Elementary and systemic views of the generation of toxic substances
Elementary and systemic views of the generation of toxic substances
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对有毒物质产生的基本和系统观点
DOI：
10.1039/c6gc90058e
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发表时间：
2016
期刊：
影响因子：
9.8
通讯作者：
Takayuki Wakaki,Kounosuke Oisakia and Motomu Kanai*
中科院分区：
文献类型：
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作者：
Wakaki Takayuki;Togo Takaya;Yoshidome Daisuke;Kuninobu Yoichiro;Kanai Motomu;Takayuki Wakaki,Kounosuke Oisakia and Motomu Kanai*
“绿色化学”一词最早提出于1991年。1绿色化学的概念在“绿色化学的十二项原则”（图1）2中得到了简要而精确的概括，该原则已被化学家们广泛认可超过25年。今天，我们面临着前所未有的环境问题，主要是由人类活动造成的。绿色化学的概念对于从科学基础上维持地球上的可居住环境极为重要。这些原则为学术界和工业界的化学研究提供了正确的方向。在这篇社论中，我们重新考虑了绿色化学十二原则中的第三条原则，即在可行的情况下，合成方法的设计应该使用和产生对人类健康和环境几乎没有毒性的物质。这第三条原则的重要性是不容否认的。以下三种主要醇氧化方法的时间依赖性转变代表了该原理的有效性（方案1）。在20世纪60年代至70年代，铬氧化物如氯铬酸吡啶盐和重铬酸吡啶盐常用于将醇氧化成醛、酮和羧酸（方案1.1）。这些试剂产生化学计量的含重金属铬的副产物，其对人类健康和环境具有显著毒性。3 Swern氧化，通常使用二甲基亚砜（DMSO），草酰氯和三乙胺在二氯甲烷溶剂中在-78 ℃下，不产生重金属副产物，因此是比氧化铬介导的过程更合适的相关转化替代方案（方案1.2）。事实上，Swern氧化是实验室规模上最常用的氧化反应之一。然而，在工业规模系统中，标准Swern氧化与几个问题相关：（1）草酰的毒性和腐蚀性
The term “Green Chemistry” was first suggested in 1991. 1 The concept of green chemistry is briefly but precisely summarized in the “Twelve Principles of Green Chemistry”(Fig. 1), 2 which have been widely recognized by chemists for over 25 years. Today, we face unprecedented environmental problems, mainly caused by human activities. The concept of green chemistry is extremely important for sustaining the habitable environments on Earth from a scientific basis. These principles provide a guideline for aiming chemical research in the right directions in both academia and industry. In this Editorial, we reconsider the 3rd principle of the Twelve Principles of Green Chemistry, ie, wherever practicable, synthetic methods should be designed to use and generate substances that possess little or no toxicity to human health and the environment. There is no denying the importance of this third principle. The time-dependent transition of the following three main alcohol oxidation methods represents the validity of this principle (Scheme 1). In the 1960s–1970s, chromium oxides such as pyridinium chlorochromate and pyridinium dichromate were frequently used for oxidation of alcohols to aldehydes, ketones, and carboxylic acids (Scheme 1.1). Those reagents generate stoichiometric amounts of heavy metal chromium-containing side products, which have significant toxicity to human health and the environment. 3 The Swern oxidation, typically using dimethylsulfoxide (DMSO), oxalyl chloride, and triethylamine in methylene chloride solvent at− 78 C, does not produce heavy metal side products, and thus is a more suitable alternative for the relevant conversion than chromium oxide-mediated processes (Scheme 1.2). Indeed, the Swern oxidation is one of the most commonly used oxidation reactions on the laboratory scale. In industrial scale systems, however, the standard Swern oxidation is associated with several problems;(1) the toxicity and corrosive properties of oxalyl