CN1037349C - 氟丙基噻唑啉衍生物和除草剂 - Google Patents
氟丙基噻唑啉衍生物和除草剂 Download PDFInfo
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- CN1037349C CN1037349C CN95191163A CN95191163A CN1037349C CN 1037349 C CN1037349 C CN 1037349C CN 95191163 A CN95191163 A CN 95191163A CN 95191163 A CN95191163 A CN 95191163A CN 1037349 C CN1037349 C CN 1037349C
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Abstract
式(1)表示的氟丙基噻唑啉、含该化合物的除草剂及合成该化合物的中间体。
Description
技术领域
本发明涉及新颖的氟丙基噻唑啉衍生物及以该衍生物为有效成分的除草剂。
背景技术
为保护水稻、小麦、玉米、大豆、棉花、甜菜等重要作物不受杂草影响和增加收成,使用除草剂是必不可少的。尤其是近年来,人们期望有一种可在这些有用作物和杂草共存的耕地,向作物和杂草的茎叶部同时施用时能选择性地仅使杂草枯死而不对作物产生伤害的选择性除草剂。另外,从防止环境污染、降低输送、施用时的经济成本等角度出发,人们对以尽可能低的药量得到很好的除草效果的除草剂进行了长期的研究。几种具有这种特性的化合物现在被作为选择性除草剂使用,但对具有这些性质的更优异的新化合物的需要依然存在。
作为与本发明化合物类似的背景技术,公开号为WO93/00336的国际专利申请公开了取代的噻唑啉类化合物,但对权利要求1所述的化合物对甜菜显示特殊的高安全性并具有优异的除草效果未作任何记载。即,本发明化合物具有从上述背景技术完全无法预期得到的特殊的效果。
发明的公开
本发明者为开发对重要作物具有选择性的除草剂进行了长期探索,研究了许多化合物的除草特性,试图寻找出除草性能更好且具有选择性的化合物。结果发现,式(1):表示的氟丙基噻唑啉衍生物及其农业上适合的盐类(以下称本发明化合物)在土壤处理、土壤混和处理及茎叶处理时,均对许多杂草显示特别强的除草效果且对重要作物甜菜具有很高的安全性,由此完成了本发明。
本发明化合物可通过选择下述反应式1~6中的任一个而容易地加以制造。〔反应式1〕〔式中,Z表示卤原子。〕即,将三嗪衍生物(2)在四氢呋喃、二甲氧基乙烷、乙腈、丙腈、二甲基甲酰胺、二氯甲烷、二氯乙烷、苯、甲苯等溶剂中,与异氰酸氯磺酰酯(chlorosulfonyl iso-cyanate)反应,接着,在三乙胺、吡啶、氢化钠、甲醇钠、乙醇钠、氢氧化钠、氢氧化钾、碳酸钾等碱的存在下,与2-亚氨基-3-氟丙基噻唑啉(3)或(4)反应,即可得到本发明化合物(1)。
三嗪衍生物(2)与异氰酸氯磺酰酯的用量比为1∶0.7~1.3(摩尔)。反应温度可在-50℃~80℃的范围内任意选择。
相对于三嗪衍生物(2)1摩尔,使用2-亚氨基-3-氟丙基噻唑啉(3)或(4)0.7~1.3摩尔,而相对于2-亚氨基-3-氟丙基噻唑啉(3)或(4)1摩尔,使用碱0.5~4.0摩尔。反应温度可在-50℃~100℃的范围内任意选择。〔反应式2〕〔式中,Z的定义同上,Y表示C1~C6低级烷基或苯基。〕
即,将2-亚氨基-3-氟丙基噻唑啉(3)或(4)与N-氯磺酰氨基甲酸苯酯(5:Y=苯基)或N-氯磺酰氨基甲酸烷基酯(5:Y=低级烷基)反应,2-亚氨基-3-氟丙基噻唑啉(3)或(4)与氨基甲酸酯衍生物(5)的摩尔比为1比0.5~3.0,最好为1比0.9~1.2。
反应温度可在-50℃~100℃的范围内任意选择,宜为-40℃~30℃。
本反应通过使用各种碱而进行。2-亚氨基-3-氟丙基噻唑啉(3)或(4)与碱的摩尔比为1比0.5~4.0。
作为合适的碱,可使用三乙胺、吡啶等有机碱、氢化钠等金属氢化物、氢氧化钠、氢氧化钾、碳酸钾等无机碱、甲醇钠、乙醇钠等金属烷氧化物。
本反应的合适溶剂是对本反应呈惰性的溶剂,例如,苯、甲苯、二甲苯等芳香烃类、二氯甲烷、氯仿、二氯乙烷等卤烃类、乙醚、异丙醚、二噁烷、四氢呋喃等醚类、乙腈、丙腈等腈类、石油醚、庚烷等烃类、丙酮、丁酮等酮类、乙酸乙酯等酯类、二甲基甲酰胺、二甲基乙酰胺、六甲基磷酰胺等酰胺类。这些溶剂可单独使用或混合使用。其中,尤其优选醚类或酰胺类。
