Search results for "Taut"
showing 10 items of 916 documents
Structural characterization of β-2′-pyridylaminocrotonoyl-2-pyridylamide by ESI-MS, NMR, single crystal X-ray analysis and ab initio methods
2003
Abstract In contradiction with earlier reports 1H, 13C and 15N NMR spectra show that β-2′-pyridylaminocrotonoyl-2-pyridylamide is the only form present in chloroform solution. According to the X-ray data the same tautomer exists also in the crystal state. The studied amide has a dimeric form where the monomer molecules are held together by two intermolecular hydrogen bonds. The NMR spectral data show that there is also an intramolecular hydrogen bond in each monomer subunit. The dilution experiments and variable-temperature 1H NMR runs show that β-2′-pyridylaminocrotonoyl-2-pyridylamide tends to form the dimers also in chloroform solution at higher concentrations. The ESI-TOF MS measurement…
Structural and spectroscopic characterisation of 2-(2'-hydroxybenzoyl)pyrrole and its O-methyl derivative
2004
Abstract Density functional theory calculations on the tautomeric and conformational equilibria of 2-(2′-hydroxybenzoyl)pyrrole (HBP) and 2-(2′-methoxybenzoyl)pyrrole (MBP) were performed. Moreover, the experimental IR and UV spectra of the same compounds were recorded and compared with the theoretical data. The presence of an intramolecular hydrogen bond in HBP can be related to the biological activities of some of its derivatives.
Proton-Coupled Electron Transfer in Ferrocenium–Phenolate Radicals
2013
Electron and proton transfer (ET, PT) can be intimately coupled, provided suitable redox and acid/base sites are available. The amide-linked ferrocene–phenol H-1 is deprotonated to the phenolate [1]– by phosphazene bases and oxidized to the ferrocenium ion [H-1]+ by silver hexafluoroantimonate. Concomitant oxidation and deprotonation yields the radical [1]•, featuring a characteristic near-IR absorption band. The ground state of [1]• is best described as the ferrocenium–phenolate zwitterion [1b]• with a dynamic dissymmetric N···H···O hydrogen bond (PT). The ferrocenium–iminolate N···H–O tautomer [1b]•-NHO′ can undergo a thermal structural rearrangement to the high-energy OH···O tautomer [1b…
Tautomerism in pyridazin-3(2H)-one: a theoretical study using implicit/explicit solvation models.
2013
Abstract The tautomeric conversion of pyridazin-3(2H)-one 1 into pyridazin-3-ol 2 has been theoretically studied using density functional theory (DFT) methods at the B3LYP/6-311++G** level. Two mechanisms have been considered for this process: (i) one in which the hydrogen is directly transferred through TS12; and (ii) another one in which a double hydrogen transfer takes place via TS1122 upon formation of the corresponding dimer. The former requires a very high activation energy of 42.64 kcal/mol as a consequence of the strain associated with the formation of the four-membered TS12, while the latter requires a much lower activation energy, 14.66 kcal/mol. Implicit, explicit, and a combinat…
Back to School : Labor-Market Returns to Higher Vocational Schooling
2019
This paper examines the labor-market returns to a new form of postsecondary vocational education: vocational master's degrees. We use individual fixed effects models on a matched sample of students and non-students from Finland to capture any time-invariant differences across individuals. We find that attendance in vocational master's programs leads to an earnings increase of more than seven percent five years after entry. The estimated effect remains positive even if selection on unobservables is twice as strong as selection on observables. Earnings gains are similar by gender and age, but they are marginally higher for those in the health sector than for those in the business or technolog…
Rakstveida pierādījumi starptautisko komerciālo šķīrējtiesu procesā
