Applications of high-temperature aqueous media for synthetic organic reactions
Applications of high-temperature aqueous media for synthetic organic reactions
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DOI：
10.1021/jo962115k
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发表时间：
1997-04-18
影响因子：
3.6
通讯作者：
Trainor, RW
中科院分区：
文献类型：
--
作者：
An, JY;Bagnell, L;Trainor, RW
研究了在水介质中在高达300 ℃的温度下的分解有机合成。用最近公开的加压微波间歇反应器（MBR）或在常规加热的高压釜中进行实验。36个例子。在这些方法中，开发了Fischer合成、按比例放大的分子内羟醛缩合、吲哚-2-羧酸的脱羧、1-乙炔基-1-环己醇的重排、香芹酮异构化为香芹酚以及苯乙炔转化为苯乙酮的方法。高温水的适用性也被证明为在食品，香料和芳香化学中重要的仿生过程，以及串联反应，如从烯丙基苯基醚形成2-甲基-2，3-二氢苯并呋喃。当需要添加酸或碱时，高温过程所需的试剂通常比沸点或沸点以下的过程所需的试剂少，并且反应通常更具选择性。在某些情况下，所需的量要低几个数量级，这对安全、经济的处理和降低污水处理成本产生了明显的影响。反应的多样性表明，高温水介质在新的制备过程的发展中可以发挥越来越重要的作用。
Preparative organic synthesis was investigated in aqueous media at temperatures up to 300 degrees C. Experiments were conducted with a recently disclosed pressurized microwave batch reactor (MBR) or in conventionally heated autoclaves. Thirty-six examples are presented. Among these, methods were developed for a Fischer synthesis, an intramolecular aldol condensation that was scaled up, decarboxylation of indole-2-carboxylic acid, Rupe rearrangement of 1-ethynyl-1-cyclohexanol, isomerization of carvone to carvacrol, and conversion of phenylacetylene to acetophenone. The applicability of high-temperature water was also demonstrated for biomimetic processes important in food, flavor, and aroma chemistry and for tandem reactions such as formation of 2-methyl-2,3-dihydrobenzofuran from allyl phenyl ether. When addition of acid or base was necessary, less agent was usually required for high-temperature processes than for those at and below boiling, and the reactions often proceeded more selectively. In some instances the requirement was orders of magnitude lower, with obvious consequences for safe, economic processing and for lowering costs of effluent disposal. The diversity of reactions indicates that high-temperature aqueous media could play an increasingly important role in the development of new preparative processes.