【作者】 路娟；

【导师】 戴立言；

【作者基本信息】 浙江大学 ， 应用化学， 2006， 硕士

【摘要】 0-取代烷基羟胺是一类用途广泛且价格昂贵的有机合成中间体,该类化合物可用作烷氧胺基化试剂,可作为环己烯酮类除草剂、新医药及新农药创制领域的基础原料。 本文在参照了多篇文献的基础上,优化了0-取代烷基羟胺的合成工艺。选择盐酸羟胺和乙酸乙酯为起始原料,经过乙酰胺化、醚化、水解三步反应合成了0-乙基羟胺,0-烯丙基羟胺,0-苄基羟胺以及0-(3-氯-2-丙烯基)羟胺。 对文献中该类化合物合成路线的改进主要体现在以下几个方面: (1)第一步中盐酸羟胺来代替硫酸羟胺,使后处理过程比较简便,并且通过一系列平行实验确定出乙酸乙酯、氢氧化钠和盐酸羟胺的最佳摩尔配比。 (2)第二步中选用合适的萃取剂实现了对产物和副产物的有效分离,其中0-烯丙基羟胺和0-(3-氯-2-丙烯基)羟胺在该步的收率均达到90%以上。 (3)第三步选用合适的后处理方法,得到纯度和收率均较高的目标化合物,其中0-(3-氯-2-丙烯基)羟胺的纯度在99%以上。 综上所述,该路线与文献中方法相比有了较大改进,所需原料便宜易得,各步反应条件温和,操作简便,收率较高。主要中间产物以及目标产品均经气相-质谱谱图确认。更多还原

【Abstract】 O-substituted hydroxylamines is an expensive intermediate in organic synthesis, which have wide applications and especially can be used as raw materials for preparing 3-hydroxycyclohex-2-enones herbicides , new medicine and pesticides.This research optimized the synthetical process on the basis of many documents, O-ethylhydroxylamine, O-allylhydroxylamine, O-benzylhydroxylamine and O-(3-chloro-2-propenyl)-hydroxylamine were synthesized starting from ethyl acetate and hydroxylamine hydrochloride via a facile, three-step procedure including acetylamination, etherification and hydrolysis.The improvements in this research for the synthetical process of O-substituted hydroxylamines mentioned in previous documents were listed as follows:(1) Hydroxylamine sulfate was replaced by hydroxylamine hydrochloride in the first step which simplified the procedure. The optimum molar ratio of ethyl acetate, sodium hydroxide and hydroxylamine hydrochloride was determined via a series of parallel experiments.(2) The effective separation of product and by-product was achieved with appropriate extraction solvents in the second step. The yields of both O-allylhydroxylamine and O-(3-chloro-2-propenyl)-hydroxylamine in this step reached more than 90%.(3) The target products were obtained with high purity and high yields by appropriate post treatment methods. The purity of O-(3-chloro-2-propenyl)-hydroxylamine reached more than 99%.In conclusion, many improvements were made with this synthetical process compared with the methods in documents, such as cheap and available raw materials, mild reaction conditions, simple operation, high yields. The main intermediate and target products were confirmed by GC/MS.更多还原