Abstract
A detailed computational study of the dehydrogenation reaction of trans-propylamine (trans-PA) in the gas phase has been performed using density functional method (DFT) and CBS-QB3 calculations. Different mechanistic pathways were studied for the reaction of n-propylamine. Both thermodynamic functions and activation parameters were calculated for all investigated pathways. Most of the dehydrogenation reaction mechanisms occur in a concerted step transition state as an exothermic process. The mechanisms for pathways A and B comprise two key-steps: H2 eliminated from PA leading to the formation of allylamine that undergoes an unimolecular dissociation in the second step of the mechanism. Among these pathways, the formation of ethyl cyanide and H2 is the most significant one (pathway B), both kinetically and thermodynamically, with an energy barrier of 416 kJ mol−1. The individual mechanisms for the pathways from C to N involve the dehydrogenation reaction of PA via hydrogen ion, ammonia ion and methyl cation. The formation of α-propylamine cation and NH3 (pathway E) is the most favorable reaction with an activation barrier of 1 kJ mol−1. This pathway has the lowest activation energy calculated of all proposed pathways.
Highlights
A detailed computational study of the dehydrogenation reaction of trans-propylamine in the gas phase has been performed using density functional method (DFT) and CBS-QB3 calculations
The potential energy diagram (PED) characterizes the energy of a molecular assembly and its value depends on the coordinates of all the atoms in the molecular system
It will be noted that α, β, and γ-carbons of propylamine with respect to the nitrogen atom are shown in certain pathways
Summary
A detailed computational study of the dehydrogenation reaction of trans-propylamine (trans-PA) in the gas phase has been performed using density functional method (DFT) and CBS-QB3 calculations. Propylamine is of significant importance in chemistry, as it constitutes a central structure block for aliphatic amines[1] It is widely utilized as a solvent in organic synthesis, and as a finishing agent for drugs, rubber, fiber, paints, pesticides, textile and r esin[2,3], and in the generation of fungicides[4,5,6]. Protonation (B + H+ → BH+) and deprotonation (dehydrogenation) (HA − H+ → A−) reactions assume a significant role in natural science and organic chemistry, where A and B are the acidic and the basic centers, respectively They are considered as the first step in several fundamental chemical mechanisms elucidated in the cited r eference[15].
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