CN85108797A - 一种新的苯甲酰苯基脲衍生物的制备方法及其作为杀虫剂的应用 - Google Patents
一种新的苯甲酰苯基脲衍生物的制备方法及其作为杀虫剂的应用 Download PDFInfo
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Abstract
本发明涉及(1)式化合物的制备方法:其中,X1和X3表示氯或氟,X2表示氢,氯化氟,X4表示氢或卤素,X5表示-CF3或OCF3,Y表示氧或硫,以及含有该化合物的杀虫组合物,一个杀死害虫的方法,及其用作杀虫剂。
Description
本发明涉及式(Ⅰ)化合物的制备方法和含有该化合物的
杀虫组合物,杀死害虫的方法,在(Ⅰ)式中,X1和X3各表示氯或氟,X2表示氢,氯或氟,X4表示氢或囟素,X5表示-CF3或-OCF3,Y表示氧或硫。
本发明涉及一种新的苯甲酰苯基脲衍生物,在稻谷产地,山地,果园,森林地带及牲畜棚,该化合物可用来作农药。
人们已经知道,苯甲酰苯基脲衍生物对于抗有机磷杀虫剂的,抗氨基甲酸酯杀虫剂的,和抗拟除虫菊酯杀虫剂的害虫是有效的。例如,在J.Agr.Food Chem,21(6),993(1973)(农业食品化学杂志)中,叙述了N-(对-氯代苯基)-N′-(2,6-二氟代苯甲酰)脲(通常称为“diflubenzuyon”)对黄热蚊,大菜粉碟,马铃薯甲虫具有杀虫活性。
但是,市场上出售的苯甲酰苯基脲衍生物的缺点是,当使用低浓度的上述化合物时,其杀虫谱只限于狭小的范围。
本发明提供的杀虫剂没有上述的缺点。
本发明者发现,通式(Ⅰ)的苯甲酰苯基脲衍生物是一种具有宽的杀
虫谱的剂,并且甚至在低浓度时,该化合物仍具有高的杀虫活性;在(Ⅰ)式中,X1和X3各表示氯原子或氟原子,X2表示氢,氯或氟原子,X4表示氢或囟素原子,X5表示-CF3或-OCF3,而Y则表示氧或硫原子。
上述通式(Ⅰ)的化合物可用下述方法(a)和(b)来制备:
方法(a):该法包括,使式(2)的2,4,5-取代的苯胺:
和式(3)的2,6-取代的苯甲酰异氰酸酯或2,6-取代的苯甲酰异硫氰酸酯发生反应;
在(2)式中,X3,X4和X5具有上述相同的含义,及在(3)式中,X1,X2和Y具有上述相同的含义。
按下述步骤容易实现这一方法,即最好先把上述(2)式的取代苯胺溶解在惰性溶剂中,然后将溶解在惰性溶剂中的,上述(3)式的2,6-取代苯甲酰异氰酸酯或2,6-取代苯甲酰异硫氰酸酯溶液,逐滴加入到(2)式的取代苯胺溶液中,而温度保持在-5℃到100℃,最好是0~40℃。
惰性溶剂的实例有,芳香烃例如苯,甲苯,二甲苯,一氯代苯,和二氯代苯;酯类例如乙酸乙酯、腈类例如乙腈、正-己烷、酮类例如丙酮;脂族氯化烃例如四氯化碳和perclene(全氯乙烯);以及醚类例如二噁烷和四氢呋喃。
反应完毕后,按照常用的方法处理产物,就得到预期的产品。
用作原料的取代苯甲酰异氰酸酯和取代苯甲酰异硫氰酸酯((3)式)是已知的化合物,它们可用传统的方法(J.Org.Chem;30(12),4306-7(1965)(有机化学杂志)和J.Am.Chem.Soc,61,632(1939)(美国化学会志))来制得。
按照下列反应:
可以制得式(2)的2,4,5-取代苯胺;反应式中的X3表示氟或氯原子,X4表示氟,氯或溴原子,而X5则表示-CF3或-OCF3。
方法(b):该法包括,使式(4)的2,4,5-取代苯基异氰酸酯或2,4,5-取代苯基异硫氰酸酯
与式(5)的2,6-取代苯甲酰胺发生反应:
在(4)式中的X3,X4,X5和Y,以及在(5)式中的X1和X2都具有上述的相同含义。
在本方法中,这两个原料化合物最好溶解在上述的惰性溶剂中,然后在30~180℃温度下,最好是在40~150℃温度下,进行反应1小时到24小时。
用作原料的,上述(4)式的2,4,5-取代苯基异氰酸酯和2,4,5-取代苯基异硫氰酸酯,可以用普通的方法(Yu Ri Go Sei Kaga Ka KyoKai-Shi,34,431(1976)和J.Am.Chem.Soc,54,781(1932))从相应的苯胺中来制取。
在本发明的(Ⅰ)式化合物中,优先选用下列化合物:
