A Definitive Study of Aliphatic and Aromatic ß-ketosulfoxides: Promising Aromatic Chelates

Erwin Boschmann; Raymond Nevin Keller

doi:doi:10.11648/j.sjc.20210901.11

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A Definitive Study of Aliphatic and Aromatic ß-ketosulfoxides: Promising Aromatic Chelates

Erwin Boschmann, Raymond Nevin Keller

Published in Science Journal of Chemistry (Volume 9, Issue 1)

Received: 15 December 2020 Accepted: 31 December 2020 Published: 15 January 2021

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Abstract

This paper begins with a detailed description of the conditions necessary for the formation of chelates in general, and ß-ketosulfoxides in particular. While symmetric chelates such as 2,4-pentanedione have been known and studied for a long time, asymmetric chelate structures, such as the aliphatic ω-(methylsulfinyl)-acetophenone, Ph-CO-CH₂-SO-CH₃, for example, have not been investigated. Our detailed studies of solubility, acidity, IR, UV, and NMR spectroscopies all indicate very low enolization and hence low chelation, if any. Nevertheless, using rather strong conditions – such as molten reagents – we experienced some evidence for reaction. We extended our studies to aromatic ketosulfoxides by fusing these into benzene, assuming that its resonating ring will not only withdraw electrons from the S=O group, but might also encourage conjugation. We focused on o-(methylsulfoxo)-acetophenone with its S=O group in one position on the benzene ring and the –OH group in an adjacent position. Three separate facts confirmed our belief that such a fused structure should undergo enolization and thus chelation. First, salicylaldehyde and 2-hydroxyacetophenone, both structurally analogous to the compound of interest o-(methylsulfoxo)-acetophenone, do show strong chelation; second, approximate linear combination of atomic orbitals-molecular orbital (LCAO-MO) calculations point to positive results; and third, a comparison of the acidity constants of six acids ranging from ω-(methylsulfinyl)-acetophenone (3 x 10^-11) to salicylic acid (1.06 x 10^-3) place the compound in question, o-(methylsulfoxo)-acetophenone, at the upper end of acidity. Indeed, metal derivatives of o-(methylsulfoxo)-acetophenone form rather easily as evidenced by O-H and S=O shifts in IR, UV, and NMR spectroscopies. Calcium forms a chelate, whereas iron and niobium form adducts.

Published in	Science Journal of Chemistry (Volume 9, Issue 1)
DOI	10.11648/j.sjc.20210901.11
Page(s)	1-8
Creative Commons	This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.
Copyright	Copyright © The Author(s), 2024. Published by Science Publishing Group

Keywords

Asymmetric Chelates, Aliphatic ß-ketosulfoxides, Aromatic ß-ketosulfoxides, Chelates, ß-ketosulfoxides

References

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[3]	G. H. Posner, in The Chemistry of Sulphones and Sulphoxides; S. Patai, Z. Rappoport, C. J. M. Stirling, Eds,; Wiley: New York, 1988, chapter 16, pages 824-849.
[4]	K. Griesbaum, A. A. Oswald, B. E. Hudson, Jr., J. Am. Chem. Soc. 85 (1963) 1972.
[5]	H. F. Walton, Principles and Methods of Chemical Analysis, 2^nd ed. Prentice-Hall, Inc., Englewood Cliffs, 1964, pages 176 and 383.
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[10]	E. J. Corey, M. Chaykovsky, J. Am. Chem. Soc. 84 (1962) 866.
[11]	H. H. Jaffe, M. Orchin, Theory and Application of Ultraviolet Spectroscopy, John Wiley and Sons, New York, 1962, page 491.
[12]	J. R. Dyer, Applications of Absorption Spectroscopy of Organic Compounds, Prentice-Hall, Englewood Cliffs, (1965), pages 11, 89.
[13]	A. O. Pedersen, G. Schroll, S. O. Lawesson, Tetrahedron 26 (1970) 4449-4471.
[14]	S. A. Abdel-Latif, H. B. Hassib, Y. M. Issa, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy Volume 67, Issues 3–4, July (2007), Pages 950-957.
[15]	L. J. Bellamy, The Infrared Spectra of Complex Molecules, Methuen and Co.., Ltd., London, 1958, chapters 9 and 22.
[16]	H. G. Korth, M. I. de Heer, P. Mulder, J. Phys. Chem. A, 106 (2002) 8779-8789.
[17]	M. C. Carreño, J. L. G. Ruano, A. M. Martin, C. Pedregal, J. H. Rodriguez, A. Rubio, J. Snachez, G. Solladie J. Org. Chem. 55 (1990) 2120-2128.
[18]	Zheng-Zheng Li, A-Hao Wen, Su-Yang Yao, Bao-Hui Ye, Inorg. Chem. 54 (2015), 2726-2733.
[19]	Su-Yang Yao, Xing-Yang Chen, Yan-Ling Ou, Bao-Hui Ye, Inorg. Chem. 56 (2017) 878-885.
[20]	Abstracted in part from a thesis submitted by Erwin Boschmann to the Graduate School of the University of Colorado in partial fulfillment for the degree of Doctor of Philosophy, Department of Chemistry, 1968; and Presented in part before the 3^rd Central Regional American Chemical Society Meeting, June 6-8, 1971, Cincinnati, Ohio. A few preliminary results were published in R. N. Keller and Erwin Boschmann, Bol. Soc. Quim. 1968, 34, 107; and Erwin Boschmann, J. Inorg. Nucl. Chem. 1973, 35, 1025 (1973).

