This work is about Maya Blue (MB), a pigment developed byMesoamerican civilizations between the 5th and 16th centuries from an aluminosilicate mineral (palygorskite) and an organic dye (indigo). Two different supramolecular quantum-mechanical models afford explanations for the unusual stability of MB based on the oxidation of the indigo molecule during the heating process and its interaction with palygorskite. A model considering indigo derivatives attached to several aluminates shows the principal features of the experimental visible spectrum of MB within the TD-DFT methodology. Another model of an indigo oxidized species confined within an inorganic supramolecular cavity system, that involves about 170 atoms, was calculated after a large configuration interaction of single excited determinants within the NDOL approximation (Montero-Cabrera et al., J Chem Phys, 2007, 127, 145102). It allows a correct reproduction and interpretation of the corresponding spectrum. This second methodology provides the most satisfactory results, being able to manage very big molecular systems at a QM level. Structural explanation for the unusual stability of MB is also provided.

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Based on experimental evidence and DFT studies, a probable cyclization route to 1,3,5-thiadiazinanes-2-thiones in aqueous medium is proposed. Experimental facts suggest the formation of a {[hydroxymethyl (substituted) carbamothioyl] sulfanyl}methanol intermediate via reaction of dithiocarbamate (DTC) and formaldehyde. Nucleophilic addition of glycine to this intermediate generates an adduct that undergoes intramolecular heterocyclization via an S(N)2 reaction. Computational calculations predict an active role of water in the reaction mechanism that promotes intramolecular cyclization.

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5-Acetoxymethyl-and 5-hydroxymethyl-2-vinylfuran were synthesized by two routes. The first route starts from 2-methylfuran and the second from furfuryl acetate. The latter route, involving successive Vilsmeier-Haack and Wittig reactions, is suitable for producing 5-acetoxymethyl-2-vinylfuran and 5-hydroxymethyl-2 vinylfuran in 68% and 60% yields, respectively.