Butler, Richard N. and Fahy, Aoife and Fox, Anthony and Stephens, John C. and McArdle, P. and Cunningham, D. and Ryder, A. (2006) One-Pot Synthesis of Fluorescent 2,5-Dihydro-1,2,3-triazine Derivatives from a Cascade Rearrangement Sequence in the Reactions of 1,2,3-Triazolium-1-aminide 1,3-Dipoles with Propiolate Esters. Journal of Organic Chemistry, 71 (15). pp. 5679-5687. ISSN 0022-3263

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Abstract

The reactions of 1,2,3-triazolium-1-aminides 1 (readily available from benzil bishydrazones) with propiolate esters leads to fluorescent 2,5-dihydro-1,2,3-triazine derivatives 2, 3 in one pot. These synthetic reactions can be carried out in acetone, in water, or under solvent-free conditions. The reactions involve a Huisgen cycloaddition followed by a sequence of rearrangements. The final ring-expansion step was blocked by linking a six-methylene hydrocarbon chain between the prospective 1,2,3-triazine C-4 and C-6 atoms, using substrate 8 which gave the fused tricyclic azapropellane product 9 exclusively. X-ray crystal structures were determined for two 2,5-dihydro-1,2,3-triazine derivatives and for compound 9. The UV absorption of the 1,2,3-triazine derivatives showed a dual absorption at ca. 310 and ca. 390 nm with fluorescent emission at ca. 480 and 528 nm (for excitation at 317 nm). The significant Stokes shift of ca. 200 nm shows the potential for biological fluorescent labeling experiments.

Item Type:	Article
Keywords:	One-Pot Synthesis; Fluorescent 2,5-Dihydro-1,2,3-triazine Derivatives; Cascade Rearrangement Sequence; 1,2,3-Triazolium-1-aminide 1,3-Dipoles; Propiolate Esters;
Academic Unit:	Faculty of Science and Engineering > Chemistry
Item ID:	7819
Identification Number:	https://doi.org/10.1021/jo060752x
Depositing User:	Dr John Stephens
Date Deposited:	27 Jan 2017 15:29
Journal or Publication Title:	Journal of Organic Chemistry
Publisher:	American Chemical Society
Refereed:	Yes
Funders:	Irish Research Council for Science Engineering and Technology (IRCSET), Science Foundation Ireland (SFI)
URI:	http://pubs.acs.org/
Use Licence:	This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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