(A)当(Ⅰ)式中的Y表示氧时:
X1和X3各表示氯或氟,
X2表示氢,氯或氟,
X4表示氢或囟素,
X5表示-CF3或-OCF3
(B)当(Ⅰ)式中的Y表示硫时:
X1表示氯或氟,
X2表示氢,氯或氟,
X3表示氟,
X4表示氟,氯或溴,X5表示-CF3或-OCF3以及
在(Ⅰ)式化合物中,下列化合物则更好:
(C)当(Ⅰ)式中的Y表示氧时:
X1,X2和X3是氟,
X4是氟,氯或溴,
X5是-CF3或-OCF3
(D)当(Ⅰ)式中的Y表示硫时:
X1,X2和X3是氟,
X4是氯,氟或溴,
X是-CF3或-OCF3以及
具有下列结构式的化合物是(Ⅰ)式化合物中最好的化合物:
本发明的(Ⅰ)式化合物可以单独用作杀虫剂,或与辅助剂一起以混合物形式用作杀虫剂,以便改进或稳定其杀虫效力,这取决于(Ⅰ)式化合物的用途。通式(Ⅰ)的化合物可以被配成,例如,粉剂,细颗粒制剂,粒剂,可湿性粉末,可流动性液体,浓缩乳剂,或有毒的饲料。
在实际应用这些不同的产品时,人们可以直接使用上述形态的产品,或在用水稀释产品到预期的浓度以后再使用。
这里所用的农药辅助剂包括载体(稀释剂)和其他辅助剂如铺展剂,乳化剂,湿润剂,分散剂,固定剂和喷散剂。液体载体的实例有,芳香烃例如甲苯和二甲苯;醇类例如丁醇,辛醇和1,2-乙二醇;酮类例如丙酮;胺类例如二甲基甲酰胺;亚砜例如二甲基亚砜;甲基萘;环己酮;动物油和植物油;脂肪酸;脂肪酸酯;石油馏分例如煤油和汽油;以及水。固体载体的实例有,粘土,高岭土,滑石,硅藻土,二氧化硅,碳酸钙,蒙脱石,膨润土,长石,石英,无水矾石和锯末。
通常被用作为乳化剂和分散剂的是表面活性剂。表面活性剂包括阴离子表面活性剂,阳离子表面活性剂,非离子表面活性剂,和两性的表面活性剂例如较高级醇的硫酸钠,氯化硬脂酰三甲基铵,聚氧乙烯烷基苯基醚,十二烷基三甲铵乙内酯。
铺展剂的实例有,聚氧乙烯壬基苯基醚和聚氧乙烯十二烷基醚。湿润剂的实例有聚氧乙烯壬基苯基醚二烷基磺基琥珀酸盐。固定剂有羧甲基纤维素,聚乙烯醇等,以及喷散剂有木素磺酸钠,十二烷基磺酸钠等。
本发明的农药可以单独使用,或与杀(真)菌剂,杀虫剂,杀螨剂,除草剂,植物生长调节剂,土壤灭菌剂,土壤调节剂或杀线虫剂以及化肥或另外的农药混合使用。
对拟除虫菊酯,当加入例如胡椒基丁醚,亚砜或saforxane作增效剂时,杀虫活性可增大数倍。
在本发明组合物中,其活性组份浓度的变化取决于农药的形态,使用方式及其他的条件。虽然活性组份可以单独使用,但是,以组合物为基准,其使用量一般为0.2~95%(重量),最好为0.5~30%(重量)。
本发明组合物使用量的变化取决于农药的形态,使用方式,周期和其他的条件。当用来控制观赏植物,森林或家畜的害虫时,每10公亩(1公亩=1002米)土地,农药的使用量为0.1~100克,最好是1.0~50克(以活性组份计算),用于消灭组生方面的害虫时,使用量为0.01~10毫克,最好是0.02~5毫克/米2(以活性组份计算),例如,对于粉剂,粒剂,和浓缩乳剂或可湿性粉末农药,以活性组份计,其使用量每10公亩土地分别为0.1~50克,0.2~100克和0.1~100克。在特殊情况下,其使用量可以超出上述范围。
本发明的杀虫剂可用于消灭的害虫的典型实例如下:
(1)鳞翅目:
桃潜蛾,小菜蛾,棉籽蠕虫,茶小卷叶蛾大豆食心虫,稻纵卷叶螟,二化螟,东方玉米螟,甘蓝夜蛾,一星粘虫,斜纹夜蛾,直纹稻苞虫,菜粉蝶,
(2)鞘翅目:
铜黄异丽金龟,日本弧丽金龟,稻鳞象甲,稻象甲,稻页泥虫,小圆皮蠹,大谷盗,玉米象,茄二十八星飘虫,绿豆象,松天牛,黄守瓜,
(3)双翅目
热带蚊,黄热蚊,家蚊,大豆荚瘿蚊,瓜种蝇,家蝇,瓜实蝇,和稻潜蝇,
(4)直翅目:
非洲蝼蛄,飞蝗,小翅稻蝗,德国小蠊,烟色大蠊,
(5)膜翅目:
菜叶蜂和梨三节叶蜂,
(6)Tylenchida:
大豆包囊线虫,稻包囊线虫,棉根癌线虫,root-lesion nematode,rice white tip mematode,菊花叶线虫(Aphelenchaides besseyi),菊花叶线虫(Aphelenchoides ritzemabosi)和松木线虫,以及
