ABSTRACT
The mechanism of aryl propargyl ether Claisen rearrangement in gas and solvent phase was investigated using DFT methods. Solvent phase calculations are carried out using N,N-diethylaniline as a solvent in the PCM model. The most favorable pathways involve a [3,3]-sigmatropic reaction followed by proton transfer in the first two steps and then deprotonation or [1,5]-sigmatropic reaction. Finally, cyclization yields benzopyran or benzofuran derivatives. The [3,3]-sigmatropic reaction is the rate-determining step for benzopyran and benzofuran with ΔG() value of 38.4 and 37.9 kcal mol(-1) at M06/6-31+G**//B3LYP/6-31+G* level in gas and solvent phase, respectively. The computed results are in good agreement with the experimental results. Moreover, it is found that the derivatives of aryl propargyl ether proceeded Claisen rearrangement and the rate-determining step may be shifted from the [3,3]-sigmatropic reaction to the tautomerization step. The NBO analysis revealed that substitution of the methyl groups on the aliphatic segment has decreased the stabilization energy E(2) and favors the aryl propargyl ether Claisen rearrangement.
ABSTRACT
A facile route has been developed to enhance compatibility between organic polyimide matrix and dispersed phase of inorganic silica particles without addition of conventional silane-coupling agent. The as-prepared hybrid sol-gel materials having reduced size of SiO2 particle dispersed in polyimide matrix were successfully synthesized through pre-catalyzed sol-gel route using an organic diamine base. The PI-silica hybrid materials through conventional polyamic acid-catalyzed sol-gel route with/without silane-coupling agent were also prepared for comparative control studies. Morphological feature of as-prepared sol-gel materials prepared from three different approaches was also compared based on the studies of transmission electron microscopy. Effects of the material composition, in three different catalyzed routes, were investigated by thermal stability, mechanical strength, optical clarity, gas barrier and water absorption measurements of polyimide and a series of polyimide-silica hybrid sol-gel materials, respectively.
