程庆彦,朱响林,王延吉,赵新强

• 1:河北工业大学绿色化工与高效节能河北省重点实验室

摘要(Abstract)：

在超声波辐射条件下,以P_2O_5为催化剂,研究了其在环己酮肟(CHO)液相贝克曼重排合成己内酰胺(CPL)中的催化性能。考察了超声功率密度、溶剂种类与数量、超声辐射时间等对环己酮肟液相贝克曼重排反应性能的影响,在常温、0.01 mol CHO、0.25 g P_2O_5、10 m L DMF、超声功率密度0.29 W×cm-2、超声辐射1.5 h的条件下,CHO的转化率为99.1%,CPL的选择性为99.4%。利用在线反应红外光谱研究了超声辐射条件下P_2O_5催化环己酮肟液相贝克曼重排反应机理:在超声波辐射存在下,DMF的羰基和CHO中处于C=N-OH邻位的亚甲基形成氢键,P_2O_5中P和O原子分别与DMF中的N、羰基碳上的H形成配位键和氢键,共同作用形成一种五元环结构使得DMF吸附在P_2O_5上;CHO吸附在P_2O_5上通过P_2O_5中的氧和磷分别和CHO中N+OH2、NOH的氢和氧形成氢键和P-OH;氢质子从氮原子转移到氧原子上,同时脱除一分子的H2O;与羰基形成氢键的亚甲基电子云密度增大,有利于亲核进攻氮正离子,形成碳正离子;H2O进攻碳正离子、失去质子、异构化形成CPL。

关键词(KeyWords)： 超声波辐射;环己酮肟;液相贝克曼重排;己内酰胺;P2O5

Abstract:

Keywords:

基金项目(Foundation):

作者(Author): 程庆彦,朱响林,王延吉,赵新强

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