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Renewable Cyclobutane-1,3-dicarboxylic Acid (CBDA) Building Block Synthesized from Furfural via Photocyclization
ACS Sustainable Chemistry & Engineering ( IF 8.4 ) Pub Date : 2020-05-22 , DOI: 10.1021/acssuschemeng.0c00708
Zhihan Wang 1 , Mark Scheuring 1 , Micah Mabin 1 , Rahul Shahni 1 , Zijun D. Wang 1 , Angel Ugrinov 2 , Jonathan Butz 1 , Qianli R. Chu 1
Affiliation  

A novel renewable building block with a semirigid structure, (1α,2α,3β,4β)-2,4-di(furan-2-yl)cyclobutane-1,3-dicarboxylic acid (CBDA-5), was synthesized from furfural. The synthesis started with a Knoevenagel condensation between furfural and malonic acid, and a subsequent decarboxylation in the same pot, which produced 2-furanacrylic acid. The corresponding ester, ethyl-2-furanacrylate, was prepared by the Fisher or Steglich esterification of 2-furanacrylic acid with ethanol. Solvent-free [2 + 2] photodimerization of crystalline ethyl 2-furanacrylate was then carried out at −20 °C under blacklight to give diethyl 2,4-di(furan-2-yl)cyclobutane-1,3-dicarboxylate (CBDE-5). Afterward, CBDE-5 was hydrolyzed to give the corresponding dicarboxylic acid, CBDA-5. Both CBDE-5 and CBDA-5 were confirmed by NMR spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, high-resolution mass spectrometry (HRMS), and single-crystal X-ray diffraction (XRD). A preliminary study showed that CBDE-5 and CBDA-5 could be used as renewable building blocks to produce fully biobased polyesters. In this study, several “green” techniques were applied to prepare renewable building blocks, including solvent-free crystallization, solvent- and metal-free photodimerization, and the use of residential blacklight as an energy-efficient, cost-effective, and operator-friendly UV (ECO-UV) irradiation source in the stereoregular photocycloaddition.

中文翻译:

通过光环化从糠醛合成可再生的环丁烷-1,3-二羧酸(CBDA)构件

由糠醛合成了一种新型的半刚性结构可再生砌块(1α,2α,3β,4β)-2,4-二(呋喃-2-基)环丁烷-1,3-二羧酸(CBDA-5) 。合成开始于糠醛和丙二酸之间的Knoevenagel缩合反应,然后在同一罐中进行脱羧,生成了2-呋喃丙烯酸。相应的酯-2-呋喃丙烯酸乙酯是通过2-呋喃丙烯酸与乙醇的Fisher或Steglich酯化反应制备的。然后在-20°C的黑光下,无溶剂的[2- + 2]结晶2-呋喃丙烯酸乙酯光致二聚,得到2,4-二(呋喃-2-基)环丁烷-1,3-二羧酸二乙酯(CBDE -5)。然后,将CBDE-5水解,得到相应的二羧酸CBDA-5。CBDE-5和CBDA-5均通过NMR光谱证实,傅里叶变换红外(FT-IR)光谱,高分辨率质谱(HRMS)和单晶X射线衍射(XRD)。初步研究表明,CBDE-5和CBDA-5可以用作可再生建筑材料,以生产完全基于生物的聚酯。在这项研究中,采用了几种“绿色”技术来制备可再生的建筑材料,包括无溶剂结晶,无溶剂和无金属的光二聚化,以及将住宅黑光用作节能,经济高效和操作员的方法。立体有规光环加成中的友好紫外线(ECO-UV)辐射源。
更新日期:2020-06-23
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