(7)半翅目:
本发明的化合物可被应用于害虫或其所在地。
由下列试验结果表明,本发明的(Ⅰ)式化合物的杀虫效力高于迄今已使用的其他苯甲酰苯基脲衍生物。
本发明将以下列实例作进一步说明。
合成实例1
4-溴-2-氯-5-三氟甲基苯胺的制备:
在室温下,在40毫升乙酸中搅拌3.9克(0.02摩尔)2-氯-5-三氟甲基苯胺和3.1克(0.03摩尔)乙酸酐2小时,然后使温度升高到110℃。在110温度下将3.5克(0.022摩尔)溴逐滴加入上述溶液中。反应完毕后,把反应混合物倒入水中,用苯萃取,并用水洗。除掉溶剂以后,在残渣上加入30毫升乙醇和30毫升浓盐酸,并在回流加热条件下加热该混合物1小时。冷却后,用10%氢氧化钠水溶液中和反应混合物,用苯萃取,并用水和盐水洗涤。在减压条件下除去溶剂后,用蒸馏法纯化残渣。
产量:5.4克
沸点:119~121℃/28mm Hg(毫米汞柱)
合成实例2
N-(4-溴-2-氟-5-三氟甲基苯基)-N′-(2,6-二氟苯甲酰)脲的制备:
将按照合成实例1的相同方法制得的2.58克(0.01摩尔)4-溴-2-氟-5-三氟甲基苯胺溶于40毫升甲苯中。把3.9克(0.0105摩尔)2,6-二氟苯甲酰异氰酸酯溶于甲苯中,配制成浓度为50%溶液,然后在低于10℃温度下,在不断搅拌情况下,将50%2,6-二氟苯甲酰异氰酸酯溶液逐滴加到上述溶液中。在25℃温度下,搅拌1小时后,就生成沉淀,并过滤沉淀。再用乙酸乙酯进行重结晶,就得到3.9克无色结晶(产率为90%)。产品的熔点为208~210℃。
合成实例3
N-(4-溴-2-氯-5-三氟甲基苯基)-N′-(2,6-二氟苯甲酰)脲的制备:
在2.36克(0.015摩尔)2,6-二氟苯甲酰胺中,加入4.8克(0.016摩尔)4-溴-2-氯-5-三氟甲基苯基异氰酸酯和50毫升甲苯,并在回流条件下加热该混合物20小时。
在生成的沉淀冷却以后,进行过滤。再用乙酸乙酯进行重结晶,就得到5.8克(产率为85%)无色结晶。其熔点为184~187℃。
合成实例4
N-(4-溴-2-氟-5-三氟甲基苯基)-N′-(2,6-二氟苯甲酰)硫脲的制备:
将1.2克硫氰酸钾溶于20毫升无水丙酮中,再另外把1.8克(0.01摩尔)2,6-二氟苯甲酰氯溶于5ml丙酮中配成溶液,并在室温下将该溶液逐滴加到上述溶液中,并同时进行搅拌。溶液滴加完毕后,在回流情况下加热该混合物10分钟,然后在反应混合物被缓慢回流加热的条件下,把溶于10ml丙酮中的,2.6克(0.01摩尔)4-溴-2-氟-5-三氟甲基苯胺的丙酮溶液,逐滴加入上述反应混合物中,再继续回流加热20分钟,冷却反应混合物,然后把它倒入冰/水中。过滤所生成的结晶,并用水和乙醇洗涤结晶,然后进行干燥。再用甲苯进行重结晶,得到3.7克无色结晶(产率为81%)其熔点为161~163℃。
按上述相同方法制备的化合物列于表1。
配方实例1
5%浓缩乳剂:
将80份二甲基亚砜和15份烷基酚/环氧乙烷缩合物与烷基苯磺酸钙的混合物(8∶2)(商品名:L-1515-21t;Takemoto Yushi公司的产品)加入到5份N-(4-溴-2-氟-5-三氟甲基苯基)-N′-(2,6-二氟苯甲酰)脲中,就制成浓缩乳剂。用水稀释后,该浓缩乳剂就冲稀成1/1000~1/4000浓度的乳化液。
配方实例2
20%可湿性粉末:
把54份高岭土,20份硅藻土,3份木素磺酸钠和3份十二烷基苯磺酸钠加入到20份N-(4-溴-2-氟-5-三氟甲基苯基)-N′-(2,6-二氟苯甲酰)脲中,就配制成可湿性粉末。
用水稀释后,该可湿性粉末就冲稀成1/1000到1/4000浓度的溶液。
配方实例3
20%可流动性液体:
在20份N-(4-溴-2-氟-5-三氟甲基苯基)-N′-(2,6-二氟苯甲酰)脲中,加入20份1,2-乙二醇,3份木素磺酸钠,3份十二烷基苯磺酸钠,0.1份防沫剂(商品名:pelex Rp;Kao SekRen公司的产品),和56.9份水,就配制成可流动性液体。用水稀释后,该产品就冲稀成1/1000~1/4000浓度的溶液。
试验实例1
杀死小菜蛾的第三龄(third instar larvae)幼虫的效果:
