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Characteristic activity of phosphorous acid in the dehydration condensation of a chitin-derived nitrogen-containing sugar alcohol
Green Chemistry ( IF 9.3 ) Pub Date : 2021-08-13 , DOI: 10.1039/d1gc02193a Cheng Yang 1, 2 , Takuya Sagawa 1, 3 , Atsushi Fukuoka 1 , Hirokazu Kobayashi 1
Green Chemistry ( IF 9.3 ) Pub Date : 2021-08-13 , DOI: 10.1039/d1gc02193a Cheng Yang 1, 2 , Takuya Sagawa 1, 3 , Atsushi Fukuoka 1 , Hirokazu Kobayashi 1
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Chitin is a potential resource for the production of renewable organonitrogen compounds, as it contains biologically fixed nitrogen. Hydrolysis of chitin followed by hydrogenation gives the sugar alcohol named 2-acetamido-2-deoxysorbitol (ADS). The dehydration condensation of ADS produces 2-acetamido-2-deoxyisosorbide (ADI), which is a prospective precursor of nitrogen-containing polymers. However, the conversion of ADS to ADI in previous works needed a large amount of CF3SO3H as a superstrong acid catalyst, which is high cost and requires special corrosion-resistant equipment. In this work, we have found that H3PO3, a weak acid, can convert ADS to ADI. Possibly, H3PO3 alters the reaction mechanism from a simple acid-catalysed dehydration cyclisation to a cyclisation via phosphite esters. Density functional theory calculations suggest that the modified pathway via the phosphite esters significantly reduces the activation energy. In addition, the reducing ability of the acid likely decreases the formation of condensation by-products.
中文翻译：
亚磷酸在甲壳素衍生含氮糖醇脱水缩合中的特征活性
几丁质是生产可再生有机氮化合物的潜在资源，因为它含有生物固定氮。几丁质水解，然后氢化，得到名为 2-乙酰氨基-2-脱氧山梨糖醇 (ADS) 的糖醇。ADS 脱水缩合产生 2-乙酰氨基-2-脱氧异山梨醇 (ADI)，它是含氮聚合物的预期前体。但以往工作中ADS向ADI的转化需要大量CF 3 SO 3 H作为超强酸催化剂，成本高，需要特殊的耐腐蚀设备。在这项工作中，我们发现 H 3 PO 3是一种弱酸，可以将 ADS 转化为 ADI。可能，H 3 PO 3将反应机理从简单的酸催化脱水环化改变为通过亚磷酸酯的环化。密度泛函理论计算表明，通过亚磷酸酯的修饰途径显着降低了活化能。此外，酸的还原能力可能会减少缩合副产物的形成。
更新日期：2021-08-31
中文翻译：
亚磷酸在甲壳素衍生含氮糖醇脱水缩合中的特征活性
几丁质是生产可再生有机氮化合物的潜在资源，因为它含有生物固定氮。几丁质水解，然后氢化，得到名为 2-乙酰氨基-2-脱氧山梨糖醇 (ADS) 的糖醇。ADS 脱水缩合产生 2-乙酰氨基-2-脱氧异山梨醇 (ADI)，它是含氮聚合物的预期前体。但以往工作中ADS向ADI的转化需要大量CF 3 SO 3 H作为超强酸催化剂，成本高，需要特殊的耐腐蚀设备。在这项工作中，我们发现 H 3 PO 3是一种弱酸，可以将 ADS 转化为 ADI。可能，H 3 PO 3将反应机理从简单的酸催化脱水环化改变为通过亚磷酸酯的环化。密度泛函理论计算表明，通过亚磷酸酯的修饰途径显着降低了活化能。此外，酸的还原能力可能会减少缩合副产物的形成。
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