Draft:Henry Joseph Shine

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Henry J Shine in 1980

Henry J Shine (Inorganic Chemist)

Born January 4,1923, London, England

Died June 25, 2024, Lubbock, Texas

Nationality UK/US

Alma mater University College London (B.Sc.), University of London (Ph.D.), Iowa State University (Post Doc.), California Institute of Technology (Post Doc.)

Doctoral advisor E. E. Turner

Other academic advisors Henry Gilman, Carl Niemann

Institutions Texas Tech University

Henry Shine was a British/American organic chemist. His principle research interests include rearrangement reactions, heavy atom kinetic isotope effects and organic cation radicals. He is most noted for his research with cation radicals and his discovery of the thianthrene cation radical¹.

Early life and education Henry Shine was born January 4, 1923 in London, England. He was the son of Nathan and Stella Shine, née Lucovicth. He attended Stepney Jewish Boys School from 1926 to 1934 before moving on to Mile End Central School and later the Lyulph Stanley Central School. Shine earned a B.Sc. 1st class honours at University College London in 1942 and a Ph.D. in organic chemistry from Bedford College, University of London in 1947.² He held post-doctoral fellowships at Iowa State College (1948), renamed Iowa State University in 1959 and the California Institute of Technology (1949).²

Career Shine began his post graduate career in chemistry as a research chemist for United States Rubber Company. In 1954 he joined the faculty of the Department of Chemistry at Texas Tech University as assistant professor. ³ He was promoted to Associate Professor in 1957, professor in 1960, designated Paul Whitfield Horn Professor in 1968 and was Chairman of the Department of Chemistry from 1969 to 1975 ². He remained at Texas Tech as Paul Whitfield Distinguished Horn Professor, Emeritus until his death in 2024. His research achievements while at Texas Tech are credited with “accelerating the process of Texas Tech’s transferring from a mainly teaching college to a tier-one research university”. ⁴

Research Shine’s earliest research focussed on the synthesis of pure hydrocarbons. This was done using Grignard reactions to make alcohols, non- isomerizing dehydrations, and subsequent hydrogenations.⁵ ⁶ In the preparation of alcohols, Shine experienced previously unknown complexities of Grignard reactions.⁷ ⁸ These reactions became the basis of his PhD dissertation. His quest to solve the Grignard mechanism took him to the United States, where he intended to work with the well-known organometallic chemist, Henry Gilman at Iowa State University.² Fortuitously, as it later turned out, Shine did not work with Gilman long. Instead, Shine spent time with George Hammond, a newly hired organic chemistry teacher. During this time, an undergraduate student asked Shine how the benzidine rearrangement took place. Neither Shine nor Hammond could answer this.⁹ ¹⁰ Hammond suggested that Shine attempt to measure the kinetic order in acid of the rearrangement of hydrazobenzene. This resulted in the discovery of second-order acid kinetics.¹¹ This discovery stimulated research into benzidine rearrangements by other laboratories, including two well-known groups (Ingold and Hughes and M. J. S. Dewar). Ingold and Hughes believed the rearrangements to be all concerted while Dewar thought them to be stepwise reactions involving p-complexes. This was resolved years later by Shine at Texas Tech where he showed that benzidine rearrangements, both acid-catalyzed and thermal, were sigmatropic, controlled by the dictates of orbital symmetry. ⁹ ¹² NH22b2+ aNHNHNH2H2NNH2H+, proving that some rearrangements are indeed concerted while other are not.

Shine’s success with heavy-atom kinetic isotope effects to the benzidine rearrangements led to their use in other rearrangements and reactions, such as the nitramine, photo-Wallach, photo-Fries, Smiles, quinamine, and Claisen rearrangements and the Diels-Alder reaction.² Ken G. Hancock of the National Science Foundation said of Shine’s benzidine rearrangement work: “It was “genuinely a benchmark study, a paradigm for the field, and a textbook case to pass along to a new generation of students. Very few chemists can claim such a splendid success in their careers.” ¹³

Shine’s interest in the rearrangement of hydrazobenzene led him to organosulfur and cation radical chemistry and subsequently to the thianthrene cation radical. When diphenyl disulfide dissolves in concentrated sulfuric acid (the acid used to promote the rearrangement), a deep purple solution forms. It took a number of years and the early use of epr spectroscopy for Shine to solve why this occurs. The purple colour was that of the thianthrene cation radical. In concentrated sulfuric acid, diphenyl disulfide is converted in part into thianthrene that is subsequently oxidized by the acid to its cation radical.² This was deduced by Shine in 1960, but required the use of epr spectroscopy, with Lawrence Piette, at Varian Associates in Palo Alto, California to prove it.¹⁴ Shine’s discovery of the thianthrene cation radical has been well documented. A chapter was devoted to it in G. R. Eaton’s Foundations of Modern epr, marking the 50th anniversary of the discovery of epr spectroscopy. ¹⁵

Much of Shine’s subsequent work involved epr spectroscopy to characterize new cation radicals of substituted thianthrenes. Shine continued researching reactions of thianthrene and studied other aromatic cation radicals, with a large variety of reactants. This work resulted in over 90 publications in ion radical and related chemistry.²

In total, Shine has over 220 publications ¹⁶ and authored the book Aromatic Rearrangements. ¹⁷

Representative publications¹⁶ ¹⁸

“The photo-Wallach rearrangement. Heavy-atom kinetic isotope effects and mechanism.” Shine, H., Subotkowski, W., Gruszecka, E. Canadian Journal of Chemisty. 64(6):1108-1115 · February 2011.

“Oxygen Transfer From Alcohols to the Thianthrene Cation Radical.” Shine, H. Phosphorus Sulfur and Silicon and the Related Elements 95(1):429-430 · May 2009.

"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.

