Dr. Henry J. Shine

Principal Research Interests

• Physical organic chemistry
• Rearrangement reactions
• Heavy atom kinetic isotope effects
• Organic cation radicals

Professor Shine's research is now concentrated on the chemistry of organic cation radicals. In this area the research group at Texas Tech University has done and is doing pioneering exploration.

In recent years, cation radical research has been concentrated on two areas. In the first, additions of thianthrene cation radical salts to cycloalkenes and alkenes have been found to give bis- and monoaddducts. In each class of adduct, addition is stereospecific, the geometry of the alkene being retained. The conversion of bis- into monoadducts, also with retention of alkyl chain configuration, has been studied. The second area is the reactions of 5-X-thianthrenium salts (X = alkyl, cycloalkyl, alkyloxy, and aryl groups) with nucleophiles such as halide and thiolate ions. Here, a range of reactions occurs, comprising SN2 substitution, E2C elimination, and ligand coupling (LC) within sulfurane intermediates. Currently, attempts are under way to distinguish between SN2 and LC when chosen 5-alkylthianthrenium salts are used.

Representative Publications

• "Ring-opening Reactions of 5-(aryl)thianthrenium Bromides with Aryl thiolates." Qian, D.Q.; Liu, B.; Shine, H.J.;  Guzman-Jimenez, I.Y.; Whitmire, K.H.  J. Phys. Org. Chem. 2002, 15, 139.
• "Reactions of 5-(Alkyl)thianthrenium and Other Sulfonium Salts with Nucleophiles." Liu, B.;  Shine, H.J.;  J. Phys. Org. Chem. 2001, 14, 81.
• "Addition of Thianthrene Cation Radical to Cycloalkenes. An Unexpected Monoadduct" Lee,  W. K.; Liu, B.; Park, C.W.; Shine, H.J.; Guzman-Jimenez, I.Y.;  Whitmire, K.H. J. Org. Chem. 1999, 64, 9206.
• "Reactions of Nucleophiles with 5-(Alkoxy)thianthrenium Ions." Liu, B.; Shine, H.J.; Zhao, W.  J. Phys. Org. Chem.1999, 12, 827.
• "Primary and Secondary 5-(Alkoxy)Perchlorates. characterization with 1H NMR Spectroscopy, Reactions with Iodide and Bromide Ions, and Thermal Decomposition." Zhao, W.; Shine, H. J.  Can. J. Chem. 1998, 76, 695.
• "Structure and Thermal Decomposition of Some 5-(Cyclohexyloxy)thianthrenium Perchlorates." Zhao, W.; Shine, H.J.;  Whittlesey, B. R. J. Org. Chem. 1997, 62, 8693.
• "The History of the Thianthrene Cation Radical." Shine, H. J. In Foundations of Modern EPR; Eaton, G. R.; Eaton, S. S.; Salikov, K. M., Eds.; World Scientific Publishers, 1997, Chap 2, 202-210.