Unrestricted.2016-11-142011-08-052016-11-142011-08http://hdl.handle.net/2346/ETD-TTU-2011-08-1689A computational study of the thermal deazetization of exo-5,6-dideuterio-2,3-diazabicyclo[2.2.1]hept-2-ene has been carried out, aiming to explain the formation of the products after the nitrogen loss. The transition state with the lowest energy suggests a concerted breaking of the C-N bonds leading over a flat diradical to the endo and exo products. Higher in energy by only 0.5 kcal/mol another transition state represents a possible exit channel, via a 1,2-hydrogen shift, to the observed syn-3,4-dideuteriocyclopentene. Only at increased temperature of reaction 1,5-dideuterio-1,4-pentadiene starts forming, a fact computationally justified by a transition state 7 kcal/mol more energetic than any of the other ones. The development of the second-generation renewable fuels from vegetable oils by chemical methods that minimize the use of toxic reagents and the formation of wasteful byproducts has been optimized. Castor and safflower oil were chosen because they are non-food crops and can be grown on marginal lands. Two possibilities were explored: base and acid-catalyzed transesterification of triglycerides. The base-catalyzed transesterification has been proven to be a remarkably efficient process. The acid-catalyzed transesterification converts the triglycerides into their esters and also converts free fatty acids pre-existing in oils, eliminating the formation of soap as by-product. Catalyzed transesterification of safflower and castor oil in the presence of guanidine and guanidine derivatives has been studied. High yields and a very good reaction timeframe have been observed for some of the guanidine catalysts. A computational investigation of the possible structures involved in the reaction’s mechanism identifies acylguanidine as a pivotal intermediate and, explains, in good correlation with the experimental results, the differences of reactivity for the catalysts used.application/pdfengexo-5,6-dideuterio-2,3-diazabicyclo[2.2.1]hept-2-eneComputational studyBiodieselSafflower oilCastor oilDissertation