接着,将3-氟丙基噻唑啉-2-亚氨基磺酰氨基甲酸苯酯(6:Y=苯基)或3-氟丙基噻唑啉-2-亚氨基磺酰氨基甲酸烷基酯(6:Y=低级烷基)和三嗪衍生物(2)在苯、甲苯、二甲苯、二噁烷等各种溶剂中加热,即可得到本发明化合物(1)。〔反应式3〕〔式中,Y的定义同上〕
即,将3-氟丙基噻唑啉-2-亚氨基磺酰胺(7)在丙酮、乙腈、二噁烷等溶剂中,于碳酸钾等无机碱或三乙胺、1,8-二氮杂二环〔5.4.0〕十-碳-7-烯(DBU)等有机碱的存在下,与氨基甲酸酯衍生物(8)反应,即可得到本发明化合物(1)。〔反应式4〕〔式中,Y的定义同上。〕
即,将3-氟丙基噻唑啉-2-亚氨基磺酰胺(7)在丙酮、丁酮、乙腈、四氢呋喃、二甲基甲酰胺、二噁烷等溶剂中,于碳酸钾、三乙胺等碱的存在下,与氯甲酸酯或碳酸酯反应,得到3-氟丙基噻唑啉-2-亚氨基磺酰氨基甲酸苯酯(6:Y=苯基)或3-氟丙基噻唑啉-2-亚氨基磺酰氨基甲酸烷基酯(6:Y=低级烷基)。接着,在苯、甲苯、二甲苯、二噁烷等溶剂中,与三嗪衍生物(2)一起加热,即可得到本发明化合物(1)。〔反应式5〕
即,将2-亚氨基-3-氟丙基噻唑啉(3)与异氰酸氯磺酰酯反应,2-亚氨基-3-氟丙基噻唑啉(3)与异氰酸氯磺酰酯的摩尔比为1比0.7~2.0,最好为1比0.9~1.5。
在本反应中,中间体1-〔3-(3-氟丙基)噻唑啉-2-亚氨基磺酰〕-3-氯磺酰脲的合成系在反应温度-50℃~50℃的范围内进行。接着,在60℃~150℃的范围内设定适合于重排反应及除去伴随重排反应而生成的氯化氢的反应温度,通过加热,即可将中间体转化成异氰酸3-氟丙基噻唑啉-2-亚氨基磺酰酯(9)。
本发明的合适溶剂是对本反应呈惰性的溶剂,例如,苯、甲苯、二甲苯等芳香烃类、氯苯、二氯苯等芳香族卤化物类、硝基苯等芳香族硝基化物类、二氯乙烷等卤烃类、二噁烷、四氢呋喃等醚类、乙腈、丙腈等腈类、石油醚、庚烷等烃类、丁酮等酮类、乙酸乙酯等酯类。这些溶剂可单独使用或混合使用。其中,尤其优选芳香族卤化物类或芳香烃类。
接着,将异氰酸3-氟丙基噻唑啉-2-亚氨基磺酰酯(9)与三嗪衍生物(2)在二氯甲烷、氯仿、二氯乙烷、乙醚、二噁烷、乙腈、丙酮、丁酮、苯、甲苯、二甲苯、氯苯、二氯苯等溶剂中反应,即可得到本发明化合物(1)。〔反应式6〕
即,将3-氟丙基噻唑啉-2-亚氨基磺酰氯(10)与三嗪衍生物(2)和氰酸钠反应,3-氟丙基噻唑啉-2-亚氨基磺酰氯(10)与三嗪衍生物(2)和氰酸钠的摩尔比为1∶0.5~1.5∶1~3。反应温度可在-20℃~50℃的范围内任意选择,优选5℃~30℃。
本反应通过使用各种碱而进行。3-氟丙基噻唑啉-2-亚氨基磺酰氯(10)与碱的摩尔比为1∶1~3。
作为合适的碱,可使用三乙胺、吡啶等有机碱类、甲醇钠、乙醇钠等金属烷氧化物类、氢化钠等金属氢化物类、氢氧化钠、氢氧化钾、碳酸钾等无机碱类,尤其优选有机碱。
本反应的合适溶剂是对本反应呈惰性的溶剂,例如,苯、甲苯、二甲苯等芳香烃类、二氯甲烷、氯仿、二氯乙烷等卤烃类、二噁烷、四氢呋喃等醚类、乙腈、丙腈等腈类、丙酮、丁酮等酮类、二甲基甲酰胺、二甲基乙酰胺、六甲基磷酰胺等酰胺类。这些溶剂可单独使用或混合使用。其中,尤其优选腈类或酰胺类。
在反应式7中,硫酰氯的量可在等摩尔量至过量之间任意选择。
本反应通过使用各种碱而进行。2-亚氨基-3-氟丙基噻唑啉(3)或(4)与碱的摩尔比为1∶0.8~5。
作为合适的碱,可使用三乙胺、吡啶等有机碱类、甲醇钠、乙醇钠等金属烷氧化物类、氢化钠等金属氢化物类、氢氧化钠、氢氧化钾、碳酸钾等无机碱类,尤其优选有机碱。
本反应的合适溶剂是对本反应呈惰性的溶剂,例如,苯、甲苯、二甲苯等芳香烃类、二氯甲烷、氯仿、二氯乙烷等卤烃类、二噁烷、四氢呋喃等醚类、乙腈、丙腈等腈类、丙酮、丁酮等酮类、二甲基甲酰胺、二甲基乙酰胺、六甲基磷酰胺等酰胺类。
这些溶剂可单独使用或混合使用。
反应温度可在-50℃~100℃的范围内任意选择,优选-20℃~50℃。
在反应式8中,叔丁醇与异氰酸氯磺酰酯的反应可参考公知的方法,例如日本专利公开公报1975年第101323号进行。
将2-亚氨基-3-氟丙基噻唑啉(3)或(4)与叔丁基氨基磺酰氯反应,2-亚氨基-3-氟丙基噻唑啉(3)或(4)与叔丁基氨基磺酰氯的摩尔比为1∶0.5~3.0,优选1∶0.9~1.2。
反应温度可在-50℃~100℃的范围内任意选择,优选-40℃~30℃。
本反应通过使用各种碱而进行。2-亚氨基-3-氟丙基噻唑啉(3)或(4)与碱的摩尔比为1∶0.5~4∶0,优选1∶0.8~2.5。作为合适的碱,可使用例如氢化钠等金属氢化物类、三乙胺、吡啶等有机碱类、氢氧化钠、氢氧化钾、碳酸钾等无机碱类、甲醇钠、乙醇钠等金属烷氧化物类,优选有机碱类。
