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Radiolytic Synthesis of Cyanogen Chloride, Cyanamide and Simple Sugar Precursors
ChemistrySelect ( IF 1.9 ) Pub Date : 2018-09-25 , DOI: 10.1002/slct.201802242
Ruiqin Yi 1 , Yayoi Hongo 1 , Isao Yoda 2 , Zachary R. Adam 3, 4 , Albert C. Fahrenbach 1
Affiliation  

Chemical evolution, from simple molecules to complex systems, is fundamental to modern origins of life research, and complex reaction networks are often supposed to have operated on the early Earth. Herein, a variety of compounds useful particularly for RNA synthesis − namely, cyanogen chloride, cyanamide, and nitrile precursors to simple sugars − are produced in short order by a chemical reaction network starting from hydrogen cyanide and driven by gamma radiolysis. The radiolytic yield of cyanamide was found to be proportional to the concentration of chloride, an often overlooked spectator anion. Aqueous irradiation of hydrogen cyanide in the presence of sodium chloride also affords cyanogen chloride, a possible intermediate in the radiolytic synthesis of cyanamide. Meanwhile, the synthesis of simple sugar precursors is proposed to proceed through a Kiliani‐Fischer homologation mechanism made possible by the reducing power of the solvated electron and hydrogen atom. Such a reaction network has the potential to serve as a model for better understanding and engineering chemical evolution of complex mixtures in the laboratory that could have happened on the early Earth.

中文翻译:

氯化氰,氰胺和简单糖前体的辐射合成

从简单分子到复杂系统的化学演化是现代生命研究起源的基础,并且通常认为复杂的反应网络已经在地球早期起作用。在此,由氰化氢开始并由伽马射线辐照驱动的化学反应网络可在短时间内生产出各种特别可用于RNA合成的化合物,即氯化氰,氰胺和单糖的腈前体。发现氰酰胺的放射产率与氯离子浓度成正比,而氯离子常常被旁观者视为负离子。在氯化钠的存在下,氰化氢的水溶液辐射也提供了氯化氰,这是氰酰胺辐射合成中的一种可能的中间体。同时,提出了通过糖化电子和氢原子的还原力使Kiliani-Fischer同源机制得以进行的简单糖前体的合成方法。这样的反应网络有可能成为更好地理解和工程化实验室中复杂混合物(可能发生在地球早期)的化学演化的模型。
更新日期:2018-09-25
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