A mechanochemical study of the effects of compression on a Diels-Alder reaction
A mechanochemical study of the effects of compression on a Diels-Alder reaction
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DOI：
10.1063/1.4960955
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发表时间：
2016-08-21
影响因子：
4.4
通讯作者：
Subramanian, Gopinath
中科院分区：
文献类型：
--
作者：
Jha, Sanjiv K.;Brown, Katie;Subramanian, Gopinath
我们研究了压缩外力对丁二烯和乙烯之间Diels-Alder （DA）反应机理的影响。在CASSCF(6,6)/6- 31g **和B3LYP/6-311++G**理论水平的力学化学框架下，采用轻推弹性带法计算了反应路径和过渡态。我们的研究结果表明，压缩静水压力降低了母体DA反应的能垒，同时抑制了不良副反应，从而直接提高了环己烯的产率。压缩压力也增加了母体DA反应的放热性，这将导致反应容器温度升高，从而间接提高环己烯的产率。我们的估计表明，我们研究中使用的压缩对应于68 MPa-1410 MPa的范围。AIP出版社出版。
We examine the effects of compressive external forces on the mechanisms of the parent Diels-Alder (DA) reaction between butadiene and ethylene. Reaction pathways and transition states were calculated using the nudged elastic band method within a mechanochemical framework at the CASSCF(6,6)/6-31G**, as well as the B3LYP/6-311++G** levels of theory. Our results suggest that compressive hydrostatic pressure lowers the energy barrier for the parent DA reaction while suppressing the undesirable side reaction, thereby leading to a direct increase in the yield of cyclohexene. Compressive pressure also increases the exothermicity of the parent DA reaction, which would lead to increased temperatures in a reaction vessel and thereby indirectly increase the yield of cyclohexene. Our estimates indicate that the compression used in our study corresponds to a range of 68 MPa-1410 MPa. Published by AIP Publishing.