SULFUR EXTRUSION REACTIONS APPLIED TO SYNTHESIS OF CORROLES AND RELATED SYSTEMS
SULFUR EXTRUSION REACTIONS APPLIED TO SYNTHESIS OF CORROLES AND RELATED SYSTEMS
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DOI：
10.1039/p19720001124
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发表时间：
1972-01-01
期刊：
影响因子：
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通讯作者：
JOHNSON, AW
中科院分区：
文献类型：
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作者：
BROADHURST, MJ;GRIGG, R;JOHNSON, AW
以5，5‘-二吡咯甲烷-5，5’-二元酸与5，5‘-二甲酰基-2，2’-联苯甲酰或双-(5-甲酰基-2-呋喃)硫化物缩合，合成了21，24-二氧杂冠醚。提出后一反应涉及一种非芳香族的中硫大环中间体，该中间体通过对旋环化成硫烷中间体，然后硫的络合损失而失去硫。这一建议的一些证据是通过制备中位硫代二氯并对它们的热分解进行研究来提供的。文中还给出了从介孔二硫杂环丙烷中挤出硫磺的例子，并讨论了在金属络合物中观察到的硫磺挤出过程中的速率增强。本文报道了21，24-二恶英腐蚀剂的亲电氢化研究。
The preparation of 21,24-dioxacorroles by condensation of dipyrromethane-5,5′-dicarboxylic acids with 5,5′-diformyl-2,2′-bifuryl or bis-(5-formyl-2-furyl) sulphide is described. It is suggested that the latter reaction involves a non-aromatic meso-thia-macrocyclic intermediate which loses sulphur by a disrotatory cyclisation to a thiiran intermediate followed by cheletropic loss of sulphur. Some evidence for this proposal is provided by the preparation of meso-thiaphlorins and a study of their thermolyses to give corroles. Further examples of sulphur extrusion from a meso-dithiaphlorin, to give a meso-thiacorrole, are given and rate enhancements, in the sulphur extrusion process, which are observed in metal complexes are discussed. Some electrophilic deuteriation studies on the 21,24-dioxa-corroles are reported.