氮杂环类化合物的反应研究

目的本文对氮杂环类化合物的反应进行研究。方法 N-甲基六氢吡啶及托品酮与溴乙腈反应制得季胺盐溴化N-甲基-N-腈甲基六氢吡啶和溴化N-甲基-N-腈甲基托品酮,得到的季胺盐在四氢呋喃中与过量氢化钠反应。结果前者反应得到甲基转移的产物,后者发生Hofmann消除反应。结论溴化N-甲基-N-腈甲基六氢吡啶在氢化钠作用下,首先发生甲基转移反应,进而与四氢呋喃中的不纯物过氧化氢物产生的甲酸酯反应生成化合物2-六氢吡啶基-2-腈基-丙醛。阿托品化合物在氢化钠作用下是首先发生Hofmann消除反应,进而环合生成化合物3-氨基-1-甲基-2,7,8,8a-四氢-环庚吡咯-4-酮。

The investigation on the reaction of N-heterocycles

Objective The reactions of quaternary ammoniumsalts of N-heterocycles were investigated. Methods The rearrangement reactions of N-heterocycles might be performed if the N-ylide intermediates can be generated. In compounds containing a β-hydrogen atom, Hofmann elimination may compete and in many cases provides the major product. We tried N-cyanomethyl-N-methylpiperidine bromide and N-cyanomethyl-N-methyltropinone bromide which were treated with sodium hydride. Results The quaternary ammonium salt N-cyanomethyl-N-methylpiperidine bromide furnished the rearrangement reactions products 2-piperidinyl-2-cyanoyl-propionaldehyde and N-cyanomethyl-atropine bromide gave Hofmann elimination product 2-piperidinyl-2-cyanoyl-propionaldehyde. Conclusion Thus we have explored the reaction quaternary ammoniumsalts of N-heterocycles with sodium hydride. Some of them performed Hofmann elimination reactions and some of them underwent rearrangement reactions. N-methylpiperidine and tropinone derivatives were tested. N-methylpiperidine derivative react with sodium borohydride to performed rearrangement reactions. Tropinone derivatives performed Hofmann elimination reaction and cyclize to produce 7.