稳定同位素标记灭蝇胺-氨基-^(15)N_2的合成

Synthesis of Stable Isotope Labeled Cyromazine-amino-^(15)N_2

根据天然丰度合成文献和检测内标的要求,确定15N标记灭蝇胺的结构和合成路线。以三聚氯氰为原料与氨水-15N反应得到2,4-二氨基-15N2-6-氯-1,3,5-三嗪,后者与环丙胺反应,两步生成目标产物。使用碳酸钠代替部分氨水,氨水利用率明显提高(从59.0%提高到80.0%)。以消耗的氨水-15N计算,灭蝇胺-15N2的总收率为68.1%(以三聚氯氰计)。产品结构经质谱和核磁共振波谱等表征,15N的同位素丰度为98.8%15N,色谱纯度为99.7%。以灭蝇胺-氨基-15N2产品为检测内标,高效液相色谱-电喷雾串联质谱检测灭蝇胺,在0.2~5 mg/kg时,线性关系良好(R=0.999 95),可作为食品安全领域的检测内标试剂。

The structure and synthesis of cyromazine-amino labeled with15 N were proposed,according to the literature of synthesis of cyromazine with natural abundance and testing requirements of the internal standard.Cyanuric chloride,as the starting material,reacted with ammonia-15 N to form 2,4-diamine-^15N2-6-chloro-1,3,5-triazine,which then reacted with cyclopropylamine to produce the desired product,cyromazine-amino-^15N2,in 2 steps.The utilization of ammonia was significantly improved（from 59.0% to 80.0%） by partial substitution of ammonia with sodium carbonate.The yield of cyromazine-amino-^15N2 was 68.1% based on cyanuric chloride.The product was characterized by means of NMR and MS.Its chemical purity was 99.7% and isotopic enrichment of 98.8%^15N.The prepared cyromazine-amino-^15N2 was used as an internal standard to detect cyromazine by LC-ESI-MS with a good linear relationship（R = 0.999 95） at 0.2 ~ 5 mg / kg range.It could be used as an internal standard in the field of food safety testing.