Silica Sulfuric Acid NaNO2 as a Novel Heterogeneous System for the Nitration of Phenols under Mild Conditions 英文参考文献.docVIP

Molecules 2002, 7, 734-742 molecules ISSN 1420-3049 Silica Sulfuric Acid/ NaNO2 as a Novel Heterogeneous System for the Nitration of Phenols under Mild Conditions Mohammad Ali Zolfigol*, Elahe Madrakian and Ezat Ghaemi Department of Chemistry, College of Science, University of Bu-Ali Sina, Zip Code 65174, Post Box No. 4135, Hamadan, I.R. Iran; Fax: (+98) 81 8272404. * Author to whom correspondence should be addressed; e-mail: zolfi@basu.ac.ir Received: 2 October 2001; in revised form: 14 October 2002/ Accepted: 14 October 2002 / Published 31 October 2002 Abstract: Nitrophenols can be obtained in moderate to high yields via nitrosation- oxidation of phenols with silica sulfuric acid, NaNO2 and wet SiO2 at room temperature. In situ generation of HNO2 and a radical cation mechanism via the nitrous acid catalyzed (NAC) pathway appear to be applicable to phenol nitration using these reagents. Keywords: Silica sulfuric acid, nitrosation-oxidation, nitration, nitrophenols. Introduction In several industrially important processes (e.g. nitration, nitrosation, etc.) a large excess of sulfuric acid is required because the water by-product slows the reaction down by diluting the acid. At the end of these processes, a large amount of “spent acid” is obtained which, in batch reactions, is usually neutralized and disposed of, while, in continuous processes, it has to be recycled by complex techniques. Also, the separation of the products from the acid is often a difficult and energy consuming process that habitually implies a basic aqueous work-up. Moreover, sulfuric acid is corrosive and is dangerous to transport and handle. Consequently, any reduction in the amount of sulfuric acid needed and/or any simplification in handling procedures would be highly convenient in terms of risk reduction, economic advantages and environment protection [1]. On the other hand, there is