本反应的合适溶剂是对本反应呈惰性的溶剂,例如,苯、甲苯、二甲苯等芳香烃类、二氯甲烷、氯仿、二氯乙烷等卤烃类、乙醚、异丙醚、二噁烷、四氢呋喃等醚类、乙腈、丙腈等腈类、石油醚、庚烷等烃类、丙酮、丁酮等酮类、乙酸乙酯等酯类、二甲基甲酰胺、二甲基乙酰胺、六甲基磷酰胺等酰胺类。这些溶剂可单独使用或混合使用。其中,尤其优选醚类或酰胺类。
在反应式8中,叔丁基的除去系用三氟醋酸进行。三氟醋酸的量可在等摩尔至过量之间任意选择。使用三氟醋酸作为溶剂也无任何问题。
反应温度可在-50℃~80℃的范围内任意选择,优选-20℃~30℃。
本反应的合适溶剂是对本反应呈惰性的溶剂,例如,苯、甲苯、二甲苯等芳香烃类、二氯甲烷、氯仿、二氯乙烷等卤烃类、乙醚、异丙醚、二噁烷、四氢呋喃等醚类、乙腈、丙腈等腈类、石油醚、庚烷等烃类、丙酮、丁酮等酮类、乙酸乙酯等酯类、二甲基甲酰胺、二甲基乙酰胺、六甲基磷酰胺等酰胺类。这些溶剂可单独使用或混合使用。〔反应式9〕
在反应式9中,3-氟丙基噻唑啉-2-亚氨基磺酰氯(10)与氨的摩尔比可在1∶2~过量的范围内任意选择。所用的氨可以是液体、气体或水溶液。反应温度可在-76℃~80℃的范围内任意选择。
本反应的合适溶剂是对本反应呈惰性的溶剂,例如,苯、甲苯、二甲苯等芳香烃类、二氯甲烷、氯仿、二氯乙烷等卤烃类、乙醚、异丙醚、二噁烷、四氢呋喃等醚类、乙腈、丙腈等腈类、石油醚、庚烷等烃类、丙酮、丁酮等酮类、乙酸乙酯等酯类、二甲基甲酰胺、二甲基乙酰胺、六甲基磷酰胺等酰胺类、甲醇、乙醇等醇类。这些溶剂可单独使用或混合使用。另外,最佳溶剂视所用的氨的状态而异。
本发明中使用的中间体3-氟丙基噻唑啉-2-亚氨基磺酰氨基甲酸苯酯(6:Y=苯基)、3-氟丙基噻唑啉-2-亚氨基磺酰氨基甲酸烷基酯(6:Y=低级烷基)、3-氟丙基噻唑啉-2-亚氨基磺酰胺(7)、异氰酸3-氟丙基噻唑啉-2-亚氨基磺酰酯(9)和3-氟丙基噻唑啉-2-亚氨基磺酰氯(10)也是新化合物。
在反应式2中,N-氯磺酰氨基甲酸苯酯(5:Y=苯基)和N-氯磺酰氨基甲酸烷基酯(5:Y=低级烷基)可参考公知的方法,例如Chemische Berichte,96,56(1963)合成。
实施发明的最佳方式
将2-氨基噻唑5g(50mmol)溶解于二甲基甲酰胺15ml中,室温下加入1-溴-3-氟丙烷8.8g(62.4mmol)。将反应混合物在80℃加热搅拌7.5小时后,放冷至室温。往反应混合物中加入乙酸乙酯300ml,室温下搅拌10分钟。通过滗析,将生成的油状物与乙酸乙酯溶液分离,重复同样的操作2次后,往油状物中加入乙酸乙酯和少量的甲醇进行结晶,过滤得到2-亚氨基-3-(3-氟丙基)噻唑啉氢溴酸盐(4:Z=Br)5.5g,熔点153~155℃。
接着,室温下,将2-亚氨基-3-(3-氟丙基)噻唑啉氢溴酸盐(4:Z=Br)1.21g(5mmol)与在甲醇20ml中的85%氢氧化钾0.33g(5mmol)搅拌1小时。减压下蒸去甲醇,往残渣中加入氯仿20ml,滤去析出的不溶物质。减压下蒸去氯仿,得到油状的2-亚氨基-3-(3-氟丙基)噻唑啉(3)0.8g。
1H-NMR(60MHz)δ(ppm,CDCl3):
1.6-2.7(2H,m) 3.84(2H,t,J=6.8Hz),
4.50(2H,dt,J=47.0Hz,5.6Hz) 5.74(1H,d,J=4.7Hz),
6.40(1H,d,J=4.7Hz) 5.5-6.8(1H,br)
将2-亚氨基-3-(3-氨丙基)噻唑啉氢溴酸盐(4:Z=Br)15g(62.2mmol)溶解于水150ml中,加入无水碳酸钾8.59g(62.2mmol),室温下搅拌10分钟。用氯仿150ml提取4次,将有机层用饱和食盐水洗涤,然后用无水硫酸钠干燥。减压蒸去溶剂,得到油状的2-亚氨基-3-(3-氟丙基)噻唑啉(3)9.45g。实施例11-〔3-(3-氟丙基)噻唑啉-2-亚氨基磺酰〕-3-(4,6-二甲氧基三嗪-2-基)脲(1)的合成
A法:将2-氨基-4,6-二甲氧基三嗪(2)0.58g(3.72mmol)溶解于干燥的四氢呋喃100ml中,室温下滴加异氰酸氯磺酰酯0.53g(3.75mmol)。搅拌10分钟后,加入2-亚氨基-3-(3-氟丙基)噻唑啉氢溴酸盐(4:Z=Br)1.0g(4.15mmol)、三乙胺0.84g(8.32mmol)和四氢呋喃10ml的混合物,室温下继续搅拌1小时。然后,减压蒸去溶剂,往所得残渣中加水100ml,用氯仿150ml提取3次。将氯仿层用水50ml洗涤,再用无水硫酸钠干燥。减压蒸去溶剂,往残渣中加入乙醚和乙腈进行结晶,然后过滤,得到目的产物1-〔3-(3-氟丙基)噻唑啉-2-亚氨基磺酰〕-3-(4,6-二甲氧基三嗪-2-基)脲(1)0.4g,熔点175~177℃。
