Abstract
Thiophene S-oxides have been prepared and their photoreactivity has been studied. In many cases, the sulfur moiety of the thiophene S-oxides is deoxygenated. Here, the corresponding thiophenes or hydroxylated thiophenes are isolated. In the case of the photoirradiation of tert-butyl substituted thiophene S-oxides, the oxygen of the sulfoxy unit is incorporated into the heterocyclic ring system and the corresponding furans have been isolated. Also, structures with two thiophene cores have been oxidized to the respective thiophene S-oxides. These molecules undergo photodeoxygenation, a reaction, which is catalysed by (non-oxidized) thiophenes.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Y. Q. Li, M. Matsuda, T. Thiemann, T. Sawada, S. Mataka and M. Tashiro, Lewis Acid-Catalysed Oxidative Cycloaddition of Thiophenes, Synlett, 1996, 461–464.
Y. Q. Li, T. Thiemann, T. Sawada, S. Mataka and M. Tashiro, Lewis Acid Catalysis in the Oxidative Cycloaddition of Thiophenes, J. Org. Chem., 1997, 62, 7926–7936.
T. Thiemann, in Collaboration with the National Cancer Institute, Bethesda, MD, USA., as part of its Developmental Therapeutics Program.
Y. Q. Li, T. Thiemann, K. Mimura, T. Sawada, S. Mataka and M. Tashiro, Oxidative Cycloaddition of Thiophenophanes-[ n](2.5)Parathiophenophane (n = 8,10–12,14), [8](2,4)Metathiophenophane and [2.2](2,5)Parametathiophenophane, Eur. J. Org. Chem., 1998, 1841–1850.
T. Thiemann, D. Ohira, K. Arima, T. Sawada, S. Mataka, F. Marken, R. G. Compton, S. D. Bull and S. G. Davies, Photochemical and Electrochemical Behaviour of Thiophene S-oxides, J. Phys. Org. Chem., 2000, 13, 648–653.
K. Tanaka, S. Wang and T. Yamabe, Polythiophene. Design of Narrow-band-gap Polymers, Synth. Metals, 1989, 30, 57.
M. C. Suh, B. Jiang and T. D. Tilley, An Efficient, Modular Synthetic Route to Oligomers based on Zirconocene Coupling: Properties for Phenylene-Thiophene 1-oxide and Phenylene-Thiophene-1,1,-dioxide Chains, Angew. Chem., Int. Ed., 2000, 39, 2870–2873.
K. Arima, S. Mataka and T. Thiemann, Synthesis by Oxidation of Thiophene S-oxide Dimers and Evaluation of their Stability, Synth. Met., submitted.
D. Ohira, Synthesis and Reactivity of Thiophene S-oxides, MSc Thesis, Kyushu University, March 2000.
T. Thiemann, New Developments in the Chemistry of Thiophene S-oxides, Kyushu Daigaku Chuo Bunseki Senta Hokoku, 2000, 18, 1–7
T. Thiemann, Chem. Abstr., 2001, 134, 326045j.
K. Arima, The Chemistry of Thiophene-, Benzothiophene-, and Dibenzothiophene S-oxides MSc Thesis, Kyushu University, March 2001.
Z. Wan and W. S. Jenks, Oxenoid Reactivity observed on the Photolysis of certain Aromatic Sulfoxides, J. Am. Chem. Soc., 1995, 117, 2667–2668.
D. D. Gregory, Z. Wan and W. S. Jenks, Photodeoxygenation of Dibenzothiophene Sulfoxide: Evidence for a Unimolecular S–O Cleavage Mechanism, J. Am. Chem. Soc., 1997, 119, 94–102.
E. Lucien and A. Greer, Electrophilic Oxidant Produced in the Photodeoxygenation of 1,2-Benzodiphenylene Sulfoxide, J. Org. Chem., 2001, 66, 4576–4579.
G. M. Gurria and G. H. Posner, Photochemical Deoxygenation of Aryl Sulfoxides, J. Org. Chem., 1973, 38, 2419–2420.
T. Thiemann, K. Kumazoe, K. Arima, S. Mataka, Studies towards Dibenzothiophene S-oxide Arrays and their Photochemical Reactivity, ECSOC 5, 2001 http://www.mdpi.net/ecsoc-5/a0050/a0050.htm.
