1,3-Dipolar Cycloaddition (Part II): Three-Component Cu(I) Catalysed Click Reactions

Cu(I) kataliziranim reakcijama sulfonil- odnosno fosforil-azida i terminalnih alkina nastaje intermedijar ketenimin koji reagira s nukleofilima kao što su voda, alkoholi, amini, piroli ili indoli, pri čemu nastaju odgovarajući amidi, imidati, amidini i supstituirani heterocikli, u jednom reakcijskom koraku. Te selektivne reakcije zbivaju se pri blagim reakcijskim uvjetima (sobna temperatura, prisustvo zraka i vode), bez steričkog i elektronskog utjecaja supstituenata na ishod reakcije.The Cu(I) catalysed reaction of sulfonyl or phosphoryl azide and terminal alkyne obtains a ketenimine intermediate that reacts with nucleophiles like water, alcohols, amines, imines, pyrroles or indoles producing corresponding amides, imidates, amidines and substituted heterocycles, in one reaction step. These selective reactions are characterised by mild reaction conditions (room temperature, presence of air and water), without steric or electron influence of substituents on the reaction outcome

Paleogeographic evolution of the Southern Pannonian Basin: 40Ar/39Ar age constraints on the Miocene continental series of notthern Croatia

The Pannonian Basin, originating during the Early Miocene, is a large extensional basin incorporated between Alpine, Carpathian and Dinaride fold-thrust belts. Back-arc extensional tectonics triggered deposition of up to 500-m-thick continental fluvio-lacustrine deposits distributed in numerous sub-basins of the Southern Pannonian Basin. Extensive andesitic and dacitic volcanism accompanied the syn-rift deposition and caused a number of pyroclastic intercalations. Here, we analyze two volcanic ash layers located at the base and top of the continental series. The lowermost ash from Mt. Kalnik yielded an 40Ar/39Ar age of 18.07 ± 0.07 Ma. This indicates that the marine-continental transition in the Slovenia-Zagorje Basin, coinciding with the onset of rifting tectonics in the Southern Pannonian Basin, occurs roughly at the Eggenburgian/ Ottnangian boundary of the regional Paratethys time scale. This age proves the synchronicity of initial rifting in the Southern Pannonian Basin with the beginning of sedimentation in the Dinaride Lake System. Beside geodynamic evolution, the two regions also share a biotic evolutionary history: both belong to the same ecoregion, which we designate here as the Illyrian Bioprovince. The youngest volcanic ash level is sampled at the Glina and Karlovac sub-depressions, and both sites yield the same 40Ar/39Ar age of 15.91 ± 0.06 and 16.03 ± 0.06 Ma, respectively. This indicates that lacustrine sedimentation in the Southern Pannonian Basin continued at least until the earliest Badenian. The present results provide not only important bench marks on duration of initial synrift in the Pannonian Basin System, but also deliver substantial backbone data for paleogeographic reconstructions in Central and Southeastern Europe around the Early–Middle Miocene transition

Identification of Disulfides from the Biodegradation of Dibenzothiophene

Several investigations have identified benzothiophene-2,3-dione in the organic solvent extracts of acidified cultures degrading dibenzothiophene via the Kodama pathway. In solution at neutral pH, the 2,3-dione exists as 2-mercaptophenylglyoxylate, which cyclizes upon acidification and is extracted as the 2,3-dione. The fate of these compounds in microbial cultures has never been determined. This study investigated the abiotic reactions of 2-mercaptophenylglyoxylate incubated aerobically in mineral salts medium at neutral pH. Oxidation led to the formation of 2-oxo-2-(2-thiophenyl)ethanoic acid disulfide, formed from two molecules of 2-mercaptophenylglyoxylate. Two sequential abiotic, net losses of both a carbon and an oxygen atom produced two additional disulfides, 2-oxo-2-(2-thiophenyl)ethanoic acid 2-benzoic acid disulfide and 2,2′-dithiosalicylic acid. The methods developed to extract and detect these three disulfides were then used for the analysis of a culture of Pseudomonas sp. strain BT1d grown on dibenzothiophene as its sole carbon and energy source. All three of the disulfides were detected, indicating that 2-mercaptophenylglyoxylate is an important, short-lived intermediate in the breakdown of dibenzothiophene via the Kodama pathway. The disulfides eluded previous investigations because of (i) their high polarity, being dicarboxylic acids; (ii) the need to lower the pH of the aqueous medium to <1 to extract them into an organic solvent such as dichloromethane; (iii) their poor solubility in organic solvents, (iv) their removal from organic extracts of cultures during filtration through the commonly used drying agent anhydrous sodium sulfate; and (v) their high molecular masses (362, 334, and 306 Da) compared to that of dibenzothiophene (184 Da)