USE OF SUBSTITUTED 3-SULFOLENES AS PRECURSORS FOR 1,3-BUTADIENES
USE OF SUBSTITUTED 3-SULFOLENES AS PRECURSORS FOR 1,3-BUTADIENES
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DOI：
10.1080/00304948909356381
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发表时间：
1989-06-01
影响因子：
1.5
通讯作者：
TSO, HH
中科院分区：
文献类型：
--
作者：
CHOU, TS;TSO, HH
1，3-丁二烯是重要的合成子，在有机合成中得到了广泛的应用。然而，它们一般对热、光和酸性条件都很敏感。另一方面，3-环丁二烯可以作为掩蔽的1，3-丁二烯，因为它们在酸性条件下和中等温度下稳定，并且3-环丁二烯与相应的1，3-丁二烯之间的相互转化只需要温和的反应条件。1，3-丁二烯与液体二氧化硫在室温下反应，通常以较高的产率得到3-环丁烯。二氧化硫在约100-130℃的温度下从3-环丁二烯中热挤出，得到清洁的二烯烃(式1)‘。SO2的加成和挤出速率随二烯上取代基的不同而不同。实际上，可以通过在二甲苯中回流，或者通过在密封管中在低沸点的溶剂中以130℃的温度加热几个小时，或者通过在较高温度下短时间的热分解来实现从3-环丁二烯中挤出二氧化硫。
1, 3-Butadienes are important synthons that have been utilized extensively in organic synthesis. However, they are in general sensitive to heat, light and acidic conditions. 3-Sulfolenes, on the other hand, may serve as masked 1, 3-butadienes because they are stable to acidic conditions and moderately elevated temperatures, and the interconversion between 3-sulfolenes and their corresponding 1, 3-butadienes requires only mild reaction conditions. Reaction of 1, 3-butadienes with liquid sulfur dioxide at room temperature normally gives the 3-sulfolenes in good yields. Thermal extrusion of sulfur dioxide from 3-sulfolenes takes place at about 100-130 C to afford the dienes cleanly (eq 1)'. The rates of SO2 addition and extrusion vary with the substituents on the diene. Practically, SO2 extrusion from 3-sulfolenes can be achieved by refluxing in xylene, or by heating at 13OoC in low-boiling solvents in a sealed tube for a few hours, or by thermolysis at a higher temperature for a short period of time.