Search results for "Methyl azide"
showing 4 items of 4 documents
Unveiling the high reactivity of cyclohexynes in [3 + 2] cycloaddition reactions through the molecular electron density theory
2018
[3 + 2] cycloaddition (32CA) reactions of cyclohexyne, a cyclic strained acetylene, with methyl azide and methoxycarbonyl diazomethane have been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G(d) computational level. These 32CA reactions, which take place through a one-step mechanism involving highly asynchronous transition state structures, proceed with relatively low activation enthalpies of 6.0 and 4.3 kcal mol-1, respectively, both reactions being strongly exothermic. The reactions are initiated by the creation of a pseudoradical center at one of the two acetylenic carbons of cyclohexyne with a very low energy cost, 1.0 kcal mol-1, which promotes the eas…
Application of SQMFF Vibrational Calculations to Transition States: DFT and ab Initio Study of the Kinetics of Methyl Azide and Ethyl Azide Thermoly…
1998
DFT including nonlocal corrections and ab initio calculations at MP2 and MP4 levels of theory have been performed in order to provide information concerning the mechanism of the rate limiting step of the thermal decomposition of methyl azide and ethyl azide. The chemically interesting points of the ground-state potential energy surface have been fully optimized, and a detailed normal-mode analysis for the reagents and the transition states is presented. The well-established scaled quantum mechanical force field method has been used to obtain reliable vibrational frequencies for these molecular structures. The force fields of transition states have been modified by using the scale factors co…
Analyse und Optimierung von Gasphasen‐Reaktionen, 18 1,2) Die Pyrolyse von Methylazid
1981
Die PE-spektroskopisch analysierte Pyrolyse von Methylazid verlauft bei 850 K und liefert als Hauptprodukt Methanimin, welches nach einer MNDO-Singulett-Hyperflache betrachtlich stabiler sein sollte als das tautomere Methylnitren. Analysis and Optimization of Gasphase Reactions, 181,2) The Pyrolysis of Methyl Azide The PE spectroscopically analyzed pyrolysis of methyl azide occurs at 850 K and yields as main product methanimine, which according to a MNDO singlet hypersurface should be considerably stabilized relative to the tautomeric methyl nitrene.
Lewis Acid Mediated Domino Reaction between 2-Cyclohexenone and Methyl Azide - A DFT Study
2005
We have studied the Lewis acid mediated domino reaction between 2-cyclohexenone and methyl azide at the B3LYP/6-31G* and B3LYP/6-31+G**//B3LYP/6-31G* levels of theory. A complete survey of the potential energy surface is presented, and the structures of the stationary points and the corresponding molecular mechanism are discussed. The calculations suggest that the product, a cyclopentanone derivative, is formed by means of a domino process that comprises three consecutive reactions. The first and rate-limiting step is a concerted 1,3-dipolar cycloaddition between the Lewis acid coordinated cyclohexenone and methyl azide that yields the corresponding bicyclic 1,2,3-triazoline. The second rea…