en) | 1989-03-31 |
JPS63150267A (ja) | 1988-06-22 |
AU598887B2 (en) | 1990-07-05 |
PH24164A (en) | 1990-03-22 |
NZ222928A (en) | 1990-04-26 |
TR23141A (tr) | 1989-04-17 |
PT86368A (en) | 1988-01-01 |
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