Thioketenes and Iminopropadienethiones RN=C=C=C=S from Isoxazolones
David Kvaskoff A and Curt Wentrup A B
+ Author Affiliations
- Author Affiliations
A School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, Qld 4072, Australia.
B Corresponding author. Email: wentrup@uq.edu.au
Australian Journal of Chemistry 63(12) 1694-1702 https://doi.org/10.1071/CH10340
Submitted: 14 September 2010 Accepted: 5 October 2010 Published: 6 December 2010
Abstract
Isoxazolones 6 undergo thermal elimination of propene and isopropylthiol to produce thioketenes 7 at 500–600°C under flash vacuum thermolysis conditions. At 700–900°C further fragmentation occurs to produce iminopropadienethiones, RNCCCS 8. In addition, 3-alkylisoxazolones 6d–e rearrange to cyanothioketenes 10d–e. Compounds 7, 8, and 10 were characterized by Ar matrix IR spectroscopy and comparison with density functional theory-calculated spectra. Thioketenes 7 reacted with amines to afford thioamides 11. Reaction of aryliminopropadienethiones 8 with amines caused cyclization to 2-aminoquinoline-4(1H)-thiones 16.
References
[1] (a) H. Bibas, D. W. J. Moloney, R. Neumann, M. Shtaiwi, P. V. Bernhardt, C. Wentrup, J. Org. Chem. 2002, 67, 2619.| Crossref | GoogleScholarGoogle Scholar | 11950308PubMed |
(b) M. Shtaiwi, C. Wentrup, J. Org. Chem. 2002, 67, 8558.
| Crossref | GoogleScholarGoogle Scholar |
[2] D. Lecoq, B. Chalmers, R. N. Veedu, D. Dvaskoff, P. V. Bernhardt, C. Wentrup, Aust. J. Chem. 2009, 62, 1631.
| Crossref | GoogleScholarGoogle Scholar |
[3] B. Fulloon, C. Wentrup, Aust. J. Chem. 2009, 62, 115.
| Crossref | GoogleScholarGoogle Scholar |
[4] C. O. Kappe, D. Kvaskoff, D. W. J. Moloney, R. Flammang, C. Wentrup, J. Org. Chem. 2001, 66, 1827.
| Crossref | GoogleScholarGoogle Scholar | 11262134PubMed |
[5] C. T. Pedersen, E. Fanghänel, R. Flammang, J. Chem. Soc., Perkin Trans. 2 2001, 356.
| Crossref | GoogleScholarGoogle Scholar |
[6] Minireviews: C. Wentrup, C. O. Kappe, M. W. Wong, Pure Appl. Chem. 1995, 67, 749.
(b) C. Wentrup, B. E. Fulloon, D. W. J. Moloney, H. Bibas, M. W. Wong, Pure Appl. Chem. 1996, 68, 891.
| Crossref | GoogleScholarGoogle Scholar |
(c) G. I. Yranzo, J. Elguero, R. Flammang, C. Wentrup, Eur. J. Org. Chem. 2001, 2209.
| Crossref | GoogleScholarGoogle Scholar |
[7] (a) R. Wolf, M. W. Wong, C. H. L. Kennard, C. Wentrup, J. Am. Chem. Soc. 1995, 117, 6789.
| Crossref | GoogleScholarGoogle Scholar |
(b) R. Wolf, S. Stadtmüller, M. W. Wong, M. Barbieux-Flammang, R. Flammang, C. Wentrup, Chem. Eur. J. 1996, 2, 1318.
| Crossref | GoogleScholarGoogle Scholar |
[8] (a) M. Hawkins, M. J. Almond, A. J. Downs, J. Phys. Chem. 1985, 89, 3326.
| Crossref | GoogleScholarGoogle Scholar |
(b) J. R. Ammann, R. Flammang, M. W. Wong, C. Wentrup, J. Org. Chem. 2000, 65, 2706.
| Crossref | GoogleScholarGoogle Scholar |
[9] A. Hassner, Azides and Nitrenes 1984, pp. 35–94 (Ed. E. F. V. Scriven) (Academic Press: Orlando, FL).
[10] J. Finnerty, U. Mitschke, C. Wentrup, J. Org. Chem. 2002, 67, 1084.
| Crossref | GoogleScholarGoogle Scholar | 11846648PubMed |
[11] (a) E. Schaumann, Tetrahedron 1988, 44, 1827.
| Crossref | GoogleScholarGoogle Scholar |
(b) C. Spanka, E. Schaumann, Science of Synthesis 2006, 23, 735.
[12] J. J. Finnerty, C. Wentrup, J. Org. Chem. 2005, 70, 9735.
| Crossref | GoogleScholarGoogle Scholar | 16292801PubMed |
[13] (a) J. J. Finnerty, C. Wentrup, J. Org. Chem. 2004, 69, 1909.
| Crossref | GoogleScholarGoogle Scholar | 15058936PubMed |
(b) C. Wentrup, J. J. Finnerty, R. Koch, Curr. Org. Chem. 2010, 14, 1586.
[14] L. George, K.-P. Netsch, G. Penn, G. Kollenz, C. Wentrup, Org. Biomol. Chem. 2006, 4, 558.
| Crossref | GoogleScholarGoogle Scholar | 16446815PubMed |
[15] D. M. Birney, Curr. Org. Chem. 2010, 14, 1658.
[16] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin,J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene,X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian 03, Revision C.01 2004 (Gaussian, Inc.: Wallingford, CT).
[17] M. W. Wong, Chem. Phys. Lett. 1996, 256, 391.
| Crossref | GoogleScholarGoogle Scholar |
[18] D. Kvaskoff, P. V. Bernhardt, R. Koch, C. Wentrup, Aust. J. Chem. 2009, 62, 1068.
| Crossref | GoogleScholarGoogle Scholar |
[19] C. Addicott, C. Wentrup, Aust. J. Chem. 2008, 61, 592.
| Crossref | GoogleScholarGoogle Scholar |
