Anomalous reaction of selenium and carbon disulfide with sodium acetylide. Synthesis of selenium analogs of 1,3-dithiole-2-thione
Anomalous reaction of selenium and carbon disulfide with sodium acetylide. Synthesis of selenium analogs of 1,3-dithiole-2-thione
复制标题
硒和二硫化碳与乙炔钠的反常反应。
DOI：
10.1021/jo00891a032
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发表时间：
1975
影响因子：
3.6
通讯作者：
V. Patel
中科院分区：
文献类型：
--
作者：
E. Engler;V. Patel
用硒和二硫化碳与乙炔钠反应，除得到预期产物外，还得到4个化合物，分别鉴定为1，3-二硫烯-2-硫酮(4)，L，3-二硫烯-2-色酮(5)，L，3-硫烯-2-塞尔酮(6)，L，3-二硒-2-硫酮(7)。在类似的反应中，硫和碳二烯与乙酰化钠反应得到相同的产物以及1，3-二硒醚-2-硒酮(8)。表一列出了在这两个反应中形成的产物的相对百分比。用硅胶(5%CHCI3+CCI4)柱层析，可以很好地分离产物。相对于1，在环中引入硒减少了在柱上的保留时间，而将1中的硫代羰基替换为硒-羰基增加了保留时间。在像6这样的化合物中，羰基中的Se对保留时间的影响比环中的更大，并且这种物质在1之后洗脱。
Treatment ofsodium acetylide with selenium and carbon disulfide gave, in addition to the expected product, 1, 3-thiaselenole-2-thione (4), four other related compounds iden-tified as 1, l, 3-dithiole-2-selone (5), l, 3-thiaselenole-2-sel-one (6), and l, 3-diselenole-2-thione (7). In a similar reac-tion, sulfur and carbon diselenide reacted with sodium acetylide to give the same products as well as 1, 3-diselenole-2-selone (8). Table I lists the relative percentages of the products formed in these two reactions. The products were easily separated by chromatography on silica gel (5% CHCI3 in CCI4). Relative to 1, the introduction of selenium into the ring reduces the retention time on the column, while replacement of the thiocarbonyl in 1 with a seleno-carbonyl increases it. In a compound such as 6, the seleni-um in the carbonyl has a greater effect on the retention time than in the ring, and this material is eluted after 1.