Organic Syntheses Involving Reactions of Acetylenes with Elemental Sulfur and Selenium

1)2）双（二乙氨基）乙炔等炔类化合物与单质硫反应生成相应的1，2-二硫代羰基化合物，而不生成1，2-二硫代噻吩。还发现了与元素硒的类似反应。3）已经开发出方便实用的四芳基噻吩和四芳基硒酚的合成方法，其中包括二芳基乙炔分别与元素硫和元素硒的反应。应用上述方法可以制备星型噻吩低聚物。4）乙炔二醇如2，5-二甲基-3-己炔-2，5-二醇与元素硫反应得到取代噻吩并[3，2-B]噻吩，从而提供了一种实用的噻吩并噻吩的一锅合成方法。5）2-氯代和2-苯氧基取代的1，1-二乙氨基乙烯与单质硫反应，得到内盐二乙氨基碳鎓二硫代羧酸盐，产率较高。

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.