Preparation of SRN1-Type Coupling Adducts from Aliphatic gem-Dinitro Compounds in Ionic Liquids 英文参考文献.docVIP

Molecules 2012, 17, 4782-4790; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Preparation of SRN1-Type Coupling Adducts from Aliphatic gem-Dinitro Compounds in Ionic Liquids Akio Kamimura * and Seiichi Toyoshima Department of Applied Molecular Bioscience, Graduate School of Medicine, Yamaguchi University, Ube 755-8611, Japan * Author to whom correspondence should be addressed; E-Mail: ak10@yamaguchi-u.ac.jp; Tel./Fax: +81-836-859-231. Received: 29 February 2012; in revised form: 2 April 2012 / Accepted: 12 April 2012 / Published: 25 April 2012 Abstract: SRN1-type coupling adducts are readily prepared by the reaction between ?-sulfonylesters or ?-cyanosulfones and gem-dinitro compounds in ionic liquids. The reactions progress smoothly and recovered ionic liquids can be used for several iterations, as long as they are washed with water to remove alkali metallic salts. The reaction rate is slower than the corresponding SRN1 reaction in DMSO, but no acceleration on irradiation or no inhibition in the presence of m-DNB are observed. Keywords: SRN1-type adducts; ionic liquids; nitro compounds; kinetics 1. Introduction The SRN1 reaction is a unique reaction that proceeds via a single electron transfer process [1–3]. The reaction usually starts with a single electron transfer that generates a radical anion species, which then gives a radical species via cleavage of the anion radical. Then, the radical reacts with a coupling partner to form products. The reaction is usually performed in either liquid ammonia or a dipolar aprotic solvent such as DMSO and HMPA. The reaction progresses through a radical chain mechanism and the reaction rate are significantly lowered by the presence of small amounts of a radical inhibitor such as p-dinitrobenzene. The SRN1 reaction is frequently used to construct aromatic compounds [4–15]. The SRN1 reaction between aliphatic compoun