Some Recent Developments on the Synthesis, Chemical Reactivity, and Theoretical Studies of Tetroxanes

The authors present a review on some recent developments on the synthesis, chemical reactivity and theoretical studies of Tetroxanes analysing their main physical chemistry properties. The authors examine the critical points of the PES of different conformers, and reaction paths at singlet ground state and triplet state of the tetroxane, leader member of the cyclic diperoxide compound family. DOI: 10.4018/ijcce.2013010105 International Journal of Chemoinformatics and Chemical Engineering, 3(1), 48-73, January-June 2013 49 Copyright © 2013, IGI Global. Copying or distributing in print or electronic forms without written permission of IGI Global is prohibited. important since they take part in transformations associated with cellular decaying, produced by enzymatic self-oxidations due to some peroxidic species. Several reaction of the decomposition (Cafferatta et al., 1984, 1986, 1990, 1991, 1995; Jorge et al., 2000, 2002; Eyler et al., 1993, 1999, 2000, 2002), thermochemical (Eyler et al., 1999; Murray et al., 1966; Wulz et al., 1970) and quantum-chemical (Jorge et al., 1994, 1999, 2000, 2001, 2002, 2002; Leiva et al., 1998, 2001; Castellanos et al., 2000; Diez & Jubert, 2000) data sets for 1,2,4-trioxanes and 1,2,4,5-tetroxanes are available. Solvent effects on the inversion barrier of 3,3,6,6,-tetramethyl1,2,4,5-tetroxane (or dimeric acetone peroxide) have been studied (Brune et al., 1971) and a conformational analysis in the liquid phase suggested that the chair conformer is more stable than the twist form (Murray et al., 1966). Although dimeric acetone peroxide has been known for more than 100 years, the crystal structure has been reported for Gelancha et al. in 2004. Groth (1967a, 1967b) reported structures of several dimeric peroxides, but dimeric acetone diperoxide was left undetermined because of a twinning problem. The aim of the present review work was to provide a complete analysis of the family of 1,2,4,5-tetroxanes, in order to report the findings obtained from experimental reactivity, physicochemical properties and those derived from studies of chemistry quantum calculations.