Paré Emily C, Brook David J R, Brieger Aaron, Badik Mick, Schinke Marie
Department of Chemistry and Biochemistry, University of Detroit Mercy, Detroit, MI 48221, USA.
Org Biomol Chem. 2005 Dec 7;3(23):4258-61. doi: 10.1039/b510075e. Epub 2005 Nov 2.
1,5-Diisopropyl-6-oxo-verdazyl free radicals were synthesized via the condensation of BOC protected isopropyl hydrazine with phosgene, deprotection with aqueous HCl, condensation with aldehydes to form tetrazanes and finally oxidation to give the free radicals. The introduction of isopropyl groups results in free radicals that show greater solubility in a variety of solvents and are more stable than their methyl substituted counterparts. ESR shows reduced hyperfine coupling to the isopropyl methine hydrogens consistent with this hydrogen being in the plane of the verdazyl ring.
1,5-二异丙基-6-氧代-连氮基自由基是通过BOC保护的异丙基肼与光气缩合、用盐酸水溶液脱保护、与醛缩合形成四氮烷,最后氧化得到自由基而合成的。异丙基的引入导致自由基在多种溶剂中具有更高的溶解度,并且比其甲基取代的同类自由基更稳定。电子顺磁共振显示与异丙基亚甲基氢的超精细偶合减少,这与该氢位于连氮基环平面内一致。