B法:将2-氨基-4,6-二甲氧基三嗪(2)0.78g(5mmol)溶解于干燥的四氢呋喃30ml中,室温下滴加异氰酸氯磺酰酯0.71g(5mmol)。搅拌30分钟后,加入2-亚氨基-3-(3-氟丙基)噻唑啉(3)0.8g(5mmol)、三乙胺0.55g(5.4mmol)和四氢呋喃20ml的混合物,室温下继续搅拌30分钟。然后,减压蒸去溶剂,往所得残渣中加水100ml,用氯仿100ml提取3次。减压蒸去溶剂后,通过制备性薄层色谱(展开溶剂:乙酸乙酯)纯化残渣。往所得粗提纯物中加入乙醚和乙腈,让其结晶,然后过滤,得到目的产物1-〔3-(3-氟丙基)噻唑啉-2-亚氨基磺酰〕-3-(4,6-二甲氧基三嗪-2-基)脲(1)0.21g。
C法:将2-氨基-4,6-二甲氧基三嗪(2)0.17g(1.1mmol)溶解于干燥的四氢呋喃30ml中,室温下滴加异氰酸氯磺酰酯0.15g(1.1mmol)。搅拌30分钟后,加入2-亚氨基-3-(3-氟丙基)噻唑啉氢溴酸盐(4:Z=Br)0.26g(1.1mmol)、三乙胺0.24g(2.4mmol)和四氢呋喃30ml的混合物,室温下继续搅拌30分钟。然后,减压蒸去溶剂,往所得残渣中加水50ml,用氯仿60ml提取3次。将氯仿层用水50ml洗涤,再用无水硫酸钠干燥。减压蒸去溶剂,往残渣中加入乙醚和乙腈进行结晶,然后过滤,得到目的产物1-〔3-(3-氟丙基)噻唑啉-2-亚氨基磺酰〕-3-(4,6-二甲氧基三嗪-2-基)脲(1)0.22g。
D法:将2-氨基-4,6-二甲氧基三嗪(2)0.61g(3.9mmol)溶解于干燥的四氢呋喃30ml中,室温下滴加异氰酸氯磺酰酯0.56g(3.9mmol)。搅拌30分钟后,加入2-亚氨基-3-(3-氟丙基)噻唑啉(3)0.63g(3.9mmol)、三乙胺0.44g(4.3mmol)和四氢呋喃50ml的混合物,室温下继续搅拌30分钟。然后,减压蒸去溶剂,往所得残渣中加水100ml,用氯仿100ml提取3次。将氯仿层用水50ml洗涤,再用无水硫酸钠干燥,减压蒸去溶剂后,往残渣中加入乙醚和乙腈,让其结晶,然后过滤,得到目的产物1-〔3-(3-氟丙基)噻唑啉-2-亚氨基磺酰〕-3-(4,6-二甲氧基三嗪-2-基)脲(1)1.1g。实施例2 f.8
将叔丁醇0.62g(8.4mmol)溶解于正己烷6ml中,在冰冷却下,加入异氰酸氯磺酰酯1.18g(8.4mmol)。在50℃加热反应液5分钟后,减压蒸去溶剂。往所得残渣中加入干燥的四氢呋喃30ml,冷却至-30℃后,加入2-亚氨基-3-(3-氟丙基)噻唑啉氢溴酸盐(4:Z=Br)2g(8.3mmol)、三乙胺1.68g(1 6.6mmol)和四氢呋喃20ml的混合物。继续在室温下搅拌90分钟后,减压蒸去溶剂,往所得残渣中加水100ml,用氯仿100ml提取3次。将氯仿层用水50ml洗涤后,再用无水硫酸钠干燥。减压蒸去溶剂,将所得结晶用乙醚洗涤,得到N-叔丁基-〔3-(3-氟丙基)噻唑啉-2-亚氨基〕磺酸胺(11)0.73g,熔点103~105℃。
将N-叔丁基-〔3-(3-氟丙基)噻唑啉-2-亚氨基〕磺酸胺(11)0.4g(1.4mmol)溶解于三氟乙酸15ml中,室温下搅拌过夜。减压蒸去三氟乙酸,经硅胶色谱,得到〔3-(3-氟丙基)噻唑啉-2-亚氨基〕磺酰胺(7)0.2g,熔点70~73℃。
将〔3-(3-氟丙基)噻唑啉-2-亚氨基〕磺酸胺(7)0.18g(0.75mmol)和N-(4,6-二甲氧基三嗪-2-基)氨基甲酸苯酯(8)0.21g(0.75mmol)溶解于干燥乙腈20ml中,室温下,加入1,8-二氮杂二环〔5.4.0〕十-碳-7-烯(DBU)0.12g(0.79mmol)。继续在室温下搅拌3小时后,减压蒸去一半溶剂,再加水50ml。然后加入浓盐酸,滤取析出的结晶,用乙醚洗涤,得到目的产物1-〔3-(3-氟丙基)噻唑啉-2-亚氨基磺酰〕-3-(4,6-二甲氧基三嗪-2-基)脲(1)0.17g。实施例3
将苯酚0.35g(3.8mmol)溶解于干燥四氢呋喃40ml中,在冰冷却下,加入异氰酸氯磺酰酯0.53g(3.8mmol)。在该温度搅拌20分钟后,冷却至-40℃。然后滴加2-亚氨基-3-(3-氟丙基)噻唑啉(3)0.67g(4.2mmol)、三乙胺0.43g(4.2mmol)和干燥四氢呋喃15ml的混合物。室温下搅拌反应液60分钟后,减压蒸去溶剂,加水50ml。用氯仿40ml提取分出的油状物3次,将氯仿层用饱和食盐水洗涤,再用无水硫酸钠干燥。减压蒸去溶剂,用制备性薄层色谱进行纯化,得到3-(3-氟丙基)噻唑啉-2-亚氨基磺酰氨基甲酸苯酯(6:Y=Ph)200mg,熔点145~147℃。
