Pyrido[1,2-a]pyrimidinones and Thiazolo[3,2-a]pyrimidinones: Precursors for Pyridyl- and Thiazolyliminopropadienones, R–N=C=C=C=O
Heidi Gade Andersen A B and Curt Wentrup A C
+ Author Affiliations
- Author Affiliations
A School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane Qld 4072, Australia.
B Current address: Cheminova A/S, 7620 Lemvig, Denmark.
C Corresponding author. Email: wentrup@uq.edu.au
Australian Journal of Chemistry 65(2) 105-112 https://doi.org/10.1071/CH11414
Submitted: 25 October 2011 Accepted: 3 December 2011 Published: 21 February 2012
Abstract
2-Pyridyliminopropadienone 6 is formed together with 2-aminopyridine on flash vacuum thermolysis (FVT) of 2-pyridylamino-pyridopyrimidinone 16a and observed by Ar matrix IR spectroscopy, but the two products recombine on warming to room temperature to regenerate the starting material. FVT of the picolinylamino-pyridopyrimidinones 16b and 16c generated mixtures of pyridyliminopropadienone 6 and picolinyliminopropadienones 19b and 19c, respectively. These reactions can be understood in terms of fragmentation of the open-chain bis(2-pyridylamino)methyleneketene intermediates 20 or the thermal interconversion of pyridopyrimidinones 16 and mesoionic pyridopyrimidinium olates 21. 2-Thiazoyliminopropadienone 28 was obtained in an analogous manner by FVT of the 2-(methylthio)thiazolopyrimidinone 24. However, the corresponding dihydro derivative 31 yielded cyanoketene 36 as the major product.
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