过渡金属化合物为高效催化剂有氧氧化生物质衍生5-羟甲基糠醛生成2,5-二甲酰基呋喃的研究

Abstract

2,5-二甲酰基呋喃(DFF)是一种由5-羟甲基糠醛或其他生物基碳水化合物衍生的重要平台分子，它在有机合成工业的众多领域中具有许多潜在用途。鉴于其目前较高的价格以及合成技术的不成熟性，对该化合物的研究近年来已然成为研究热点。为了将来能够实现DFF工业化生产，已开发了一些技术用于该产品的高效生产。在本研究中，一些过渡金属化合物以及镧系化合物被用作有氧催化氧化生物质模型化合物5-羟甲基糠醛(5-HMF)获取高附加值DFF产品转化反应过程的催化剂，这些催化剂包括Nb2O5，V2O5，C3F9O9S3Yb·xH2O，Na3VO4，KVO3以及MnO2。由气相色谱分析(GC)以及气质分析(GC-MS)的结果可知：Nb2O5和Na3VO4对该转化反应没有明显的催化活性。此外，当以C3F9O9S3Yb·xH2O和MnO2为催化剂时，没有DFF生成，但生成了其他氧化产物比如5-乙酰氧基甲基-2-呋喃醛。其中，发现KVO3和V2O5在有氧选择性催化氧化5-HMF生成DFF的反应中是两种高效的催化剂。 2,5-diformylfuran (DFF) is one of the important platform molecules derived from 5-hydroxymethyl- furfural (HMF) or other bio-based carbohydrates, which has lots of potential applications in many fields of organic synthesis industry. This compound has become a research focus in recent years due to its relatively high price and immature synthesis technology. To realize the industrial production of DFF in the future, many methods have been attempted to achieve this product efficiently. In this research, some transition metal compounds and lanthanides, including Nb2O5, V2O5, C3F9O9S3Yb·xH2O, Na3VO4, KVO3 and MnO2, were adopted as plausible high-efficiency catalysts in aerobic oxidation of biomass-derived model molecule 5-Hydroxymethylfurfural (HMF) with the purpose of achieving high value-added DFF. The results from gas chromatographic analysis (GC) and gas chromatography-mass spectrometer (GC-MS) showed that Nb2O5 and Na3VO4 seem to have no obvious catalytic activity in this reaction. Moreover, no DFF was formed with C3F9O9S3Yb·xH2O and MnO2, other oxidation products such as 5-acetoxymethyl-2-furaldehyde were formed; KVO3 and V2O5 were found to be efficient catalysts for the aerobic selective oxidation reaction from HMF to DFF.