将3-(3-氟丙基)噻唑啉-2-亚氨基磺酰氨基甲酸苯酯(6:Y=Ph)60mg(0.22mmol)、2-氨基-4,6-二甲氧基三嗪(2)34mg(0.22mmol)和无水苯8ml的混合物加热回流3小时,反应液冷却后,减压蒸去溶剂,用乙醚、乙腈洗涤,得到目的产物1-〔3-(3-氟丙基)噻唑啉-2-亚氨基磺酰〕-3-(4,6-二甲氧基三嗪-2-基)脲(1)50mg。
本发明化合物的施用药量视施用场所、施用季节、施用方法、目标杂草、栽培作物等而异,一般在每公顷(ha)0.0001~1kg有效成分量的范围内,优选0.001~0.5kg/公顷。
另外,本发明化合物可根据需要制成制剂或于喷洒时与其它除草剂、各种杀虫剂、杀菌剂、植物生长调节剂、增效剂、防护剂等合用。
尤其是,通过与其它除草剂合用,可期望由施用药量减少而产生的成本降低,由混合药剂的协同作用而产生的除草谱的扩大以及更好的除草效果。在这种情况下,可同时与多种公知的除草剂合用。可与本发明化合物合用的除草剂的种类有例如Farm Chemicals Handbook 1990年版中记载的化合物等。
作为除草剂施用本发明化合物时,一般与合适的载体,例如粘土、滑石粉、膨润土、硅藻土、白炭黑等固体载体或水、醇类(异丙醇、丁醇、苄醇、糖醇等)、芳香烃类(甲苯、二甲苯等)、醚类(茴香醚等)、酮类(环己酮、异佛尔酮等)、酯类(乙酸丁酯等)、酰胺类(N-甲基吡咯烷酮等)或卤烃类(氯苯等)等液体载体混用,根据需要,可添加表面活性剂、乳化剂、分散剂、渗透剂、铺展剂、增粘剂、防冻剂、防结块剂,稳定剂等,制成液剂、乳剂、可湿性粉剂、干流动剂(a dry flowable)、流动剂(a flowable)、粉剂、粒剂等任意剂型以供实用。
下面具体给出使用本发明化合物的制剂的配伍例。但本发明的配伍剂不受它们限定。在下面的配伍例中,“份”表示重量份数。〔可湿性粉剂〕
本发明化合物 5~80份
固体载体 10~85份
表面活性剂 1~10份
其它 1~5份
其它成分可以是如防结块剂等。〔乳剂〕
本发明化合物 1~30份
液体载体 30~95份
表面活性剂 5~15份〔流动剂〕
本发明化合物 5~70份
液体载体 15~65份
表面活性剂 5~12份
其它 5~30份
其它成分可以是如防冻剂、增粘剂等。〔粒状可湿性粉剂(干流动剂)〕
本发明化合物 20~90份
固体载体 10~60份
表面活性剂 1~20份
〔粒剂〕
本发明化合物 0.1~10份
固体载体 90~99.9份
其它 1~5份〔配伍例1〕可湿性粉剂
本发明化合物 20份
Zeeklite A 76份
(高岭土类粘土,Zeeklite工业公司产品)
Sorpol 5039 2份
(非离子型表面活性剂和阴离子型表面活性剂的混合物,东邦化学工业公司产品)
Carplex(防结块剂) 2份
(白炭黑,盐野义制药公司产品)
将上述成分均匀混合、粉碎,制成可湿性粉剂。〔配伍例2〕可湿性粉剂
本发明化合物 40份
Zeeklite A 54份
Sorpol 5039 2份
Carplex(防结块剂) 4份
将上述成分均匀混合、粉碎,制成可湿性粉剂。〔配伍例3〕乳剂
本发明化合物 5份
二甲苯 75份
二甲基甲酰胺 15份
Sorpol 2680 5份
(非离子型表面活性剂和阴离子型表面活性剂的混合物,东邦化学工业公司产品)
将上述成分均匀混合,制成乳剂。〔配伍例4〕流动剂
本发明化合物 25份
Agrizole S-710 10份
(非离子型表面活性剂,花王公司产品)
Lunox 1000C 0.5份
(阴离子型表面活性剂,东邦化学工业公司产品)
1%Rodopol水 20份
(增粘剂,Rhone-Poulenc公司产品)
水 44.5份
将上述成分均匀混合,制成流动剂。〔配伍例5〕流动剂
本发明化合物 40份
Agrizole S-710 10份
Lunox 1000℃ 0.5份
1%Rodopol水 20份
水 29.5份
将上述成分均匀混合,制成流动剂。〔配伍例6〕粒状可湿性粉剂(干流动剂)
本发明化合物 75份
Isoban No.1 10份
(阴离子型表面活性剂,Kuraray Isoprene化学公司产品)
Vanilex N 5份
(阴离子型表面活性剂,山阳国策浆粕公司产品)
Carplex#80 10份
(白炭黑,盐野义制药公司产品)
将上述成分均匀混合、磨粉,制成干流动剂。〔配伍例7〕粒剂
本发明化合物 1份
膨润土 55份