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APA Style

Erwin Boschmann, Raymond Nevin Keller. (2021). A Definitive Study of Aliphatic and Aromatic ß-ketosulfoxides: Promising Aromatic Chelates. Science Journal of Chemistry, 9(1), 1-8. https://doi.org/10.11648/j.sjc.20210901.11

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ACS Style

Erwin Boschmann; Raymond Nevin Keller. A Definitive Study of Aliphatic and Aromatic ß-ketosulfoxides: Promising Aromatic Chelates. Sci. J. Chem. 2021, 9(1), 1-8. doi: 10.11648/j.sjc.20210901.11

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AMA Style

Erwin Boschmann, Raymond Nevin Keller. A Definitive Study of Aliphatic and Aromatic ß-ketosulfoxides: Promising Aromatic Chelates. Sci J Chem. 2021;9(1):1-8. doi: 10.11648/j.sjc.20210901.11

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@article{10.11648/j.sjc.20210901.11,
  author = {Erwin Boschmann and Raymond Nevin Keller},
  title = {A Definitive Study of Aliphatic and Aromatic ß-ketosulfoxides: Promising Aromatic Chelates},
  journal = {Science Journal of Chemistry},
  volume = {9},
  number = {1},
  pages = {1-8},
  doi = {10.11648/j.sjc.20210901.11},
  url = {https://doi.org/10.11648/j.sjc.20210901.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.sjc.20210901.11},
  abstract = {This paper begins with a detailed description of the conditions necessary for the formation of chelates in general, and ß-ketosulfoxides in particular. While symmetric chelates such as 2,4-pentanedione have been known and studied for a long time, asymmetric chelate structures, such as the aliphatic ω-(methylsulfinyl)-acetophenone, Ph-CO-CH2-SO-CH3, for example, have not been investigated. Our detailed studies of solubility, acidity, IR, UV, and NMR spectroscopies all indicate very low enolization and hence low chelation, if any. Nevertheless, using rather strong conditions – such as molten reagents – we experienced some evidence for reaction. We extended our studies to aromatic ketosulfoxides by fusing these into benzene, assuming that its resonating ring will not only withdraw electrons from the S=O group, but might also encourage conjugation. We focused on o-(methylsulfoxo)-acetophenone with its S=O group in one position on the benzene ring and the –OH group in an adjacent position. Three separate facts confirmed our belief that such a fused structure should undergo enolization and thus chelation. First, salicylaldehyde and 2-hydroxyacetophenone, both structurally analogous to the compound of interest o-(methylsulfoxo)-acetophenone, do show strong chelation; second, approximate linear combination of atomic orbitals-molecular orbital (LCAO-MO) calculations point to positive results; and third, a comparison of the acidity constants of six acids ranging from ω-(methylsulfinyl)-acetophenone (3 x 10-11) to salicylic acid (1.06 x 10-3) place the compound in question, o-(methylsulfoxo)-acetophenone, at the upper end of acidity. Indeed, metal derivatives of o-(methylsulfoxo)-acetophenone form rather easily as evidenced by O-H and S=O shifts in IR, UV, and NMR spectroscopies. Calcium forms a chelate, whereas iron and niobium form adducts.},
 year = {2021}
}

