取代基和促进剂对偏苯三酸生物可再生合成中Diels-Alder环加成反应的影响,RSC Advances

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取代基和促进剂对偏苯三酸生物可再生合成中Diels-Alder环加成反应的影响
RSC Advances ( IF 3.9 ) Pub Date : 2020-8-18 , DOI: 10.1039/d0ra04318d
Tuhin Suvra Khan ₁ , Shelaka Gupta ₂ , Maaz Ahmad ₃ , Md Imteyaz Alam ₃ , M Ali Haider ₃

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通过利用密度泛函理论 (DFT) 模拟，提出了一种生产氧代降冰片烯的有效途径，氧代降冰片烯是一种通过生物质衍生的二烯和亲双烯体的 Diels-Alder (DA) 反应生产生物基偏苯三酸 (TMLA) 的前体。有人提出二烯如 5-羟甲基糠醛 (HMF)、2,5-二甲基呋喃 (DMF)、呋喃二羧酸 (FDCA) 和生物质衍生的亲二烯体（乙烯衍生物，例如丙烯醛、丙烯酸等）的 DA 反应.) 导致形成中间产物氧代降冰片烯，它是生产 TMLA 的前体。DA 反应的活化势垒与二烯和亲双烯体上存在的取代基类型相关。在亲二烯体中，发现丙烯醛是与二烯DMF、HMF和羟甲基糠酸（HMFA）的环加成反应的最佳候选物，其具有低活化能（<40 kJ mol ^{-1 ）。}FMO 间隙和（IP_二烯+ EA_亲二烯体)/2 都被认为是富电子二烯和缺电子二烯体的 DA 反应的合适描述符。其他溶剂对 DA 反应的活化势垒没有显着影响。相反，由于 FMO 间隙的减少，路易斯酸的存在被认为降低了活化势垒。

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Effect of substituents and promoters on the Diels–Alder cycloaddition reaction in the biorenewable synthesis of trimellitic acid

An efficient route to produce oxanorbornene, a precursor for the production of bio-based trimellitic acid (TMLA) via the Diels–Alder (DA) reaction of biomass-derived dienes and dienophiles has been proposed by utilizing density functional theory (DFT) simulations. It has been suggested that DA reaction of dienes such as 5-hydroxymethyl furfural (HMF), 2,5-dimethylfuran (DMF), furan dicarboxylic acid (FDCA) and biomass-derived dienophiles (ethylene derivatives e.g., acrolein, acrylic acid, etc.) leads to the formation of an intermediate product oxanorbornene, a precursor for the production of TMLA. The activation barriers for the DA reaction were correlated to the type of substituent present on the dienes and dienophiles. Among the dienophiles, acrolein was found to be the best candidate showing a low activation energy (<40 kJ mol⁻¹) for the cycloaddition reaction with dienes DMF, HMF and hydroxy methyl furoic acid (HMFA). The FMO gap and (IP_diene + EA_dienophile)/2 were both suggested to be suitable descriptors for the DA reaction of electron-rich diene and electron-deficient dienophile. Further solvents did not have a significant effect on the activation barrier for DA reaction. In contrast, the presence of a Lewis acid was seen to lower the activation barrier due to the reduction in the FMO gap.

更新日期：2020-08-18

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