N-酰基-N-间氟苄基-6-氨基香豆素的合成及除草活性

Synthesis and Herbicidal Activity of N-Acyl-N-(m-fluoro-benzyl)-6-amino-coumarin

以N-间氟苄基-6-氨基香豆素为先导,利用活性亚结构拼接原理,设计、合成了一系列N-酰基-N-间氟苄基-6-氨基香豆素衍生物,其结构用1H NMR、ESI-MS和元素分析表征,N-三氟乙酰基取代的化合物d5结构经X-ray单晶衍射进一步确证.采用琼脂小杯法和盆栽法对合成化合物的除草活性进行了初步研究.结果表明,100 mg/L分别为N-氯乙酰基、N-溴乙酰基、N-三氟乙酰基、N-(2,4-二氯苯氧乙酰基)取代的化合物d2,d3,d5和d17对反枝苋根、茎的抑制率大于75%,优于乙草胺EC;1500 g/ha分别为N-溴乙酰基、N-(2,4-二氯苯氧乙酰基)取代的化合物d3和d17对反枝苋等双子叶杂草茎叶处理的抑制率达76%以上;同剂量化合物d17对单子叶作物小麦、玉米和水稻安全.

Based on the structure of lead compound N-（m-fluoro-benzyl）-6-amino-coumarin, a series of novel N-acyl-N-（m-fluoro-benzyl）-6-amino-coumarins were designed and synthesized through the principle of bioactive substructure combination. Their structures were characterized by 1H NMR, ESI-MS and elemental analysis. N-trifluoroacetyl substituted compound d5 was further confirmed by X-ray single crystal diffraction. The herbicidal activities of synthesized compounds were evaluated as well. The results indicated that compounds substituted respectively by N-chloracetyl, N-bromoacetyl, N-trifluoroacetyl and N-（2,4-dichlorophenoxyacetyl） compounds d2, d3, d5 and d17 exhibited marked inhibition against the roots and stems of Amaranthus retroflexus with inhibitory rates above 75% at 100 mg/L, more active than acetochlor EC. In post-emergence treatment experiment, compounds d3 and d17 substituted respectively by N-bromoacetyl and N-（2,4-dichlorophenoxyacetyl） showed more than 76% inhibition against A. retroflexus and other dicotyledons at 1500 g/ha in greenhouse. Compound d17 is safe to monocotyledonous crops wheat, corn and rice at 1500 g a.i./hm2.