Type of Document	Dissertation
Author	Angueira Batista, Ernesto Jose
Author's Email Address	e_angueira@hotmail.com
URN	etd-08122005-131639
Title	Novel Superacidic Ionic Liquid Catalysts for Arene Functionalization
Degree	Doctor of Philosophy
Department	Chemical Engineering
Advisory Committee	Advisor Name Title White, Mark G. Committee Chair Agrawal, Pradeep K. Committee Member Jones, Christopher W. Committee Member Ludovice, Peter J. Committee Member Sherrill, David Committee Member
Keywords	Equilibrium Thermodynamics Chloroaluminates Molecular Modeling 27Al NMR 13C NMR 1H NMR Arene Functionalization Ionic Liquids Superacidic Toluene Carbonylation
Date of Defense	2005-08-09
Availability	unrestricted
Abstract There is a continuing interest in the subject of arene carbonylation, especially in strong acids and environmentally-benign alternatives are sought to HF/BF3 and to AlCl3 as conversion agents. Ionic liquids offer a powerful solvent for useful conversion agents such as aluminum chloride. The IL’s permit AlCl3 to be used at lower HCl partial pressures than with other solvents. The superior reactivity demonstrated by acidic, chloroaluminate IL’s is probably due to their enhanced solvation power for HCl and CO. Addition of HCl gas increased reactivity of the system by forming Brønsted acids, and toluene carbonylation is a Brønsted demanding reaction. It was found that reaction is stoichiometric in Al species and only intrinsically acidic IL’s are active for toluene carbonylation, therefore it was possible to correlate observed conversion with predicted amounts of Lewis + Brønsted acids. Molecular modeling provided information about the different species present in these IL’s and predicted 1H NMR, and 27Al NMR spectrum. Predictions suggested that three types of HCl species are present; and these predictions were confirmed using data of 13C-labeled acetone and its 13C-NMR spectra. These data showed that only one of the three types of HCl in the IL were super acidic. Reactivity towards arene formylation can be tuned by adjusting the ligands R and R’ in the organic cation and by changing the anion. This reactivity tuning can be exploited in a process where high acidity is required for the conversion of substrate but where separation of product from IL is facilitated by low acidity.
Files	Filename       Size       Approximate Download Time (Hours:Minutes:Seconds)     28.8 Modem   56K Modem   ISDN (64 Kb)   ISDN (128 Kb)   Higher-speed Access    angueirabatista_ernesto_j_200512_phd.pdf 3.49 Mb 00:16:09 00:08:18 00:07:16 00:03:38 00:00:18