A Mannich-Type Condensation of Ethylenedinitramine with Carbethoxyhydrazine and Formaldehyde

Abstract

Notesrestricted in PhS02• radical. Our entropy of activation (AS *) of -7 eu is in good accord with Bartlett's6 observation of lowering of AS* in ¿erí-butyl perester decomposition.Experimental Section Kinetics.-The sulfur dioxide was expelled from the melted reaction mixture (243-297°) by a stream of nitrogen which was purified by passing through alkaline alcoholic solution of pyrogallol. The S02 was then absorbed in aqueous sodium hydroxide and titrated in the presence of 1% H2O2. The reaction mixture consisted of 0.0025 mol of phenyl sulfone and 0.05 g-atom of sulfur.Mass Spectrometry.-A Nier-type double collector mass spectrometer, MS-6, produced at the Institute Jo£ef Stefan, Ljubljana, Yugoslavia, was used. For the isotope effect determination natural abundance of sulfur-34 was utilized. Samples of SO2 gas from the reaction carried out to about 2% completion, and to complete decomposition of phenyl sulfone, respectively, were collected in a liquid air trap and purified in a vacuum line, and the 32S/34S mass ratios were determined as previously described.6