Branched Diol Monomers from the Sequential Hydrogenation of Renewable Carboxylic Acids
Branched Diol Monomers from the Sequential Hydrogenation of Renewable Carboxylic Acids
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DOI：
10.1002/cctc.201600710
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发表时间：
2016-10
期刊：
影响因子：
4.5
通讯作者：
Charles S. Spanjers;Deborah K Schneiderman;Jay Z. Wang;Jingyue Wang;M. Hillmyer;Kechun Zhang;Paul J. Dauenhauer
中科院分区：
文献类型：
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作者：
Charles S. Spanjers;Deborah K Schneiderman;Jay Z. Wang;Jingyue Wang;M. Hillmyer;Kechun Zhang;Paul J. Dauenhauer
用生物衍生替代品替代石化聚合物的一个突出挑战是将生物质有效转化为有用的单体。在这项工作中，我们展示了在水介质中使用非均相催化剂从五碳和六碳酸合成多功能醇的实用方法。该过程的设计以热力学计算为指导，这表明需要进行两次连续的高压氢化：一是在高温下将酸还原为内酯；二是在高温下将酸还原为内酯。二、内酯在低温下进一步还原为相应的二醇或三醇。例如，在 240 °C 下，中康酸转化为 (α 或 β)-甲基-γ-丁内酯，其转换频率为 1.2 min−1，选择性超过 Pd/C，选择性为 95%。随后，在 100 °C 下，Ru/C 将 (α 或 β)-甲基-γ-丁内酯转化为 2-甲基-1,4-丁二醇，产率为 80%。该工艺是生产内酯、二醇和三醇的有效方法，这些都是合成生物支化聚酯的有价值的单体。
A prominent challenge in replacing petrochemical polymers with bioderived alternatives is the efficient transformation of biomass into useful monomers. In this work, we demonstrate a practical process for the synthesis of multifunctional alcohols from five‐ and six‐carbon acids using heterogeneous catalysts in aqueous media. Design of this process was guided by thermodynamic calculations, which indicate the need for two sequential high‐pressure hydrogenations: one, reduction of the acid to a lactone at high temperature; two, further reduction of the lactone to the corresponding diol or triol at low temperature. For example, the conversion of mesaconic acid into (α or β)‐methyl‐γ‐butyrolactone was achieved with 95 % selectivity at a turnover frequency of 1.2 min−1 over Pd/C at 240 °C. Subsequent conversion of (α or β)‐methyl‐γ‐butyrolactone into 2‐methyl‐1,4‐butanediol was achieved with a yield of 80 % with Ru/C at 100 °C. This process is an efficient method for the production of lactones, diols, and triols, all valuable monomers for the synthesis of bioderived branched polyesters.