Research ArticleOpen AccessGoogle Scholar indexed

Thermal Decomposition of Diphenyl Tetroxane in Chlorobenzene Solution

¹ Laboratorio de Investigación en Tecnología Ambiental, Facultad de Ciencias Exactas, Naturales y Agrimensura de la Universidad Nacional del Nordeste, Corrientes, Argentina
² Laboratorio de Investigación en Tecnología Ambiental, Facultad de Ciencias Exactas, Naturales y Agrimensura de la Universidad Nacional del Nordeste, Corrientes, Argentina
³ Laboratorio de Investigación en Tecnología Ambiental, Facultad de Ciencias Exactas, Naturales y Agrimensura de la Universidad Nacional del Nordeste, Corrientes, Argentina
⁴ Laboratorio de Investigación en Tecnología Ambiental, Facultad de Ciencias Exactas, Naturales y Agrimensura de la Universidad Nacional del Nordeste, Corrientes, Argentina
⁵ Laboratorio de Investigación en Tecnología Ambiental, Facultad de Ciencias Exactas, Naturales y Agrimensura de la Universidad Nacional del Nordeste, Corrientes, Argentina
⁶ Laboratorio de Investigación en Tecnología Ambiental, Facultad de Ciencias Exactas, Naturales y Agrimensura de la Universidad Nacional del Nordeste, Corrientes, Argentina
⁷ Laboratorio de Investigación en Tecnología Ambiental, Facultad de Ciencias Exactas, Naturales y Agrimensura de la Universidad Nacional del Nordeste, Corrientes, Argentina

International Journal of Organic Chemistry·Volume 09 (2019)·Pages 1–9·Published 11 January 2019·DOI10.4236/ijoc.2019.91001

Abstract

The thermal decomposition of Cyclic Diperoxide of Benzaldehyde 3,6-diphenyl-1,2,4,5-tetroxane, (DFT) in chlorobenzene solution in the studied temperature range (130 ° C - 166 ° C) satisfactorily satisfies a first order law up to 60% conversions of diperoxide. DFT would decompose through a mechanism in stages and initiated by the homolytic breakdown of one of the peroxidic bonds of the molecule, with the formation of the corresponding intermediate biradical. The concentration studied was very low, so that the effects of secondary reactions of decomposition induced by free radicals originated in the reaction medium can be considered minimal or negligible. The activation parameters for the unimolecular thermal decomposition reaction of the DFT are ΔH# = 30.52 ± 0.3 kcal · mol -1 and ΔS# = -6.38 ± 0.6 cal · mol -1 K -1 . The support for a step-by-step mechanism instead of a process concerted is made by comparison with the theoretically calculated activation energy for the thermal decomposition of 1,2,4,5-tetroxane.

KeywordsDFTThermal DecompositionChlorobenzeneMechanism

Jorge, N.L. and Castro, E.A. (2009) Structure and Properties. Trends in Organic Chemistry, 13, 65-74.
Smith, M.B. and March, J. (2007) March’s Advances Organic Chemistry. 6th Edition, Wiley & Sons, New Jersey.
Acuna, P. and Morales, G. (2011) Síntesis de poliestireno de alto impacto (hips) a partir de diferentes iniciadores multifuncionales: efecto de la estructura y del contenido de oxígeno activo del iniciador. Rev. Iberoam. Polim., 12, 160-168.
Dong, Y., McCulloug, K.J., Wittlin S., Chollet, J. and Vennerstrom J.L. (2010) The Structure and Antimalarial Activity of Dispiro-1,2,4,5-Tetraoxanes Derived from (+)-Dihydrocarvone. Bioorganic & Medicinal Chemistry Letters, 20, 6359-6361. https://doi.org/10.1016/j.bmcl.2010.09.113
Atheaya, H., Khan, S.I., Mamgaina, R. and Rawata, D.S. (2008) Synthesis, Thermal Stability, Antimalarial Activity of Symmetrically and Asymmetrically Substituted Tetraoxanes. Bioorganic & Medicinal Chemistry Letters, 18, 1446-1452. https://doi.org/10.1016/j.bmcl.2007.12.069
Creek, D.J., Ryan, E., Charman, W.N., Chiu, F.C., Prankerd, R.J., Vennerstrom, J.L. and Charman, S.A. (2009) Stability of Peroxide Antimalarials in the Presence of Human Hemoglobin. Antimicrobial Agents and Chemotherapy, 53, 3496-3500. https://doi.org/10.1128/AAC.00363-09
Oxley, J.C., Smith, J.L. and Chen, H. (2002) Decomposition of a Multiperoxidic Compound: Triacetone Triperoxide (TATP). Propellants, Explosives, Pyrotechnics, 27, 209-216. https://doi.org/10.1002/1521-4087(200209)27:4 3.0.CO;2-J
Leiva, L.C.A., Jorge, N.L., Romero, J.M., Cafferata, L.F.R., Gómez Vara, M.E. and Castro, E.A. (2008) Decomposition of the Acetone Cyclic Diperoxide in Octanol Solution. Journal of the Argentine Chemical Society, 96, 110-122.
Profeta, M.I., Romero, J.M., Leiva, L.C.A., Jorge, N.L., Gómez Vara, M.E. and Castro, E.A. (2011) Solvent Effect of Oxygen in the Thermolisys Decomposition of the Acetone Diperoxide. International Journal of Chemoinformatics and Chemical Engineering, 1, 96-102. https://doi.org/10.4018/ijcce.2011010107
Jorge, N.L., Romero, J.M., Grand, A. and Hernández-Laguna, A. (2012) Gas Phase Thermolysis Reaction of Formaldehyde Diperoxide. Kinetic Study and Theoretical Mechanisms. Chemical Physics, 39, 37-45. https://doi.org/10.1016/j.chemphys.2011.11.019
Jorge, N.L., Hernandez-Laguna, A. and Castro, E.A. (2013) Some Recent Developments on the Synthesis, Chemical Reactivity, and Theoretical Studies of Tetroxanes. International Journal of Chemoinformatics and Chemical Engineering, 3, 48-73. https://doi.org/10.4018/ijcce.2013010105

Menu

Thermal Decomposition of Diphenyl Tetroxane in Chlorobenzene Solution

Abstract

References (18)