将含有列于表1上的本发明化合物或对照化合物的5%浓缩乳剂稀释到给定浓度(5.0ppm),配制成水溶液,然后把2片五叶期到六叶期(hexefoliate stages)的甘蓝叶浸入该水溶液中10秒钟。取出凉干后,将甘蓝叶放入高度为5厘米的塑料容器内。然后把10只小菜蛾的幼虫(第三龄态)放入容器内。再将容器放在可控制温度的房间内,温度为25℃。4天以后,统计死亡的昆虫数,以计算其死亡率。结果排列如下:
死亡率
A:90%或更高
B:从50%到小于90%
C:从20%到小于50%
D:小于20%
用作对照化合物的是N-(对-氯代苯基)-N′-(2,6-二氟甲酰)脲(控制A)和N-(4-溴-2-氟苯基)-N′-(2,6-二氟苯甲酰)脲(控制B)(该化合物公布在日本专利Laid-Open说明书No148847/1983)
试验结果见表2
表2杀死小菜蛾的第三龄期幼虫的效果
效果 死亡率(5.0ppm)
化合物
对照化合物A D
对照化合物B D
化合物 2 A
化合物 4 A
化合物 7 A
化合物 8 A
化合物 9 A
化合物 10 A
化合物 11 A
化合物 12 A
化合物 13 A
化合物 14 A
试验实例2:
杀死斜纹夜蛾的第三龄期幼虫的效果:
把5片甘蓝叶浸入含有给定浓度的本发明化合物和对照化合物的水溶液(1.0ppm)中,取出凉干后,将甘蓝叶放入其体积为10×15×5(高度)厘米的塑料容器内,再按实验实例1相同的方法把10只第三龄的斜纹夜蛾的幼虫放入容器内。4天以后,统计死亡的昆虫数目。结果的排列顺序与试验1中的相同。试验结果见表3。
表3杀死斜纹夜蛾幼虫的效果
效果 死亡率(1.0ppm)
化合物
对照化合物A C
对照化合物B B
化合物 1 A
化合物 2 A
化合物 3 A
化合物 4 A
化合物 7 B
化合物 8 A
化合物 9 A
化合物 10 A
化合物 11 A
化合物 12 A
化合物 13 A
化合物 14 A
试验实例3:
杀死家蚊(house masquitoes)的效果
在直径为9厘米的塑料杯中,加入200ml优质水。然后在杯中放入20只第三龄的家蚊幼虫(在Ageo城获得的),并加入20%本发明化合物(见表1)的可湿性粉末或20%与试验实例1相同的控制化合物的可湿性粉末,这样就使农药稀释到给定浓度(0.01ppm)。一星期以后,统计死亡昆虫数。试验结果列于表4。
结果的排列顺序与试验实例1相同。
表4杀死家蚊幼虫的效果
效果 死亡率(0.01ppm)
化合物
对照化合物A C
对照化合物B B
化合物 1 A
化合物 2 A
化合物 3 A
化合物 4 A
化合物 5 A
化合物 7 A
化合物 8 A
化合物 9 A
化合物 10 A
化合物 11 A
化合物 12 A
化合物 13 A
化合物 14 A
Claims (22)
3、按照权项1和2所述的方法,其特征在于,
X1和X3表示氯或氟,
X2表示氢,氯或氟,
X4表示氢或囟素,和
X5表示-CF3或-OCF3,以及Y表示氧。
4、按照权项1和2所述的方法,其特征在于,
X1表示氯或氟,
X2表示氢,氯或氟,
X3表示氟,
X4表示氟,氯或溴,
X5表示-CF3或-COF3和Y表示硫。
5、按照权项3所述的方法,其特征在于,
X1,X2和X3表示氟,
X4表示氟,氯或溴,
X5表示-CF3或-OCF3和Y表示氧。
6、按照权项4所述的方法,其特征在于,
X1,X2和X3表示氟,
X4表示氯,氟或溴,
X5表示-CF3或-OCF3和Y表示硫。
7、按照权项1和2所述的方法,所制得的化合物具有下例结构式:
10、按照权项9所述的杀虫组合物,其特征在于
X1和X3表示氯或氟,
X2表示氢,氯或氟,
X4表示氢或囟素,和
X5表示-CF3或-OCF3,以及Y表示氧。
11、按照权项9所述的杀虫组合物,其特征在于
X1表示氯或氟,
X2表示氢,氯或氟,
X3表示氟,
X4表示氟,氯或溴,
X5表示-CF3或-OCF3和Y表示硫。
12、按照权项10所述的杀虫组合物,其特征在于
X1,X2和X3表示氟,
X4表示氟,氯或溴,
X5表示-CF3或-OCF3和Y表示氧。
13、按照权项11所述的组合物,其特征在于,
X1,X2和X3表示氟,
