Pyrolytic elimination of ethylene from ethoxyquinolines and ethoxyisoquinolines: A computational study

TL;DR

This computational study investigates the thermodynamics and kinetics of ethylene elimination from various ethoxyquinolines and ethoxyisoquinolines, revealing favored keto formation pathways and pressure-dependent rate increases.

Contribution

The paper provides detailed computational analysis of decomposition pathways, transition states, and rate constants for ethylene elimination in ethoxyquinolines and isoquinolines, using advanced quantum chemical methods.

Findings

Keto formation pathway has lower energy transition state.

Ethylene elimination is kinetically and thermodynamically favored.

Rate constants increase with pressure up to 1 bar.

Abstract

This work reports thermodynamics and kinetics of unimolecular thermal decomposition of some ethoxyquinolines and ethoxyisoquinolines (1-ethoxyisoquinoline (1-EisoQ), 2- ethoxyquinoline (2-EQ), 3-ethoxyquinoline (3-EQ), 3-ethoxyisoquinoline (3-EisoQ), 4- ethoxyquinoline (4-EQ), 4-ethoxyisoquinoline (4-EisoQ), 5-ethoxyquinoline (5-EQ), 5- ethoxyisoquinoline (5-EisoQ), 8-ethoxyquinoline (8-EQ) and 8-ethoxyisoquinoline (8-EisoQ) using density functional theory (BMK, MPW1B95, M06-2X/cc-pvtz) and ab initio (CBS-QB3) calculations. In the course of the decomposition of the investigated systems, ethylene is eliminated with the production of either keto or enol tautomer. The six-membered transition state structure encountered in the path of keto formation is much lower in energy than the fourmembered transition state required to give enol form. Rate constants and activation energies for the decomposition of 1-EisoQ, 2-EQ, 3-EQ, 3-EisoQ, 4-EQ, 4-EisoQ, 5-EQ, 5-EisoQ, 8- EQ, and 8-EisoQ have been estimated at different temperatures and pressures using conventional transition state theory combined with Eckart tunneling (TST/Eck) and the statistical Rice-Ramsperger-Kassel-Marcus (RRKM) theories. The tunneling correction is significant at temperatures up to 1000 K. Rate constants results reveal that ethylene elimination with keto production is favored kinetically and thermodynamically over the whole temperature range of 400-1200 K and the rates of the processes under study increase with the rising of pressure up to 1 bar.