滑石粉 44份
将上述成分均匀混合、粉碎后,加入少量水,搅拌、混合、捏合,用挤出式造粒机造粒,干燥,制成粒剂。
使用时,可将上述可湿性粉剂、乳剂、流动剂、粒状可湿性粉剂用水稀释50~1000倍,以每公顷0.0001~1kg有效成份的剂量施用。
本发明化合物作为旱地的甜菜用的除草剂,可用于土壤处理法、土壤混和处理法或茎叶处理法使用。作为本发明化合物的目标的旱田杂草,例如有以龙葵(Solanum migrum)、蔓陀萝(Datura stramonium)等为代表的茄科(Solanaceae)杂草、苘麻(绒毛叶)(Abutilon theophrasti)、剌黄花稔(Sida spinosa)等为代表的锦葵科(Malvaceae)杂草、以圆叶牵牛(Ipomoea purpurea)等蕃薯类(Ipomoeaspps.)和打碗花类(Calystegiaspps.)等为代表的旋花科(Convolvulaceae)杂草、以凹头苋(Amaranthus lividus)、野苋(皱果苋)(Amaranthus viridis)等为代表的苋科(Amaranthaceae)杂草、以苍耳(Xanthium strumarium)、美洲豚草(Am-brosia artemisiaefolia)、向日葵(Helianthus annuus)、hairy galinsoga(Galinso-ga ciliat)、田蓟(Cirsium arvense)、欧洲千里光(Senecio vulgaris)、一年蓬(飞蓬)(Erigeron annus)等为代表的菊科(Compositae)杂草、以蔊菜(Rorippa indi-ca)、野原芥(Sinapis arvensis)、荠菜(Capsella brusapastoris)等为代表的十字花科(Cruciferae)杂草、以马蓼(Polygonum blumei)、荞麦蔓(卷茎蓼)(Polygonumconvolvulus)等为代表的蓼科(Polygonaceae)杂草、以马齿苋(Portulace oler-acea)等为代表的马齿苋科(Portulacaceae)杂草、以藜(Chenopodium album)、小藜(Chenopodium ficifolium)、地肤(Kochia scoparia)等为代表的藜科(Chenopodiaceae)杂草、以繁缕(Stellaria media)等为代表的石竹科(Caryophyllaceae)杂草、以大婆婆纳(Veronica persica)等为代表的玄参科(Scrophulariaceae)杂草、以鸭跖草(Commelina communis)等为代表的鸭跖草科(Commelinaceae)杂草、以宝盖草(Lamium amplexicaule)、小野芝麻(Lami-um purpureum)等为代表的唇形科(Labiatae)杂草、以斑地锦(Euphorbiasupina)、美洲地锦草(Euphorbia maculata)等为代表的大戟科(Euphorbiacea)杂草、以无剌猪殃殃(Galium spurium)、猪殃殃(Galium aparine)、茜草(Rubiaakane)等为代表的茜草科(Rubiaceae)杂草、以田堇菜(Viola arvensis)等为代表的堇菜科(Violaceae)杂草、以大果田菁(Sesbania exaltata)、决明(Cassia ob-tusifolia)等为代表的豆科(Leguminosae)杂草等阔叶杂草、以野生高梁(Sorgham bicolor)、秋稷(Panicum dichotomiflorum)、阿拉伯高梁(Sorghumhalepense)、稗(Echinochloa crus-galli)、升马唐(Digitaria adscendens)、乌麦(Avena fatua)、蟋蟀草(Eleusine indica)、狗尾草(Setaria viridis)、看麦娘(Alopecurus aequalis)等为代表的禾本科杂草(Graminaceous weeds)、以莎草(Cyperus rotundus)、铁荸荠(Cyperus esculentus)等为代表的莎草科杂草(Cyperaceous weeds)、以小麦(Triticum vulgare)、大麦(Hordeum vulgare)等为代表的自生自长的作物(Volunteer weeds)等。
下面结合以下试验例,具体说明本发明化合物作为除草剂的有用性。试验例1 通过土壤处理而进行的除草效果试验
