Kadu Rahul, Batabyal Monojit, Kadyan Heena, Koner Apurba Lal, Kumar Sangit
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Bhopal, Bhopal By-pass Road, Bhauri, Bhopal-462066, India.
Dalton Trans. 2019 May 28;48(21):7249-7260. doi: 10.1039/c8dt04832k.
A copper catalyzed efficient synthetic method has been developed to access bis(N-arylbenzamide) selenides from 2-halo-N-arylbenzamide substrates and disodium selenide in HMPA at 110 °C. The developed protocol tolerates substituents in both N-aryl and benzamide rings of the 2-halobenzamide substrates and provides an array of bis(N-arylbenzamide) selenides in practical yields. The resulting selenides were transformed into hypervalent spirodiazaselenuranes by oxidation using aqueous hydrogen peroxide. (N-(1-Naphthyl)) spirodiazaselenurane is also structurally characterized by a single crystal X-ray study. Hydroxy-substituted spiroselenuranes have been prepared by careful demethylation of methoxy-substituted selenides followed by oxidation by hydrogen peroxide. Antioxidant properties for the decomposition of hydrogen peroxide and for the deactivation of radicals of hydroxy-substituted spiroselenuranes have been studied by the thiol assay and 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. Both hydroxy-substituted spiroselenuranes exhibit dual mimic functions of glutathione peroxidase (GPx) selenoenzyme and α-tocopherol for decomposition of hydrogen peroxide and deactivation of radicals, respectively.
已开发出一种铜催化的高效合成方法，可在110℃下于六甲基磷酰胺（HMPA）中，由2-卤代-N-芳基苯甲酰胺底物和硒化二钠制备双（N-芳基苯甲酰胺）硒化物。所开发的方案能耐受2-卤代苯甲酰胺底物的N-芳基和苯甲酰胺环中的取代基，并以实际产率提供一系列双（N-芳基苯甲酰胺）硒化物。通过使用过氧化氢水溶液氧化，将所得的硒化物转化为高价螺二氮杂硒环烷。（N-（1-萘基））螺二氮杂硒环烷也通过单晶X射线研究进行了结构表征。通过对甲氧基取代的硒化物进行仔细的脱甲基，然后用过氧化氢氧化，制备了羟基取代的螺硒环烷。通过硫醇测定法和2,2-二苯基-1-苦基肼基（DPPH）测定法，研究了羟基取代的螺硒环烷对过氧化氢分解和自由基失活的抗氧化性能。两种羟基取代的螺硒环烷分别表现出谷胱甘肽过氧化物酶（GPx）硒酶和α-生育酚对过氧化氢分解和自由基失活的双重模拟功能。