“Benzidine rearrangements. 16. The use of heavy-atom kinetic isotope effects in solving the mechanism of the acid-catalyzed rearrangement of hydrazobenzene. The concerted pathway to benzidine and the nonconcerted pathway to diphenyline.” Shine, H., Zmuda, H., Ha Park, K., et al. Journal of the American Chemical Society, 104(9) May 1982.

“Cation radicals. 47. Reaction of perylene cation radical with fluoride ion and of perylene with xenon difluoride. Formation of 1-fluoro-, 3-fluoro-, and a difluoroperylene. Complications with chloride ion imp.” Stephenson, M., Shine, H. The Journal of Organic Chemistry, 46(15) · July 1981.

“Ion radicals. Reactions of thianthrene cation radical perchlorate with amino compounds.” Kim, K., Shine, H., The Journal of Organic chemistry, 39 (17) August 1974.

“The Mechanism of the Benzidine Rearrangement. I. The Effect of Acid Concentration on Rate.” Hammond, G., Shine, H. Journal of the American Chemical Society, 72(1) . January 1950. 

Personal life Shine married Sellie Shine (nee Schneider) in 1953. They have two children, Stephanie and Trevor Shine.

Awards, honours and grants²

Faculty Research Award (1982) ² Faculty Research Award (1982) ² Texas Tech Dads Association Distinguished Faculty Research Award (1983) ² Senior U.S. Scientist Award, Alexander von Humboldt Foundation (1986-1987) ² President’s Academic Achievement Award (1991) ² Texas Tech Dads Association Faculty Distinguished Leadership Award (1994) ² Shine is Included in the American Chemical Society list of famous organic Chemists ¹⁹ The annual Henry J. Shine Endowed Lectures series was created in 1999 ²⁰ Grants/funding Research Corporation and the Petroleum Research Fund The National Science Foundation The Air Force Office of Scientific Research Continuous research grant from the Robert A. Welch Foundation every year from 1955 to 2007 ² ²¹

References

¹ Kim, K., Shine, H., Ion radicals. XXX. Reactions of thianthrene cation radical perchlorate with amino compounds. The Journal of Organic chemistry, 39 (17) August 1974, DOI: 10.1021/jo00931a017

² Bartsch R.A., “Professor Henry J Shine, A Tribute” ARKIVOC Volume 2003 Part (xii) pp 1-214m Commemorative Issue in Honor of the 80th Anniversary of Prof. Henry J. Shine.

³ Shine H., An Early History of Chemistry at Texas Tech University, 1925-1975. Bulletin, History of Chemistry, V. 27, Number 2, (2002)

⁴ Rise and Shine, Texas Tech Today, Glenys Young, February 23 2023

⁵ Shine, H. J.; Turner, E. E., Five new tertiary carbinols and four new aliphatic hydrocarbons, Journal of the American Chemical Society, 1949, 71, 2589.

⁶ Shine, H. J.; Turner, E. E., The synthesis of 2:3:5-trimethylhexane and of 2:4:6trimethylheptane, Journal of the Institute of Petroleum, 1950, 36, 70.

⁷ Shine, H. J.; Turner, E. E., Grignard compounds as condensing agents, Nature ,1946, 158, 170.

⁸ Shine, H. J.; Turner, E. E., The anomalous reactions of Grignard reagents, Journal of the Institute of Petroleum, 1950, 36, 73

⁹ Shine, H. J., A Personal History of the Benzidine Rearrangement, Bulletin for the History of Chemistry, 1996, 19, 77.

¹⁰ Shine, H. J., Reflections on the ?-complex theory of benzidine rearrangements, Journal of Physical Organic Chemistry, 1989, 2, 491.

¹¹ G. S.; Shine, H. J., The Mechanism of the Benzidine Rearrangement, Hammond, Journal of the American Chemical Society, 1950, 72, 1950.

¹² Shine, H. J.; Zmuda, H.; Park, K. H.; Kwart, H.; Horgan, A. G.; Collins, C.; Maxwell, B. E., Mechanism of the benzidine rearrangement. Kinetic isotope effects and transition states. Evidence for concerted rearrangement, Journal of the American Chemical Society, 1981, 103, 955.

¹³ A Chemist’s Holy Grail, Texas Tech Research, Michael Sommermeyer, PP 9 – 14, Summer 1993, ISSN 1055-9159

¹⁴ Shine, H. J.; Piette, L., Ion-radicals. The Reaction of Thioaromatic Compounds with Acids. II. Diphenyl Disulfide, Thianthrene and Thianthrene Oxides, J. Am. Chem. Soc. 1962, 84, 4798.

¹⁵ Shine, H. J., Foundations of Modern EPR, Eaton, G. R.; Eaton, S. S.; Salikov, K. M., Eds., World Scientific Publishing Co., Singapore, 1997, pp 202-212

¹⁶ ResearchGate 2019, https://www.researchgate.net/profile/Henry_Shine/2 ¹⁷ Henry J Shine, Aromatic Rearrangements, 66-25767, Elsevier Publishing Company, 1967, 405 pages

¹⁸ Texas Tech University Department of Chemistry and Biochemistry faculty profile: Dr. Henry J. Shine. https://www.depts.ttu.edu/chemistry/Faculty/shine

¹⁹ American Chemical Society, Division of Organic Chemistry, “Famous Organic Chemists”. https://www.organicdivision.org/famous-organic-chemists/#S

²⁰ Dr. Henry J. Shine: An Inventory of His Papers, 1944-2009 and undated, at the Southwest Collection/Special Collections Library, Biographical Sketch (https://legacy.lib.utexas.edu/taro/ttusw/00388/tsw-00388.html

²¹ The Welch Foundation, 5555 San Felipe, Suite 1900, Houston, Texas, 77056