56790-61-5Relevant academic research and scientific papers
Synthesis of cyclic selenenate/seleninate esters stabilized by ortho-nitro coordination: Their glutathione peroxidase-like activities
Singh, Vijay P.,Singh, Harkesh B.,Butcher, Ray J.
, p. 1431 - 1442 (2013/01/11)
The syntheses of selenenate/seleninate esters and related derivatives by aromatic nucleophilic substitution (SNAr) reactions of 2-bromo-3-nitrobenzylalcohol (13) and 2-bromo-3-nitrobenzaldehyde (17) with Na2Se2/nBuSeNa are
The Markedly Enhanced Basicity of Selenenamides vs Sulfenamides and the Mechanism of the Methanolysis of o-Nitro- and 2,4,6-Tri-tert-butylbenzeneselenenamides
Kice, John L.,Kutateladze, Andrei G.
, p. 917 - 923 (2007/10/02)
Measurement in acetonitrile-methanol of the basicity of selenenamides shows that they are approximately 3 pK units more basic than the corresponding sulfenamides.Since other explanations do not seem tenable, this apparently results from the fact that selenium is less electronegative than sulfur, although it is somewhat surprising that the small difference in the electronegativity of the two elements should lead to such a large difference in basicity.In the same solvent the kinetics of the acid-catalyzed methanolyses (eq 2) of o-nitro- and 2,4,6-tri-tert-butylbenzeneselenenamides are similar (large dependence of rate on , unusual dependence of rate on +>) to those for the methanolysis of the corresponding o-nitrobenzenesulfenamides.In the latter case the kinetics have been shown to be indicative of a mechanism where a sulfuranide (3, eq 5) is the key intermediate on the reaction coordinate; as a consequence, a similar kind of mechanism (eq 6) involving a hypervalent selenium intermediate (4) is proposed for eq 2.The unusual dependence on +> is because acid-catalyzed reversion of 4 to protonated selenenamide (2-H+) and methanol (step k-6) is faster under certain conditions than cleavage of 4 to give the final products (step k7).Comparison of the methanolysis kinetics of o-nitro (2a) and 2,4,6-tri-tert-butylbenzeneselenenamides (2c) shows that the coordination of an o-nitro group to selenium that stabilizes 2a and 2a-H+ does not appear to change the mechanism for methanolysis although it does cause the partitioning of 4 (k-6+>/k7) to be much less favorable to the formation of products (step k7).
Mechanism of the Facile Formation and Hydrolysis of Esters of o-Nitrobenzeneselenenic Acid: New Insight into the Mechanism of Nucleophilic Substitution Reactions of o-Nitrobenzeneselenenyl Derivatives
Kang, Sang-Ihn,Kice, John L.
, p. 295 - 301 (2007/10/02)
o-Nitrobenzeneselenenic acid (1) undergoes rapid acid-catalyzed esterification by alcohols to afford alkyl o-nitrobenzeneselenenates, o-O2NC6H4SeOR (2), in high yield.The mechanism of esterification of 1 and of its reverse, the hydrolysis of 2, has been i
