1120-85-0Relevant articles and documents
Mechanistic studies of the copolymerization reaction of aziridines and carbon monoxide to produce poly-β-peptoids
Darensbourg, Donald J.,Phelps, Andrea L.,Le Gall, Nathalie,Jia, Li
, p. 13808 - 13815 (2004)
The coupling of carbon monoxide and aziridines has been shown to be selective for comonomer-alternating enchainment in the presence of PhCH 2C(O)Co(CO)4 to afford poly-β-peptoids. In this article, we have investigated the mechanistic aspects of the reaction of CO and N-butylaziridine by means of in situ infrared spectroscopy employing CH 3C(O)Co(CO)3L (L = PPh3 (1) and P(otolyl) 3 (2)) as precatalysts. Precatalyst 1 exists in solution under catalytic conditions as an equilibrium mixture of 1 and CH3C(O)Co(CO) 4, and affords both poly-β-butylalanoid and the corresponding lactam. By way of contrast, precatalyst 2 which possesses the sterically bulky and labile P(o-tolyl)3 ligand, affords only the acyl cobalt tetracarbonyl species in solution during catalysis with concomitant selective production of the copolymer. Kinetic studies conducted with precatalyst 2 showed the coupling reaction to have a first order dependence on catalyst, a first order dependence on N-butylaziridine, and only a slight dependence on the concentration of CO over the pressure range 17-69 bar. The working mechanistic model for the copolymerization reaction involves first aziridine insertion into the cobalt-acyl bond, rate determining ring opening by the cobaltate species, followed by the migratory CO insertion.
Acid-Catalyzed Decomposition of 1-Alkyltriazolines: A Mechanistic Study
Smith, Richard H.,Wladkowski, Brian D.,Taylor, Jesse E.,Thompson, Erin J.,Pruski, Brunon,et al.
, p. 2097 - 2103 (2007/10/02)
1-Alkyltriazolines are five-membered cyclic triazenes containing the unusual Z-configuration for the triazene moiety.The hydrolytic decomposition of these compounds in aqueous or mixed acetonitrile-aqueous buffers leads predominantly to the formation of the corresponding 1-alkylaziridines and lesser amounts of 2-(alkylamino)ethanols, alkylamines, and acetaldehyde.The latter two products presumably result from hydrolysis of a rearrangement produkt, N-ethylidenealkylamine.Neither the nature of the 1-alkyl group nor the pH of the medium greatly influences the product distribution, although decomposition in purely aqueous buffers slightly reduces the aziridine yields.The rate of hydrolysis of 1-alkyltriazolines is about twice as fast as that of the analogous acyclic 1,3,3-trialkyltriazenes and varies in the order tert-butyl > isopropyl > ethyl > butyl > methyl > propyl > benzyl.The mechanism of the decomposition is specific acid-catalyzed (A1) involving rapid reversible protonation followed by rate-limiting formation of a 2-(alkylamino)ethyldiazonium ion.The slopes of the log kobs versus pH plots are near -1.0.The solvent deuterium isotope effect, kH2O/kD2O, is in all cases methyl > ethyl.
A process for the production of high energy material
-
, (2008/06/13)
-
