作者:Daolai Sun、Fumiya Sato、Yasuhiro Yamada、Satoshi Sato
DOI:10.1246/bcsj.20120247
日期:2013.2.15
Solvent-free Diels–Alder reactions were carried out by heating a mixture of a volatile diene, such as 1,3-butadiene, isoprene, or 2,3-dimethyl-1,3-butadiene, and a dienophile, such as methyl vinyl ketone, methyl acrylate, or maleic anhydride, in a closed batch reactor. High yields of Diels–Alder products were obtained without using solvents and catalysts within a short reaction time in most of the reactions. In particular, several reactions of dienophiles with 1,3-butadiene, which is known as a diene with low reactivity because of its gaseous form, also proceeded with high yields of Diels–Alder products in the closed batch reactor under conditions pressured by the reactant vapor. Solvent-free reactions provided high yields compared to reactions in solvent since the reaction heat directly resulted in increasing the reaction temperature and pressure. Energy in the exothermic reaction was used effectively in the closed batch system under solvent-free conditions.
无溶剂的Diels-Alder反应是在一个封闭的批式反应器中,通过加热混合挥发性的二烯烃(如1,3-丁二烯、异戊二烯或2,3-二甲基-1,3-丁二烯)与二烯亲电试剂(如甲基乙烯酮、甲基丙烯酸酯或马来酸酐)而进行的。大多数反应在短时间内在不使用溶剂和催化剂的情况下获得了高产率的Diels-Alder产物。特别是,一些公认由于其气态形式而反应活性较低的1,3-丁二烯与二烯亲电试剂的反应,在封闭批式反应器中,在反应物蒸气压力条件下,也以高产率进行了Diels-Alder产物生成。与溶剂中的反应相比,无溶剂反应提供了更高的产率,因为反应热直接导致了反应温度和压力的升高。在无溶剂条件下,封闭批式系统中有效地利用了放热反应的能量。