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The Role of Iodine Catalyst in the Synthesis of 22-Carbon Tricarboxylic Acid and Its Ester: A Case Study

机译:碘催化剂在22-碳三羧酸合成及其酯中的作用:一种案例研究

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摘要

Here, 22-carbon tricarboxylic acid (C22TA) and its ester (C22TAE) were prepared via the Diels−Alder reaction of polyunsaturated fatty acids (PUFAs) and their esters (PUFAEs) as dienes with fumaric acid (FA) and dimethyl fumarate (DF) as dienophiles, respectively. The role of an iodine catalyst for the synthesis of C22TA and C22TAE in the Diels−Alder type reaction was investigated using a spectroscopic approach. The chemical structures of the products were characterized using proton nuclear magnetic resonance (1H-NMR) and electrospray ionization mass spectrometry (ESI-MS) analysis. Results showed that nonconjugated dienes can react with dienophiles through a Diels−Alder reaction with an iodine catalyst, and that iodine transformed the nonconjugated double bonds of dienes into conjugated double bonds via a radical process. DF was more favorable for the Diels−Alder reaction than FA. This was mainly because the dienophile DF contained an electron-withdrawing substituent, which reduced the highest and lowest occupied molecular orbital (HOMO−LUMO) energy gap and accelerated the Diels−Alder reaction. By transforming nonconjugated double bonds into conjugated double bonds, iodine as a Lewis acid increased the electron-withdrawing effect of the carbonyl group on the carbon−carbon double bond and reduced the energy difference between the HOMO of diene and the LUMO of dienophile, thus facilitating the Diels−Alder reaction.
机译:在这里,22 - 碳三羧酸(C22TA)及其酯(C22TAE)通过的多不饱和脂肪酸(PUFA)和它们的酯(PUFAEs)与富马酸(FA)和富马酸二甲酯二烯的Diels-Alder反应(DF制备)作为亲双烯体,分别。使用分光方法碘催化剂C22TA和C22TAE在狄尔斯阿德耳类型反应合成的作用进行了研究。使用质子核磁共振(1H-NMR)和电喷雾电离质谱(ESI-MS)分析该产物的化学结构进行了表征。结果表明,非共轭二烯可以通过与碘催化剂狄尔斯 - 阿尔德反应中与亲二烯体反应,和碘经由自由基过程转化二烯的非共轭双键为共轭双键。 DF是比FA的Diels-Alder反应更有利。这主要是因为亲二烯体DF含有吸电子取代基,其降低的最高和最低占据分子轨道(HOMO-LUMO)能隙,加速了Diels-Alder反应。通过将非共轭双键为共轭双键,碘作为路易斯酸增加碳 - 碳双键的羰基的吸电子效应和降低的二烯的HOMO和亲双烯体的LUMO之间的能量差,从而有利于的Diels-Alder反应。

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