稳定同位素标记D5-氯氰菊酯的合成

Synthesis of Isotope-labeled D5-Cypermethrin

摘要:

以丰度98% atom D的D6-苯酚为起始原料，经氘氧化钾在无水甲苯中回流脱水成盐，然后与间溴苯甲醛通过乌尔曼缩合反应得到关键标记中间体D5-间苯氧基苯甲醛，再与氰化钠及DV-菊酰氯通过“相转移催化氰醇一步法”得到稳定同位素标记的D5-氯氰菊酯，以投入的氘代苯酚的物质的量计算产率为20%。目标产物结构经MS、NMR和HPLC等加以表征确认，液相色谱纯度大于98%，液质丰度98% atom D，该标记中间体亦可用于其他同位素标记拟除虫菊酯类化合物的合成。

Abstract:

This paper describes an novel synthesis of D5-cypermethrin with D6-phenol (98% atom D) as the labeled precursor. D6-phenol was dehydrated by potassium deuterium oxide in anhydrous toluene, and then reacted with 3-bromobenzaldehyde to obtain the key labeled intermediate D5-3-phenoxy-benzaldehyde through Ullmann Condensation Reaction. Finally, D5-cypermethrin was obtained by “phase transfer catalysis cyanohydrins reaction” with sodium cyanide and 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarbonyl chloride by one-step method. The yield based on the amount of substance of deuterium-substituted phenol was 20%. As-synthesized product was con-firmed by MS, NMR and HPLC to be target compound. Its chemical purity is higher than 98%, and isotopic abundance is higher than 98% (atom D). This method could also be used to synthesize other labeled pyrethroids.