SIO2-SO4催化剂的制备 (中英文)

Silica sulfuric acid/NaNO2 as a novel heterogeneous system for production of thionitrites and disulfides under mild conditions

在温和的条件下以硅磺酸的亚硝酸钠作为一种新型的非均相体系制备硫代亚硝酸盐

和二硫化物

Mohammad Ali Zolfigol

Department of Chemistry, College of Science, Bu-Ali Sina University, P.O. Box 4135, Hamadan 65174, Iran

Received 9 April 2001; revised 23 August 2001; accepted 13 September 2001

穆罕默德·阿里·Zolfigol

学院，理学院化学系，布阿里新浪，P.O.Box 4135，哈马丹65174，伊朗收稿日期2001年4月9号修订日期2001年8月23日发表日期2001年9月13号Abstract-Neat chlorosulfonic acid reacts with silica gel to give silica sulfuric acid in which sulfuric acid is immobilized on the surface of silica gel via covalent bond. Thiols can be readily converted to their corresponding thionitrites with a combination of silica sulfuric acid, wet SiO2and sodium nitrite in dichloromethane at room temperature. Disulfides result from the homolytic cleavage of the sulfur-nitrogen bond of the unstable thionitrites and subsequent coupling of the resultant thiyl radicals. 2001 Elsevier Science Ltd. All rights reserved.

摘要规整氯磺酸反应，用硅胶，得到二氧化硅硫酸，其中硫酸是通过共价键固定在硅凝胶的表面上。硫醇类，可以很容易地转换为用硫酸，在室温下在二氯甲烷中的溶胀的二氧化硅和亚硝酸钠的组合其相应的硫醇类亚硝酸盐。二硫化物的不稳定硫醇类亚硝酸盐和随后耦合，所得到的硫中心自由基的硫氮键的均裂。2001 Elsevier科学有限公司保留所有权利。

Any reduction in the amount of sulfuric acid needed and/or any simplification in handling procedures is required for risk reduction, economic advantage and environment protection. In addition, there is current research and general interest in heterogeneous systems because of the importance such systems have in industry and in developing technologies. In continuation of our studies on the application of inorganic acidic salts we found that silica gel reacts with chlorosulfonic acid to give silica sulfuric acid (I). It is interesting to note that the reaction is easy and clean without any work-up procedure because HCl gas is evolved from the reaction vessel immediately (Scheme 1).

任何减少硫磺酸用量或处理程序的简化，都要符合减少风险，确立经济优势和环保要求。此外，目前的研究和普遍关心的是异构系统，因为这样的系统对工业和技术发展很重要。在无机酸性盐的应用上继续我们的研究，我们发现，硅胶硫酸（I）与氯磺酸反应。有趣的是，该反应是容易和清洁的，因为HCl气体立即从反应容器（图1）放出，没有任何工作程序。

We hoped that the silica sulfuric acid (I) would be a superior proton source to all of the reported acidic solid supports or acidic resins such as polystyrene sulfonic acid and Nafion-H3 for running reactions under heterogeneous conditions. Therefore, we were interested in using this inorganic acidic resin (I) for the in situ generation of HNO2 when used in conjunction with NaNO2, wet SiO2 and an organic solvent. On the other hand, thionitrites have not been as widely studied as their oxygen counterparts alkyl nitrites, generally because of their reduced stability. However, in recent years there has been much interest generated in the chemistry and biochemistry of nitrosothiols, since (a) they are being