Search results for "tautomer"
showing 10 items of 141 documents
Theoretical studies on cycloaddition reactions
2014
Cycloaddition reactions represent one of the most powerful processes in organic chemistry. The most common types of cycloaddition reactions are the Diels-Alder (DA) and the 1,3-dipolar cycloaddition reactions (1,3-DCs) which lead to five and six membered rings, respectively. In our ongoing efforts to contribute to the understanding of DA and 1,3-DCs; we studied the following using the B3LYP/6-31G(d) level of theory: 1. The 1,3-DCs of the pyridinium-3-olates and pyrazinium-3-olates with methyl acrylate and methyl methacrylate [1,2]. 2. The competitive hetero-DA and 1,3-DCs of methyl glyoxylate oxime and its tautomeric nitrone with cyclopentadiene in the absence and in the presence of BF3 as …
Understanding the formation of [3+2] and [2+4] cycloadducts in the Lewis acid catalysed reaction between methyl glyoxylate oxime and cyclopentadiene:…
2013
The formation of the formal [3+2] and [2+4] cycloadducts in the Lewis acid (LA) catalysed reaction of cyclopentadiene (Cp, 1) with methyl glyoxylate oxime (MGO, 2a) has been theoretically studied using DFT methods. Coordination of BF3 LA to the oxygen atom of MGO 2a not only increases the electrophilicity of the oxime, but also makes the corresponding tautomeric BF3:nitrone complex 8b the reactive species. The reaction is characterised by the nucleophilic attack of Cp 1 on the carbon atom of the corresponding BF3:nitrone complex 8b. The subsequent ring closure at the end of the reaction allows the formation of the [3+2] or [2+4] cycloadducts. ELF bonding analysis of selected points on the i…
Spectroscopic behavior of metal–drug complexes. Infrared spectra of Cu(II) dimer complexes with acetazolamide (H2acm) and an analogue sulfonamide (B-…
1999
Abstract The infrared spectra of the drugs H2acm and B-H2ats, and their copper(II) dimer complexes with stoichiometries [Cu(acm)(NH3)2(OH2)]2·H2O and [Cu(B-ats)(NH3)2]2 are reported and discussed. The Raman spectra of H2acm and B-H2ats are also reported. An assignment of H2acm and B-H2ats modes in the complexes is proposed in comparison with the modes of the free ligands. The spectral modifications due to the deprotonation and coordination effects are analyzed. The ν(N–H) modes of the sulfonamido, carbonamido and Nring–H of the imine tautomer have been accurately assigned. Important information about the S–O and S–N vibrations has been obtained.
(Z)-Ethyl 2-oxo-3-(1,2-dihydroquinolin-2-ylidene)propanoate
2010
Both independent molecules in the asymmetric unit of the tautomeric title compound, C14H13NO3, a synthetic product obtained from 2-lithiomethylquinoline and diethyl oxalate, crystallize in the enaminone form with a Z configuration around the double bond. Intramolecular N—H...O hydrogen bonds occur, generating an S(6) graph-set motif. In the crystal, weak intermolecular C—H...O and π–π stacking interactions [centroid–centroid distances = 3.7020 (14)–3.7429 (13)Å] define a three-dimensional supramolecular network.
ChemInform Abstract: A Simple and Efficient Route to 1,4-Diketones from Squaric Acid.
2010
Abstract Squaric acid derivatives react with organolithium compounds at room temperature to afford with excellent yields after hydrolysis, symmetrical and unsymmetrically substituted oxygenated 1,4 diketones bearing alkyl, aryl or heteroaryl groups at the carbonyl positions. In the case of aromatic or heteroaromatic ketones the enol tautomers are also obtained.
An Efficient and Simple Entry to N-Substituted beta-Enamino Acid Derivatives from 2-Alkyl-2-oxazolines and 2-Alkyl-2-thiazolines.
1996
Reaction of azaenolates of 2-alkyl-oxa(thia)zolines 6 with imidoyl chlorides 7 as electrophiles to furnish masked N-substituted beta-enamino acid derivatives 1-2 in 70-90% yield is described. Alternative routes are discussed. Compounds 1-2 generally appear in one tautomeric form, imino or enamino, depending on the nature of the imidoyl chloride. The configuration of the enamino moiety (Z) and the conformation (s-cis) of compounds 1-2 obtained were established by an NMR study and unequivocally set by nuclear Overhauser effect difference experiments. An X-ray structure of compound 1e is also reported, showing a strong intramolecular NH.N hydrogen bond. Ab initio calculations (HF/3-21G and HF/…
A study of the enolization of some alkyl ketones in lyomesophases formed by alkylammonium surfactants
1988
The kinetics of enolization of acetone, 3-pentanone, and 6-undecanone have been studied in lyotropic systems in the isotropic, nematic, and lamellar phases. The data, analysed in terms of spontaneous and acid-catalyzed rate constants, do not show any relevant influence of the physical nature of the phase. Effects are instead observed in relation to the length of the alkyl chains of the ketones and the type of the amphiphilic molecule. 6-undecanone has a surprising effect in stabilizing ordered mesophases.
On the aromaticity of uracil and its 5-halogeno derivatives as revealed by theoretically derived geometric and magnetic indexes
2020
AbstractThe problem of aromaticity in heterocyclic rings of uracil and its 5-halogenoderivatives (5XU) was analyzed theoretically by calculating modified harmonic oscillator model of aromaticity (HOMA) for Heterocycle Electron Delocalization (HOMHED), nucleus-independent chemical shift parameters (NICS) and the so-called scan experiments, using helium-3 atom as a magnetic probe. The impact of halogen electronegativity on C5 atom’s NBO charges was also investigated. Water, as a polar environment, has a negligible impact on 5XU aromaticity. The most stable diketo tautomer shows a very low aromaticity while the “rare” dihydroxy form (tautomer No 6) is aromatic and resembles benzene. This is in…
Spin crossover in soft matter
2014
Abstract This review article is devoted to the study of the spin crossover phenomenon in soft matter. Spin crossover compounds, though known for decades, bear the potential for practical applications in switching, sensing and display devices. Having arrived at a reasonable understanding of the spin transition process in solid and liquid states, one trend in this research field is to extend the knowledge into soft matter. The review begins with a brief description of Langmuir–Blodgett thin films based on FeII coordination compounds since it represents the first study of the spin crossover phenomenon in soft matter. The following section illustrates the FeII, FeIII and CoII complexes reported…
Reaktionen von Benzothiet mit Iminen
1993
Reactions of Benzothiete with Imines A great variety of compounds 3a–w containing CN double bonds was studied in the reaction with benzothiete (1). H, alkyl, aryl, OR, SR and NR groups can be attached to the imino function. The azomethines 3a–f, the thiazolines 3g–i, the lactim 3n, the oximes 3r–t, the isoxazolinone 3u and the azine 3v show [8π + 2π] cycloaddition reactions yielding derivatives of 1,3-benzothiazine (4a–i, n, r–v). In the case of 4n, s, t secondary reactions occur, initiated by elimination processes. [8π + 2π] Cycloadditions account also for the reactions 3e 10, 11, 3o 18(I), and 3q 19; however, CC double bonds are representing the 2π component in these examples. The thiazol…