2016
Starptautiskās komerciālās šķīrējtiesas procesā nav vienoti procesuāli noteikumi, kas regulētu ar pierādījumiem saistītus jautājumus, līdz ar to pastāvošā prakse attiecībā uz pierādījumu iegūšanu ir daudzveidīga. To īpaši ietekmē apstāklis, ka dažādos tiesību lokos izpratne par pierādījumiem atšķiras. Tas savukārt noved pie tā, ka attiecībā uz vienu no efektīvākajiem pierādījumu iegūšana veidiem – rakstveida pierādījumu izprasīšanu, starptautisko komerciālo šķīrējtiesu procesos valda nevienprātība un tā tiek dažādi realizēta. Bez tam neskaidrību šī pierādījuma iegūšanas veida realizācija rada augušā elektronisko dokumentu nozīme mūsdienu biznesa vidē. Pētījuma mērķis ir, analizējot šķīrējti…
Ārējās tirdzniecības problēmas Latvijā
2015
Maģistra darbā „Ārējās tirdzniecības problēmas Latvijā” tiek pētīti un salīdzināti Latvijas eksporta un importa dati. Maģistra darba mērķis ir, pamatojoties uz zinātnisko literatūru, normatīvo aktu izpēti un statistisko datu analīzi, sniegt ārējās tirdzniecības teorētisko pamatojumu, izanalizēt ārējās tirdzniecības dinamiku un struktūru Latvijā, kā arī veikt ārējās tirdzniecības problēmu analīzi Latvijas nozīmīgākajās nozarēs. Darba mērķa sasniegšanai galvenie darba uzdevumi: •pamatojoties uz zinātnisko literatūru, izpētīt starptautisko tirdzniecības vēsturi un to nozīmi mūsdienās; •izanalizēt Latvijas ārējās tirdzniecības dinamiku un struktūru un to svārstību ietekmējošos iemeslus; •izvirz…
Straight Access to Indoles from Anilines and Ethylene Glycol by Heterogeneous Acceptorless Dehydrogenative Condensation.
2017
The development of original strategies for the preparation of indole derivatives is a major goal in drug design. Herein, we report the first straight access to indoles from anilines and ethylene glycol by heterogeneous catalysis, based on an acceptorless dehydrogenative condensation, under noninert conditions. In order to achieve high selectivity, a combination of Pt/Al2O3 and ZnO have been found to slowly dehydrogenate ethylene glycol generating, after condensation with the amine and tautomeric equilibrium, the corresponding pyrrole-ring unsubstituted indoles.
ChemInform Abstract: Cross-Dehydrogenative Couplings Between Indoles and β-Keto Esters: Ligand-Assisted Ligand Tautomerization and Dehydrogenation vi…
2014
Cross-dehydrogenative coupling reactions between β-ketoesters and electron-rich arenes, such as indoles, proceed with high regiochemical fidelity with a range of β-ketoesters and indoles. The mechanism of the reaction between a prototypical β-ketoester, ethyl 2-oxocyclopentanonecarboxylate, and N-methylindole has been studied experimentally by monitoring the temporal course of the reaction by (1)H NMR, kinetic isotope effect studies, and control experiments. DFT calculations have been carried out using a dispersion-corrected range-separated hybrid functional (ωB97X-D) to explore the basic elementary steps of the catalytic cycle. The experimental results indicate that the reaction proceeds v…
Cross-Dehydrogenative Couplings between Indoles and beta-Keto Esters: Ligand-Assisted Ligand Tautomerization and Dehydrogenation via a Proton-Assiste…
2014
Cross-dehydrogenative coupling reactions between β-ketoesters and electron-rich arenes, such as indoles, proceed with high regiochemical fidelity with a range of β-ketoesters and indoles. The mechanism of the reaction between a prototypical β-ketoester, ethyl 2-oxocyclopentanonecarboxylate, and N-methylindole has been studied experimentally by monitoring the temporal course of the reaction by (1)H NMR, kinetic isotope effect studies, and control experiments. DFT calculations have been carried out using a dispersion-corrected range-separated hybrid functional (ωB97X-D) to explore the basic elementary steps of the catalytic cycle. The experimental results indicate that the reaction proceeds v…