在长33cm、宽33cm、深8cm的塑料箱中放入已杀菌的洪积土,混合播种乌麦(燕麦)、鼠尾看麦娘、意大利黑麦草(Italian ryegrass)、小麦(自生自长的作物)、大麦(自生自长的作物)、野苋、繁缕、猪殃殃、荞麦蔓、马蓼、藜、野原芥(Kedlock)、甜菜,覆盖约1.5cm厚的土后,按规定的剂量,在土壤表面均匀地施药。施药时,将按上述配伍例等适当调配制成的可湿性粉剂用水稀释,再用小型喷雾器喷洒在所有土壤表面。喷洒药水4周后,按下述判断标准,用目测检查药水对作物的植物毒性及对各种杂草的除草效果。结果见表1。
本发明化合物对甜菜具有选择性。
判断标准
5… 除草率 90%以上(几乎完全枯死)
4… 除草率 70~90%
3… 除草率 40~70%
2… 除草率 20~40%
1… 除草率 5~20%
0… 除草率 5%以下(几乎无效)
下列字母分割代表:
A:乌麦、B:鼠尾看麦娘、C:意大利黑麦草、D:小麦、E:大麦、F:野苋、G:繁缕、H:猪殃殃、I:荞麦蔓、J:马蓼、K:藜、L:野原芥、a:甜菜试验例2 通过茎叶处理而进行的除草效果试验
在长33cm、宽33cm、深8cm的塑料箱中放入已杀菌的洪积土,混合播种乌麦、鼠尾看麦娘、意大利黑麦草(Italian ryegrass)、小麦(自生自长的作物)、大麦(自生自长的作物)、野苋、繁缕、猪殃殃、荞麦蔓、马蓼、藜、野原芥(Kedlock)、甜菜,覆盖约1.5cm厚的土后,将箱子在25~30℃的室温放置14天以培育植物,按规定的剂量,在茎叶上均匀地施药。施药时,将按上述配伍例等适当调配的可湿性粉剂用水稀释,再用小型喷雾器喷洒在所有杂草的茎叶部。喷洒药水4周后,按试验例1的判断标准检查药水对作物的植物毒性及对各种杂草的除草效果。结果见表2。表中字母的含义和比较化合物与试验例1相同。试验例3 通过在田地茎叶处理而进行的除草效果试验
在旱地成行播种甜菜,在甜菜的行与行之间混合播种乌麦、鼠尾看麦娘、狗尾草、藜、繁缕、野苋、野原芥、马蓼、马齿苋、荞麦蔓、猪殃殃,接着,仅将播种杂草的行间部分的土壤混和。在播种甜菜和杂草后第25日,用水将可湿性粉剂的除草剂稀释成悬浮液并按一定剂量在茎叶部均匀施药。施用的水量为每公顷500升,每单位处理区域为4m2。施药前,在药水中添加非离子型表面活性剂至1000ppm浓度。施药后第18天,按试验例1的标准检查药水对各杂草的除草效果及对甜菜的植物毒性。结果见表3。
表中字母分别代表:
A:乌麦、B:鼠尾看麦娘、M:狗尾草、K:藜、G:繁缕、F:野苋、L:野原芥、J:马蓼、N:马齿苋、I:荞麦蔓、H:猪殃殃、a:甜菜
表1
比较化合物(A):记载在公布号为WO93/00336的国际专利申请中的化合物
编号 | 药量(kg/ha) | A | B | C | D | E | F | G | H | I | J | K | L | a |
本发明化合物(1) | 0.010.040.16 | 025 | 035 | 025 | 023 | 003 | 455 | 055 | 055 | 003 | 005 | 055 | 035 | 000 |
比较化合物(A) | 0.010.040.16 | 001 | 003 | 005 | 005 | 000 | 355 | 005 | 000 | 003 | 000 | 005 | 055 | 000 |
表2
编号 | 药量(kg/ha) | A | B | C | D | E | F | G | H | I | J | K | L | a |
本发明化合物(1) | 0.00250.010.04 | 555 | 245 | 355 | 235 | 255 | 555 | 555 | 355 | 455 | 455 | 355 | 555 | 000 |
比较化合物(A) | 0.00250.010.04 | 034 | 023 | 025 | 023 | 002 | 255 | 055 | 024 | 034 | 024 | 225 | 055 | 000 |
比较化合物(A)与试验例1的相同。
表3
比较化合物(A)与试验例1的相同。
编号 | 药量(kg/ha) | A | B | M | K | G | F | L | J | N | I | H | a | |
本发明化合物(1) | 0.00250.050.10 | 555 | 555 | 455 | 555 | 555 | 555 | 555 | 555 | 555 | 555 | 555 | 000 | |
比较化合物(A) | 0.050.100.20 | 555 | 455 | 455 | 555 | 555 | 555 | 555 | 555 | 455 | 555 | 055 | 055 | 000 |
