Abstract
Photochemistry of 4-phenyl-1,2,3-thiadiazole (PT) and 4,5-diphenyl-1,2,3-thiadiazole (DPT) in solution was studied at room temperature using UV-vis and IR transient absorption spectroscopies (λex = 266 nm). Ultrafast techniques show a very fast rise (<0.3 ps) of thiirene and thioketene species, formed from 1,2,3-thiadiazoles in the singlet excited state. The remarkable unimolecular stability of thiirenes in solution is observed. On a millisecond time scale thiirenes with phenyl substituents undergo an intermolecular reaction (dimerization of thiirene–thioketene complexes) leading to 1,3-dithiole derivatives.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Y. Y. Morzherin, T. V. Glukhareva, V. A. Bakulev, Rearrangements and transformations of 1,2,3-thiadiazoles in organic synthesis (Review), Chem. Heterocycl. Compd., 2003, 39, 679–706.
V. A. Bakulev and W. Dehaen, The Chemistry of 1,2,3-Thiadiazoles, John Wiley & Sons. Inc., New York, 2004.
W. Kirmse, 100 years of the Wolff rearrangement, Eur. J. Org. Chem., 2002, 2193–2256.
E. Schaumann, The chemistry of thioketenes, Tetrahedron, 1988, 44, 1827–1871.
A. Krantz, J. Laureni, Characterization of matrix-isolated antiaromatic three-membered heterocycles. Preparation of the elusive thiirene molecule, J. Am. Chem. Soc., 1981, 103, 486–496.
A. Krantz, J. Laureni, A methodology for the preparation and characterization of three-membered, potentially antiaromatic molecules. Preparation of matrix-isolated thiirene and selenirene, J. Am. Chem. Soc., 1977, 99, 4842–4844.
A. Krantz, J. Laureni, Matrix photolysis of 1,2,3-thiadiazole. On the possible involvement of thiirene, J. Am. Chem. Soc., 1974, 96, 6768–6770.
M. Torres, A. Clement, J. E. Bertie, H. E. Gunning, O. P. Strausz, Low-temperature matrix isolation of thiirenes, J. Org. Chem., 1978, 43, 2490–2493.
G. Burdzinski, M. Sliwa, Y. Zhang, S. Delbaere, Early events in the photochemistry of 1,2,3-thiadiazole studied by ultrafast time-resolved UV-Vis and IR spectroscopies, J. Phys. Chem. A, 2011, 115, 14300–14305.
U. Timm, H. Meier, Markierungsexperimente zur fragmentierung von 1,2,3-thiadiazolen, J. Heterocycl. Chem., 1979, 16, 1295–1296.
U. Timm, U. Merkle, H. Meier, Die bildung von phenylthiiren, Chem. Ber., 1980, 113, 2519–2529.
G. Seybold, C. Heibl, Thioketene aus 1,2,3-thiadiazolen und 1,3-dithietanderivaten, Chem. Ber., 1977, 110, 1225–1238.
H. Murai, M. Torres, O. P. Strausz, Detection of thiobenzoylphenylmethylene by electron spin resonance spectroscopy, J. Am. Chem. Soc., 1979, 101, 3976–3979.
T. Jørgensen, C. T. Pedersen, R. Flammang, C. Wentrup, Formation of thioketenes by thermal fragmentation of 1,2-dithiol-3-ones, J. Chem. Soc., Perkin Trans. 2, 1997, 173–177.
W. Kirmse, L. Horner, Photolyse von 1.2.3-thiodiazolen, Liebigs Ann. Chem., 1958, 614, 4–18.
K.-P. Zeller, H. Meier, E. Muller, Zur photolyse von 1,2,3-thiadiazolen I, Tetrahedron Lett., 1971, 6, 537–540.
H. Kato, M. Kawamura, T. Shiba, M. Ohta, Photolysis of mesoionic 2,5-diphenyl-1,3-dithiol-4-one: a probable 4π-antiaromatic intermediate, J. Chem. Soc. D, 1970, 959–960.
H. Kato, T. Shiba, N. Aoki, H. Iijima, H. Tezuka, Photochemical and thermal reactions of heterocycles. Part 3. Photoisomerisation, photofragmentation, and photodimerisation of mesoionic 1,3-dithiol-4-one and -4-imine derivatives, J. Chem. Soc., Perkin Trans. 1, 1982, 1885–1889.
H. Bregy, H. Heimgartner, J. Helbing, A time-resolved spectroscopic comparison of the photoisomerization of small β-turn-forming thioxopeptides, J. Phys. Chem. B, 2009, 113, 1756–1762.
G. Buntinx, R. Naskrecki, O. Poizat, Subpicosecond transient absorption analysis of the photophysics of 2,2′-bipyridine and 4,4′-bipyridine in solution, J. Phys. Chem., 1996, 100, 19380–19388.
M. Sliwa, M. Mouton, C. Ruckebusch, L. Poisson, A. Idrissi, S. Aloise, L. Potier, J. Dubois, O. Poizat, G. Buntinx, Investigation of ultrafast photoinduced processes for salicylidene aniline in solution and gas phase: toward a general photo-dynamical scheme, Photochem. Photobiol. Sci., 2010, 9, 661–669.
T. Pedzinski, A. Markiewicz, B. Marciniak, Photosensitized oxidation of methionine derivatives. Laser flash photolysis studies, Res. Chem. Intermed., 2009, 35, 497–506.
A. P. Scott, L. Radom, Harmonic vibrational frequencies: an evaluation of Hartree–Fock, Møller–Plesset, quadratic configuration interaction, density functional theory, and semiempirical scale factors, J. Phys. Chem., 1996, 100, 16502–16513.
A. Shafiee, I. Lalezari, Mechanism of the stereoselective formation of 1,4-dithiafulvens from 1,2,3-thiadiazoles and base (1), J. Heterocycl. Chem., 1973, 10, 11–15.
G. Burdzinski, J. Rehault, J. Wang, M. S. Platz, A study of the photochemistry of diazo Meldrum’s acid by ultrafast time-resolved spectroscopies, J. Phys. Chem. A, 2008, 112, 10108–10112.
G. Burdzinski, Y. Zhang, J. Wang, M. S. Platz, Concerted Wolff rearrangement in two simple acyclic diazocarbonyl compounds, J. Phys. Chem. A, 2010, 114, 13065–13068.
W. I. Jones, P. E. Hoggard, The crystal and molecular structure of 2,3,5,6-tetraphenyl-1,4-dithiin, Heterocycles, 2002, 57, 353–356.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Burdzinski, G., Sliwa, M., Zhang, Y. et al. Photochemical formation of thiirene and thioketene in 1,2,3-thiadiazoles with phenyl substituents studied by time-resolved spectroscopy. Photochem Photobiol Sci 12, 895–901 (2013). https://doi.org/10.1039/c3pp25453d
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1039/c3pp25453d