Indole Synthesis Using Silver Catalysis

Indoles are amongst the most important class of heteroaromatics in organic chemistry, being commonly found in biologically active natural products and therapeutically useful compounds. The synthesis of indoles is therefore important and several methods for their synthesis that make use of silver(I) catalysts and reagents have been developed in recent years. This Focus Review contains, to the best of our knowledge, a comprehensive coverage of silver-mediated indole forming reactions since the first reaction of this type was reported in 2004

Quantitative Structure–Property Relationship Studies on Ostwald Solubility and Partition Coefficients of Organic Solutes in Ionic Liquids

Article discussing quantitative structure-property relationship studies on Ostwald solubility and partition coefficients of organic solutes in ionic liquids

Photochemistry of Furyl- and Thienyldiazomethanes: Spectroscopic Characterization of Triplet 3-Thienylcarbene

Photolysis (λ \u3e 543 nm) of 3-thienyldiazomethane (1), matrix isolated in Ar or N2 at 10 K, yields triplet 3-thienylcarbene (13) and α-thial-methylenecyclopropene (9). Carbene 13 was characterized by IR, UV/vis, and EPR spectroscopy. The conformational isomers of 3-thienylcarbene (s-E and s-Z) exhibit an unusually large difference in zero-field splitting parameters in the triplet EPR spectrum (|D/hc| = 0.508 cm–1, |E/hc| = 0.0554 cm–1; |D/hc| = 0.579 cm–1, |E/hc| = 0.0315 cm–1). Natural Bond Orbital (NBO) calculations reveal substantially differing spin densities in the 3-thienyl ring at the positions adjacent to the carbene center, which is one factor contributing to the large difference in D values. NBO calculations also reveal a stabilizing interaction between the sp orbital of the carbene carbon in the s-Z rotamer of 13 and the antibonding σ orbital between sulfur and the neighboring carbon—an interaction that is not observed in the s-E rotamer of 13. In contrast to the EPR spectra, the electronic absorption spectra of the rotamers of triplet 3-thienylcarbene (13) are indistinguishable under our experimental conditions. The carbene exhibits a weak electronic absorption in the visible spectrum (λmax = 467 nm) that is characteristic of triplet arylcarbenes. Although studies of 2-thienyldiazomethane (2), 3-furyldiazomethane (3), or 2-furyldiazomethane (4) provided further insight into the photochemical interconversions among C5H4S or C5H4O isomers, these studies did not lead to the spectroscopic detection of the corresponding triplet carbenes (2-thienylcarbene (11), 3-furylcarbene (23), or 2-furylcarbene (22), respectively)

A General Treatment of Solubility 4. Description and Analysis of a PCA Model for Ostwald Solubility Coefficients

Article discussing a general treatment of solubility and a description and analysis of a principal component analysis (PCA) model for Ostwald solubility coefficients

Asymmetric total synthesis of (+)-virosine a via sequential nucleophilic cyclizations onto an activated formamide

Abstract: The first synthesis of tetracyclic alkaloid virosine A is reported. The natural alkaloid was prepared in only 13 steps, in an enantioenriched form. The azabicyclo[2.2.2]octane core was efficiently assembled using a key Vilsmeier–Haack and Mannich cyclizations sequence performed in one pot

Novi pristup spektrofotometrijskom određivanju metronidazola i tinidazola koristeći p-dimetilaminobenzaldehid

