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吡喃木糖和o-乙酰基吡喃木糖热解形成羟基乙醛的机理研究

, PP. 185-194

Keywords: 吡喃木糖,o-乙酰基,热解,羟基乙醛,密度泛函理论

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Abstract:

?以半纤维素主要成分木聚糖的两种单体——吡喃木糖和o-乙酰基吡喃木糖为模型化合物,运用密度泛函理论(dft),采用b3lyp方法和6-31+g(d,p)基组进行计算,研究了吡喃木糖热解形成haa的6条可能的反应路径和o-乙酰基吡喃木糖热解形成haa的3条可能的反应路径。由此确定了吡喃木糖热解形成haa的最优路径为:吡喃木糖首先开环得到链式木糖,然后c3羟基和c2氢脱水,随后经重排和逆醇醛缩合反应生成包含c4/c5的haa;该路径的决速步骤为脱水反应,能垒为253.3kj/mol。o-乙酰基吡喃木糖热解形成haa的最优路径为:o-乙酰基吡喃木糖首先支链断裂脱出乙酸(aa),开环后的链式中间体经氢转移反应得到包含c4/c5的haa;该路径的决速步骤为最后的氢转移反应,能垒为317.6kj/mol。

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