Studies on the acylation of 4-(2-aminoethylthio)-7-nitrobenzofurazan: the role of bases in promoting the formation of fluorescent S-acyl derivatives through S–N Smiles rearrangement

The acylation of 4-(2-aminoethylthio)-7-nitrobenzofurazan has been investigated. Depending on the use of the base, a competitive Smiles rearrangement occurs during the acylation step leading to the formation of N-acyl and/or fluorescent S-acyl derivatives. The acylating agent also affects the ratio of N/S acylated isomers

The synthesis of Waltherione F and analogues with modifications at the 2- and 3-positions as potential antitrypanosomal agents

Chagas disease also know as American Trypanosomiasis (AT) is a tropical parasitic disease endemic in South America, is caused by Trypanosoma cruzi which is transmitted by the blood‐sucking insect vectors called triatomine bugs. Quinoline alkaloids from the root extract of Waltheria indica are known to possess antitrypanosomal activity. Waltherione F 3, one of those alkaloids, was synthesised in 5 steps in 11% overall yield. A key step in the sequence utilised the Conrad‐Limpach synthesis for the formation of the quinolin‐4(1H)‐one ring system. Our synthetic strategy was designed to enable the modification of the 2‐ and 3‐positions of the scaffold, allowing the generation of a diverse library of analogues to support our on‐going medicinal chemistry program that is looking for new agents to tackle this devastating disease

Evidence for a p dimer in the electrochemical reduction of 1,3,5-trinitrobenzene : a reversible N2-fixation system

Premi a l'excel·lència investigadora. Àmbit de les Ciències Experimentals. 200

Gold catalysts for the synthesis of aromatic azocompounds from nitroaromatics in one step

[EN] One-step selective hydrogenation of nitroaromatics to obtain symmetric azocompounds with high yields has been performed with a gold supported on cerium oxide catalysts. Au/TiO2 and Au/CeO2 catalysts direct the reaction by two different pathways and with different selectivities. In situ FTIR studies reveal that the surface concentration of the intermediate nitrosobenzene is decisive in directing the reaction trough the different reaction pathways. In this way, while on Au/TiO2 a fast hydrogenation of the nitrosobenzene intermediate leads to a low surface concentration of the nitrosocompound, on Au/CeO2 nitrosobenzene is more stabilized on the catalyst surface leading to a lower hydrogenation and a higher coupling rate, resulting in high selectivities to azobenzene. On Au/CeO2, the relative weak adsorption of the azo with respect to the azoxycompound on the catalyst surface avoids the consecutive hydrogenation of azocompounds to the corresponding anilines until all the azoxy has been consumed. Asymmetric azobenzenes have also been obtained with very high yields on TiO2, through the Mills reaction.The authors wish to acknowledge the financial support from the Spanish Ministries of Education and Science and Economy and Competitiveness under the project Consolider-Ingenio 2010 (CSD2009-00050 "Development of more efficient catalysts for the design of sustainable chemical processes and clean energy production") and the Severo Ochoa program (SEV-2012-0267), respectively. D.C. thanks the Spanish MEC for postgraduate scholarship, project MAT2006-14274-C02-01.Cómbita Merchán, DF.; Concepción Heydorn, P.; Corma Canós, A. (2014). Gold catalysts for the synthesis of aromatic azocompounds from nitroaromatics in one step. Journal of Catalysis. 311:339-349. https://doi.org/10.1016/j.jcat.2013.12.014S33934931

A Greatly Under-Appreciated Fundamental Principle of Physical Organic Chemistry

If a species does not have a finite lifetime in the reaction medium, it cannot be a mechanistic intermediate. This principle was first enunciated by Jencks, as the concept of an enforced mechanism. For instance, neither primary nor secondary carbocations have long enough lifetimes to exist in an aqueous medium, so SN1 reactions involving these substrates are not possible, and an SN2 mechanism is enforced. Only tertiary carbocations and those stabilized by resonance (benzyl cations, acylium ions) are stable enough to be reaction intermediates. More importantly, it is now known that neither H3O+ nor HO− exist as such in dilute aqueous solution. Several recent high-level calculations on large proton clusters are unable to localize the positive charge; it is found to be simply “on the cluster” as a whole. The lifetime of any ionized water species is exceedingly short, a few molecular vibrations at most; the best experimental study, using modern IR instrumentation, has the most probable hydrated proton structure as H13O6+, but only an estimated quarter of the protons are present even in this form at any given instant. Thanks to the Grotthuss mechanism of chain transfer along hydrogen bonds, in reality a proton or a hydroxide ion is simply instantly available anywhere it is needed for reaction. Important mechanistic consequences result. Any charged oxygen species (e.g., a tetrahedral intermediate) is also not going to exist long enough to be a reaction intermediate, unless the charge is stabilized in some way, usually by resonance. General acid catalysis is the rule in reactions in concentrated aqueous acids. The Grotthuss mechanism also means that reactions involving neutral water are favored; the solvent is already highly structured, so the entropy involved in bringing several solvent molecules to the reaction center is unimportant. Examples are given

Raman spectroscopic detection of the T-HgII-T base pair and the ionic characteristics of mercury

Developing applications for metal-mediated base pairs (metallo-base-pair) has recently become a high-priority area in nucleic acid research, and physicochemical analyses are important for designing and fine-tuning molecular devices using metallo-base-pairs. In this study, we characterized the HgII-mediated T-T (T-HgII-T) base pair by Raman spectroscopy, which revealed the unique physical and chemical properties of HgII. A characteristic Raman marker band at 1586 cm−1 was observed and assigned to the C4=O4 stretching mode. We confirmed the assignment by the isotopic shift (18O-labeling at O4) and density functional theory (DFT) calculations. The unusually low wavenumber of the C4=O4 stretching suggested that the bond order of the C4=O4 bond reduced from its canonical value. This reduction of the bond order can be explained if the enolate-like structure (N3=C4-O4−) is involved as a resonance contributor in the thymine ring of the T-HgII-T pair. This resonance includes the N-HgII-bonded state (HgII-N3-C4=O4) and the N-HgII-dissociated state (HgII+ N3=C4-O4−), and the latter contributor reduced the bond order of N-HgII. Consequently, the HgII nucleus in the T-HgII-T pair exhibited a cationic character. Natural bond orbital (NBO) analysis supports the interpretations of the Raman experiments