A new approach to the spectrophotometric determination of metronidazole (MZ) and tinidazole (TZ) has been developed. The procedure involves coupling of diazotized nitroimidazoles with p-dimethylaminobenzaldehyde (DMAB) to form a greenish-yellow solution. Optimal temperature and time for diazotization were 0 oC (iced) and 3 minutes and 30 oC and 2 minutes for coupling was, respectively, for both MZ and TZ. Coloured adducts of MZ and TZ showed peaks at 406 nm and 404 nm, respectively, which were selected as analytical wavelengths. The reaction with p-DMAB occurred in a 1:1 mole ratio. Beer’s law was obeyed within the 4.8–76.8 µg mL1 concentration range with low limits of detection. The azo adducts were stable for over a week. Molar absorptivities were 1.10 x 103 (MZ) and 1.30 x 103 L mol1 cm1 (TZ). Overall recoveries of MZ and TZ from quality control samples were 103.2 ± 1.3 and 101.9 ± 1.3 % over three days. There was no interference from commonly utilized tablet excipients. No significant difference was obtained between the results of the new method and the BP titrimetric procedures. The azo approach using the p-dimethylaminobenzaldehyde procedure described in this paper is simple, fast, accurate and precise. It is the first application of DMAB as a coupling component in the diazo coupling reaction.U radu je opisan novi način spektrofotometrijskog određivanja metronidazola (MZ) i tinidazola (TZ). Postupak uključuje reakciju diazotiranog nitroimidazola s p-dimetilaminobenzaldehidom (DMAB), pri čemu nastaje zelenkasto-žuta otopina. Optimalna temperatura i vrijeme za diazotaciju su 0 oC (ledena kupelj) i 3 minute, a za reakciju kondenzacije 30 oC i 2 minute. Obojeni adukti imaju maksimum apsorpcije pri 406, odnosno 404 nm pa su te valne duljine izabrane za analitički postupak. Reakcija s p-DMAB zbiva se u množinskom omjeru 1:1. Reakcija slijedi Beerov zakon u koncentracijskom rasponu 4,8–76,8 µg mL1 s niskim granicama detekcije. Azo adukti su stabilni preko tjedan dana. Molarna apsorptivnost bila je 1,10 × 103 (MZ), odnosno 1,30 × 103 L mol1 cm1 (TZ). Ukupni povrat MZ i TZ iz kontrolnih uzoraka bio je 103,2 ± 1,3, odnosno 101,9 ± 1,3 % tijekom tri dana. Nije zamijećena nikakva interferencija uobičajenih pomoćnih tvari koje se koriste za tabletiranje. Ne postoji značajna razlika između rezultata dobivenih novom metodom i rezultata dobivenih BP titrimetrijskim postupkom. Metoda određivanja opisana u ovom radu je jednostavna, brza, pogodna, točna i precizna i po prvi puta uključuje DMAB u reakciji diazo kopulacije

Environment influences on the aromatic character of nucleobases and amino acids

Geometric (HOMA) and magnetic (NICS) indices of aromaticity were estimated for aromatic rings of amino acids and nucleobases. Cartesian coordinates were taken directly either from PDB files deposited in public databases at the finest resolution available (≤1.5 Å), or from structures resulting from full gradient geometry optimization in a hybrid QM/MM approach. Significant environmental effects imposing alterations of HOMA values were noted for all aromatic rings analysed. Furthermore, even extra fine resolution (≤1.0 Å) is not sufficient for direct estimation of HOMA values based on Cartesian coordinates provided by PDB files. The values of mean bond errors seem to be much higher than the 0.05 Å often reported for PDB files. The use of quantum chemistry geometry optimization is strongly advised; even a simple QM/MM model comprising only the aromatic substructure within the QM region and the rest of biomolecule treated classically within the MM framework proved to be a promising means of describing aromaticity inside native environments. According to the results presented, three consequences of the interaction with the environment can be observed that induce changes in structural and magnetic indices of aromaticity. First, broad ranges of HOMA or NICS values are usually obtained for different conformations of nearest neighborhood. Next, these values and their means can differ significantly from those characterising isolated monomers. The most significant increase in aromaticities is expected for the six-membered rings of guanine, thymine and cytosine. The same trend was also noticed for all amino acids inside proteins but this effect was much smaller, reaching the highest value for the five-membered ring of tryptophan. Explicit water solutions impose similar changes on HOMA and NICS distributions. Thus, environment effects of protein, DNA and even explicit water molecules are non-negligible sources of aromaticity changes appearing in the rings of nucleobases and aromatic amino acids residues

Effect of base–acid properties of the mixtures of water with methanol on the solution enthalpy of selected cyclic ethers in this mixture at 298.15 K

The enthalpies of solution of cyclic ethers: 1,4- dioxane, 12-crown-4 and 18-crown-6 in the mixture of water and methanol have been measured within the whole mole fraction range at T = 298.15 K. Based on the obtained data, the effect of base–acid properties of water– methanol mixtures on the solution enthalpy of cyclic ethers in these mixtures has been analyzed. The solution enthalpy of cyclic ethers depends on acid properties of water– methanol mixtures in the range of high and medium water contents in the mixture. Based on the analysis performed, it can be assumed that in the mixtures of high methanol contents, cyclic ethe