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TY  - JOUR
T1  - A Definitive Study of Aliphatic and Aromatic ß-ketosulfoxides: Promising Aromatic Chelates
AU  - Erwin Boschmann
AU  - Raymond Nevin Keller
Y1  - 2021/01/15
PY  - 2021
N1  - https://doi.org/10.11648/j.sjc.20210901.11
DO  - 10.11648/j.sjc.20210901.11
T2  - Science Journal of Chemistry
JF  - Science Journal of Chemistry
JO  - Science Journal of Chemistry
SP  - 1
EP  - 8
PB  - Science Publishing Group
SN  - 2330-099X
UR  - https://doi.org/10.11648/j.sjc.20210901.11
AB  - This paper begins with a detailed description of the conditions necessary for the formation of chelates in general, and ß-ketosulfoxides in particular. While symmetric chelates such as 2,4-pentanedione have been known and studied for a long time, asymmetric chelate structures, such as the aliphatic ω-(methylsulfinyl)-acetophenone, Ph-CO-CH2-SO-CH3, for example, have not been investigated. Our detailed studies of solubility, acidity, IR, UV, and NMR spectroscopies all indicate very low enolization and hence low chelation, if any. Nevertheless, using rather strong conditions – such as molten reagents – we experienced some evidence for reaction. We extended our studies to aromatic ketosulfoxides by fusing these into benzene, assuming that its resonating ring will not only withdraw electrons from the S=O group, but might also encourage conjugation. We focused on o-(methylsulfoxo)-acetophenone with its S=O group in one position on the benzene ring and the –OH group in an adjacent position. Three separate facts confirmed our belief that such a fused structure should undergo enolization and thus chelation. First, salicylaldehyde and 2-hydroxyacetophenone, both structurally analogous to the compound of interest o-(methylsulfoxo)-acetophenone, do show strong chelation; second, approximate linear combination of atomic orbitals-molecular orbital (LCAO-MO) calculations point to positive results; and third, a comparison of the acidity constants of six acids ranging from ω-(methylsulfinyl)-acetophenone (3 x 10-11) to salicylic acid (1.06 x 10-3) place the compound in question, o-(methylsulfoxo)-acetophenone, at the upper end of acidity. Indeed, metal derivatives of o-(methylsulfoxo)-acetophenone form rather easily as evidenced by O-H and S=O shifts in IR, UV, and NMR spectroscopies. Calcium forms a chelate, whereas iron and niobium form adducts.
VL  - 9
IS  - 1
ER  -

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Author Information

Erwin Boschmann

Department of Chemistry and Chemical Biology, Indiana University Purdue University Indianapolis, Indianapolis, Indiana, United States
Raymond Nevin Keller

Department of Chemistry, University of Colorado, Boulder, Colorado, United States

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Erwin Boschmann, Raymond Nevin Keller. (2021). A Definitive Study of Aliphatic and Aromatic ß-ketosulfoxides: Promising Aromatic Chelates. Science Journal of Chemistry, 9(1), 1-8. https://doi.org/10.11648/j.sjc.20210901.11

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ACS Style

Erwin Boschmann; Raymond Nevin Keller. A Definitive Study of Aliphatic and Aromatic ß-ketosulfoxides: Promising Aromatic Chelates. Sci. J. Chem. 2021, 9(1), 1-8. doi: 10.11648/j.sjc.20210901.11

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AMA Style

Erwin Boschmann, Raymond Nevin Keller. A Definitive Study of Aliphatic and Aromatic ß-ketosulfoxides: Promising Aromatic Chelates. Sci J Chem. 2021;9(1):1-8. doi: 10.11648/j.sjc.20210901.11