K. Kumazoe, K. Arima, S. Mataka, D. Walton and T. Thiemann, Photochemistry of substituted dibenzothiophene S-oxides and oxygenated bis-dibenzothiophenes, J. Chem. Res. (S), 2003, 60–61
K. Kumazoe, K. Arima, S. Mataka, D. Walton and T. Thiemann, J. Chem. Res. (M), 2003, 248–263.
T. Umezawa, T. Matsui, Y. Sugihara, A. Ishii and J. Nakayama, Thermolysis of Selenophene 1,1-dioxides, Heterocycles, 1998, 48, 61–69.
H. Nagasawa, Y. Sugihara, A. Ishii and J. Nakayama, Thiophene 1,1-dioxide: Synthesis, Isolation and Properties, Bull. Chem. Soc. Jpn., 1999, 72, 1919–1926.
The free energy of activation for the inversion in the case of 2,5-di- tert-octylthiophene S-oxide has been calculated via variable-temperature1H NMR measurements to be Δ G#26 = 14.8 kcal mol−1: W. L. Mock, Stable Thiophene Sulfoxides, J. Am. Chem. Soc., 1970, 92, 7610–7612
ab initio calculations for thiophene S-oxide itself have led to a similar value (Δ G# = 11.2 kcal mol−1): W. S. Jencks, N. Matsunaga, M. Gordon, Effects of Conjugation and Aromaticity on Sulfoxide Bond, J. Org. Chem., 1996, 61, 1275–1283.
T. Thiemann, D. Ohira, Y. Li, T. Sawada, S. Mataka, K. Rauch, M. Noltemeyer and A. de Meijere, [4 + 2] Cycloaddition of Thiophene S-Monoxides to Activated Methylenecyclopropanes, J. Chem. Soc., Perkin Trans. 1, 2000, 2968–2976.
J. Nakayama, T. Yu, Y. Sugihara and A. Ishii, Synthesis and Characterization of Thiophene 1-Oxides kinetically stabilized by bulky Substituents at the 3- and 4-Positions, Chem. Lett., 1997, 499–500.
P. J. Fagan, W. A. Nugent and J. C. Calabrese, Metallacycle Transfer from Zirconium to Main Group Elements: A Versatile Synthesis of Heterocycles, J. Am. Chem. Soc., 1994, 116, 1880–1889.
F. Meier-Brocks and E. Weiss, Tetraphenylzirkonacyclopentadien-Derivate als Synthone für Tetrathiophenmonoxid und substituierte Germanole, J. Organomet. Chem., 1993, 453, 33–45.
B. Jiang and T. D. Tilley, General, Efficient Route to Thiophene-1-Oxides and well-defined, mixed Thiophene–Thiophene-1-oxide Oligomers, J. Am. Chem. Soc., 1999, 121, 9744–9745.
For a preparation of 5,5′-dibromo-3,3′-dioctyl-2,2′-bithienyl (39), see: J. Xu, S. C. Ng and H. S. O. Chan, A new Approach to the Synthesis of substituted Bithiophene and Polymers containing Thiophene, Tetrahedron Lett., 2001, 42, 5327–5329.
for a preparation of 34, see: C. Troyanowsky, Synthesis of β-thienylacetylenes, Bull. Soc. Chim. Fr., 1955, 424–426.
for a preparation of 35, see: S. Gronowitz and T. Raznikiewicz, 3-Bromothiophene, Org. Synth., 1973, Coll. Vol. 5, 149–151.
for a preparation analogous to that of 36 used for this report, see: P. Bäuerle, F. Pfau, H. Schlupp, F. Würthner, K.-U. Gaudl, M. B. Caro and P. Fischer, Synthesis and Structural Characterization of Alkyl Oligothiophenes - the first isomerically pure Dialkylsexithiophene, J. Chem. Soc., Perkin Trans. 2, 1993, 489–494.
K. Sawada, K. S. Choi, M. Kuroda, T. Taniguchi, A. Ishii, M. Hoshino and J. Nakayama, Preparation of Tetraarylthiophenes and Tetraarylselenophenes by reaction of Diacetylenes with elemental Sulfur, Sulfur Lett., 1993, 15, 273–283.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Arima, K., Ohira, D., Watanabe, M. et al. The photochemistry of thiophene S-oxides. Photochem Photobiol Sci 4, 808–816 (2005). https://doi.org/10.1039/b505577f
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1039/b505577f