X4表示氟,氯或溴,
X5表示-CF3或-OCF3和Y表示硫。
17、按照权项16所述的方法,其特征在于X1和X3表示氯或氟,X2表示氢,氯或氟,X4表示氢或囟素,X5表示-CF3或-OCF3,和Y表示氧。
18、按照权项16所述的方法,其特征在于X1表示氯或氟,X2表示氢,氯或氟,X3表示氟,X4表示氟,氯或溴,X5表示-CF3或-OCF3,和Y表示硫。
19、按照权项16所述的方法,其特征在于X1,X2和X3表示氟,X4表示溴,氯或氟,X5表示-CF3或-OCF3和Y表示氧。
20、按照权项16所述的方法,其特征在于X1,X2和X3表示氟,X4表示氯,氟或溴,X5表示-CF3或-OCF3和Y表示硫。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP268435/84 | 1984-12-21 | ||
JP59268435A JPS61148157A (ja) | 1984-12-21 | 1984-12-21 | ベンゾイルフエニル尿素誘導体およびそれを含有する害虫防除剤 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN85108797A true CN85108797A (zh) | 1986-09-24 |
Family
ID=17458450
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN198585108797A Pending CN85108797A (zh) | 1984-12-21 | 1985-12-19 | 一种新的苯甲酰苯基脲衍生物的制备方法及其作为杀虫剂的应用 |
Country Status (13)
Country | Link |
---|---|
US (1) | US4734436A (zh) |
JP (1) | JPS61148157A (zh) |
CN (1) | CN85108797A (zh) |
AU (1) | AU5152585A (zh) |
BR (1) | BR8506427A (zh) |
DE (1) | DE3544501A1 (zh) |
ES (2) | ES8706618A1 (zh) |
FR (1) | FR2576018A1 (zh) |
GB (1) | GB2168702B (zh) |
HU (1) | HUT41233A (zh) |
IT (1) | IT1214646B (zh) |
NL (1) | NL8503512A (zh) |
ZA (1) | ZA859337B (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62111903A (ja) * | 1985-11-11 | 1987-05-22 | Nippon Kayaku Co Ltd | 殺虫組成物 |
JPS62175452A (ja) * | 1986-01-28 | 1987-08-01 | Sumitomo Chem Co Ltd | ベンゾイル尿素誘導体、その製造法およびそれを有効成分として含有する殺虫剤 |
DE3740807A1 (de) * | 1987-12-02 | 1989-06-15 | Bayer Ag | Substituierte benzoyl(thio)harnstoffe |
KR100194535B1 (ko) * | 1995-12-27 | 1999-06-15 | 우종일 | 아릴 벤조일 우레아 유도체 및 이를 함유하는 농약조성물 |
KR100194534B1 (ko) * | 1996-06-29 | 1999-06-15 | 우종일 | 2-클로로-3,5-비스 (트피플루오르메틸) 페닐 벤조일 우레아 유도체 및 이의 제조방법 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3793213A (en) * | 1969-10-23 | 1974-02-19 | Armour Dial Inc | Germicidal process and detergent compositions |