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@article{10.11648/j.sjc.20210901.11,
  author = {Erwin Boschmann and Raymond Nevin Keller},
  title = {A Definitive Study of Aliphatic and Aromatic ß-ketosulfoxides: Promising Aromatic Chelates},
  journal = {Science Journal of Chemistry},
  volume = {9},
  number = {1},
  pages = {1-8},
  doi = {10.11648/j.sjc.20210901.11},
  url = {https://doi.org/10.11648/j.sjc.20210901.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.sjc.20210901.11},
  abstract = {This paper begins with a detailed description of the conditions necessary for the formation of chelates in general, and ß-ketosulfoxides in particular. While symmetric chelates such as 2,4-pentanedione have been known and studied for a long time, asymmetric chelate structures, such as the aliphatic ω-(methylsulfinyl)-acetophenone, Ph-CO-CH2-SO-CH3, for example, have not been investigated. Our detailed studies of solubility, acidity, IR, UV, and NMR spectroscopies all indicate very low enolization and hence low chelation, if any. Nevertheless, using rather strong conditions – such as molten reagents – we experienced some evidence for reaction. We extended our studies to aromatic ketosulfoxides by fusing these into benzene, assuming that its resonating ring will not only withdraw electrons from the S=O group, but might also encourage conjugation. We focused on o-(methylsulfoxo)-acetophenone with its S=O group in one position on the benzene ring and the –OH group in an adjacent position. Three separate facts confirmed our belief that such a fused structure should undergo enolization and thus chelation. First, salicylaldehyde and 2-hydroxyacetophenone, both structurally analogous to the compound of interest o-(methylsulfoxo)-acetophenone, do show strong chelation; second, approximate linear combination of atomic orbitals-molecular orbital (LCAO-MO) calculations point to positive results; and third, a comparison of the acidity constants of six acids ranging from ω-(methylsulfinyl)-acetophenone (3 x 10-11) to salicylic acid (1.06 x 10-3) place the compound in question, o-(methylsulfoxo)-acetophenone, at the upper end of acidity. Indeed, metal derivatives of o-(methylsulfoxo)-acetophenone form rather easily as evidenced by O-H and S=O shifts in IR, UV, and NMR spectroscopies. Calcium forms a chelate, whereas iron and niobium form adducts.},
 year = {2021}
}

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TY  - JOUR
T1  - A Definitive Study of Aliphatic and Aromatic ß-ketosulfoxides: Promising Aromatic Chelates
AU  - Erwin Boschmann
AU  - Raymond Nevin Keller
Y1  - 2021/01/15
PY  - 2021
N1  - https://doi.org/10.11648/j.sjc.20210901.11
DO  - 10.11648/j.sjc.20210901.11
T2  - Science Journal of Chemistry
JF  - Science Journal of Chemistry
JO  - Science Journal of Chemistry
SP  - 1
EP  - 8
PB  - Science Publishing Group
SN  - 2330-099X
UR  - https://doi.org/10.11648/j.sjc.20210901.11
AB  - This paper begins with a detailed description of the conditions necessary for the formation of chelates in general, and ß-ketosulfoxides in particular. While symmetric chelates such as 2,4-pentanedione have been known and studied for a long time, asymmetric chelate structures, such as the aliphatic ω-(methylsulfinyl)-acetophenone, Ph-CO-CH2-SO-CH3, for example, have not been investigated. Our detailed studies of solubility, acidity, IR, UV, and NMR spectroscopies all indicate very low enolization and hence low chelation, if any. Nevertheless, using rather strong conditions – such as molten reagents – we experienced some evidence for reaction. We extended our studies to aromatic ketosulfoxides by fusing these into benzene, assuming that its resonating ring will not only withdraw electrons from the S=O group, but might also encourage conjugation. We focused on o-(methylsulfoxo)-acetophenone with its S=O group in one position on the benzene ring and the –OH group in an adjacent position. Three separate facts confirmed our belief that such a fused structure should undergo enolization and thus chelation. First, salicylaldehyde and 2-hydroxyacetophenone, both structurally analogous to the compound of interest o-(methylsulfoxo)-acetophenone, do show strong chelation; second, approximate linear combination of atomic orbitals-molecular orbital (LCAO-MO) calculations point to positive results; and third, a comparison of the acidity constants of six acids ranging from ω-(methylsulfinyl)-acetophenone (3 x 10-11) to salicylic acid (1.06 x 10-3) place the compound in question, o-(methylsulfoxo)-acetophenone, at the upper end of acidity. Indeed, metal derivatives of o-(methylsulfoxo)-acetophenone form rather easily as evidenced by O-H and S=O shifts in IR, UV, and NMR spectroscopies. Calcium forms a chelate, whereas iron and niobium form adducts.
VL  - 9
IS  - 1
ER  -

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