1-N-哌嗪-4-N-甲醛在维尔斯迈尔反应中固相负载的应用。

The use of solid-phase supported 1-N-piperazine-4-N-carboxaldehyde in Vilsmeier reactions.

作者信息

Rivero I A, Espinoza K A, Ochoa A

机构信息

Centro de Graduados e Investigación, Instituto Tecnológico de Tijuana, Apartado Postal 1166, 22000 Tijuana, B.C. México.

出版信息

J Comb Chem. 2004 Mar-Apr;6(2):270-4. doi: 10.1021/cc0200742.

DOI:10.1021/cc0200742

PMID:15002976

Abstract

A Vilsmeier salt supported on solid phase was prepared using piperazine bound to Merrifield resin. Piperazine was selected because it contains two secondary amines: one of the amines is protected upon binding to the resin, and the second was formylated to give resin-1-N-piperazine-4-N-carboxaldehyde (9). Activation of the formamide with either bis(trichloromethyl)carbonate (BTC) or POCl(3) afforded the Vilsmeier salt 10. Several olefins were used to test the supported Vilsmeier reagent. The in-solution activation with BTC and POCl(3) of various secondary amides was also evaluated: dimethylformamide (1), N-methyformanilide (4), 4-formylmorpholine (5), and 1,4-dicarboxylpiperazine (6), which showed that amides with one additional heteroatom increase the yields in the Vilsmeier salt formation.

摘要

使用与 Merrifield 树脂结合的哌嗪制备了负载在固相上的 Vilsmeier 盐。选择哌嗪是因为它含有两个仲胺：其中一个胺在与树脂结合时被保护，另一个被甲酰化得到树脂 -1-N-哌嗪-4-N-甲醛（9）。用双（三氯甲基）碳酸酯（BTC）或三氯氧磷（POCl₃）活化甲酰胺得到 Vilsmeier 盐 10。使用几种烯烃来测试负载的 Vilsmeier 试剂。还评估了用 BTC 和 POCl₃ 对各种仲酰胺进行溶液活化：二甲基甲酰胺（1）、N-甲基甲酰苯胺（4）、4-甲酰基吗啉（5）和 1,4-二羧基哌嗪（6），结果表明带有一个额外杂原子的酰胺会提高 Vilsmeier 盐形成的产率。