US3686418A (en) * | 1969-10-23 | 1972-08-22 | Armour & Co | N-acyl-n{40 -(halogenated aryl ureas as antibacterial agents) |
US3989842A (en) * | 1970-05-15 | 1976-11-02 | U.S. Philips Corporation | Certain substituted benzoyl urea insecticides |
US4013717A (en) * | 1970-05-15 | 1977-03-22 | U.S. Philips Corporation | Benzoyl phenyl urea derivatives having insecticidal activities |
NL160809C (nl) * | 1970-05-15 | 1979-12-17 | Duphar Int Res | Werkwijze ter bereiding van benzoylureumverbindingen, alsmede werkwijze ter bereiding van insekticide prepara- ten op basis van benzoylureumverbindingen. |
DE2531279C2 (de) * | 1975-07-12 | 1983-07-14 | Bayer Ag, 5090 Leverkusen | N-(3-Trifluormethyl-4-halogen-phenyl)- N'-benzoyl-harnstoffe, Verfahren zu ihrer Herstellung und ihre Verwendung als Insektizide |
DE2837086A1 (de) * | 1978-08-24 | 1980-03-06 | Bayer Ag | Substituierte n-phenyl-n'-benzoyl- thioharnstoffe, verfahren zu ihrer herstellung und ihre verwendung als schaedlingsbekaempfungsmittel |
US4399152A (en) * | 1980-04-03 | 1983-08-16 | Duphar International B.V. | Substituted benzoyl ureas as insecticides |
DE3161657D1 (en) * | 1980-11-22 | 1984-01-19 | Celamerck Gmbh & Co Kg | Urea derivatives, preparation and use |
JPS57126418A (en) * | 1981-01-29 | 1982-08-06 | Yamanouchi Pharmaceut Co Ltd | Antiallergic agent |
CA1238650A (en) * | 1982-03-01 | 1988-06-28 | Hiroshi Nagase | Urea derivatives, their production and use |
DE3217620A1 (de) * | 1982-05-11 | 1983-11-17 | Bayer Ag, 5090 Leverkusen | 2,5-dihalogenbenzoyl-(thio)harnstoffe, verfahren zu ihrer herstellung und ihre verwendung als schaedlingsbekaempfungsmittel |
US4529819A (en) * | 1982-08-02 | 1985-07-16 | The Dow Chemical Company | Method for making benzoylphenylureas |
