Organic Syntheses Involving Reactions of Acetylenes with Elemental Sulfur and Selenium

1)建立了1，2-二硫化合物的简便合成方法，它包括元素硫与带有大量取代基的乙炔的反应，如叔丁基和1-金刚烷基。2)我们发现二(二乙氨基)乙炔等亚胺与元素硫反应生成相应的1，2-二硫代羰基化合物，而不是1，2-二硫化合物。3)研究了二芳基乙炔分别与元素硫和硒发生反应的四芳基噻吩类和四芳基硒基苯类化合物的简便实用的合成方法。4)2，5-二甲基-3-己炔-2，5-二醇等2，5-二甲基-3-己炔-2，5-二醇与元素硫反应生成取代的硫代[3，2-b]噻吩类化合物，从而提供了一锅法合成噻吩类化合物的实用方法。5)2-氯和2-苯氧基取代的1，1-二(二乙氨基)乙烯与元素硫反应生成二(二乙氨基)二硫代甲酸二乙酯内盐。

1) A convenient symthesis of 1, 2-dithietes, which involves reaction of elemental sulfur with acetylenes carrying bulky substituents such as tert-butyl and 1-adamantyl, has been established.2) It was found that ynamines such as bis(diethlamino)acetylene react with elemental sulfur to give the corresponding 1, 2-dithiocarbonyl compounds but not the 1, 2-dithietes. A similar reaction with elemental selenium was also found.3) Convenient and practical syntheses of tetraarylthiophenes and tetraarylselenophenes, which involve reactions of diarylacetylenes with elemental sulfur and selenium, respectively, have been deveised. Application of the above method allowed the preparation of a star-burst type of thiophene oliogomers.4) Acetylenediols such as 2, 5-dimethl-3-hexyne-2, 5-diol react with elemental sulfur to give substituted thieno[3, 2-b]shiophenes, thus providing a practical one-pot synthesis of thienothiophenes. The reaction is also applicable to the preparation of selenolo[3, 2-b]selenophenes.5) 2-Chloro and 2-phenoxy substituted 1, 1-bis(diethylamino)ethylenes react with elemental sulfur to afford an inner salt, bis(diethylamino)carbeniumdithiocarboxylate in excellent yields.