比较化合物(B) | 0.0250.050.100.20 | 0011 | 5555 | 4455 | 3344 | 5555 | 2355 | 5555 | 5555 | 2444 | 5555 | 5555 | 0000 |
比较化合物(B)是市售的商品名为SATARI的甜菜用除草剂的活性成分,系使用本公司的合成品。
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JP104794 | 1994-01-11 | ||
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JP6310585A JPH07242665A (ja) | 1994-01-11 | 1994-12-14 | フルオロプロピルチアゾリン誘導体及び除草剤 |
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CN97112763.8A Pending CN1208037A (zh) | 1994-01-11 | 1997-06-16 | 用于合成氟丙基噻唑啉衍生物的中间体 |
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WO1997038581A1 (en) * | 1996-04-16 | 1997-10-23 | E.I. Du Pont De Nemours And Company | Herbicidal mixtures |
US20030212116A1 (en) * | 1999-12-28 | 2003-11-13 | Toshio Niki | Heterocyclic imino compounds and fungicides and insecticides for agricultural and horitcultural use |
RU2003105683A (ru) * | 2000-07-28 | 2004-08-20 | Хенкель Кгаа (De) | Новый амилолитический фермент из bacillus sp.а7-7(dsm12368), а также моющее и чистящее средство с этим новым амилолитическим ферментом |
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Title |
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CHEMICAL ABSTRALTS VOL.112 1989.1.1 77097号 * |
CHEMICAL ABSTRALTS VOL.112 1989.1.1 77097号;HETEROCYCLES,VOL.32NO.11 1991.1.1 VANELLE PATRICET AN ELECTRON TNANSFER REACTION INTH IMIDAGOJS2-BJTHAGOLE S * |
HETEROCYCLES,VOL.32NO.11 1991.1.1 VANELLE PATRICET AN ELECTRON TNANSFER REACTION INTH IMIDAGOJS2-BJTHAGOLE S * |
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HUT74889A (en) | 1997-02-28 |
CN1138331A (zh) | 1996-12-18 |
SK85096A3 (en) | 1997-02-05 |
CZ205296A3 (en) | 1996-10-16 |
JPH07242665A (ja) | 1995-09-19 |
HU214648B (hu) | 1998-04-28 |
EP0739893A4 (zh) | 1996-11-20 |
EP0739893A1 (en) | 1996-10-30 |
US5763365A (en) | 1998-06-09 |
CN1208037A (zh) | 1999-02-17 |
BG100697A (en) | 1997-02-28 |
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