IT1161228B (it) * | 1983-04-22 | 1987-03-18 | Montedison Spa | Benzoil-uree ad attivita' insetticida |
-
1984
- 1984-12-21 JP JP59268435A patent/JPS61148157A/ja active Pending
-
1985
- 1985-12-05 GB GB08530022A patent/GB2168702B/en not_active Expired
- 1985-12-05 ZA ZA859337A patent/ZA859337B/xx unknown
- 1985-12-09 US US06/806,601 patent/US4734436A/en not_active Expired - Fee Related
- 1985-12-17 DE DE19853544501 patent/DE3544501A1/de not_active Withdrawn
- 1985-12-19 CN CN198585108797A patent/CN85108797A/zh active Pending
- 1985-12-19 NL NL8503512A patent/NL8503512A/nl not_active Application Discontinuation
- 1985-12-20 FR FR8519010A patent/FR2576018A1/fr active Pending
- 1985-12-20 ES ES550207A patent/ES8706618A1/es not_active Expired
- 1985-12-20 HU HU854920A patent/HUT41233A/hu unknown
- 1985-12-20 AU AU51525/85A patent/AU5152585A/en not_active Abandoned
- 1985-12-20 BR BR8506427A patent/BR8506427A/pt unknown
- 1985-12-23 IT IT8523362A patent/IT1214646B/it active
-
1987
- 1987-04-01 ES ES557484A patent/ES8801897A1/es not_active Expired
Also Published As
Publication number | Publication date |
---|---|
NL8503512A (nl) | 1986-07-16 |
HUT41233A (en) | 1987-04-28 |
IT1214646B (it) | 1990-01-18 |
FR2576018A1 (fr) | 1986-07-18 |
ZA859337B (en) | 1986-08-27 |
DE3544501A1 (de) | 1986-06-26 |
ES8706618A1 (es) | 1987-07-01 |
ES8801897A1 (es) | 1988-03-01 |
GB2168702B (en) | 1988-04-27 |
US4734436A (en) | 1988-03-29 |
JPS61148157A (ja) | 1986-07-05 |
GB2168702A (en) | 1986-06-25 |
BR8506427A (pt) | 1986-09-02 |
GB8530022D0 (en) | 1986-01-15 |
ES550207A0 (es) | 1987-07-01 |
AU5152585A (en) | 1986-06-26 |
ES557484A0 (es) | 1988-03-01 |
IT8523362A0 (it) | 1985-12-23 |
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