1H NMR and kinetics studies of the reaction of 4-methyl, 4-bromo and 3-trifluoromethyl benzyltriflones with aromatic nitro-compounds

AbstractRate measurements are reported for the reactions in methanol of carbanions derived from benzyltriflones, 2a–c, with 4-nitrobenzofurazan derivatives, 4a and 4b, to give anionic σ-adducts. 1H NMR studies in DMSO-d6 of the reaction of benzyltriflones, 2, and 4-nitrobenzofurazan, 4a, in the presence of triethylamine are consistent with products formed by the elimination of trifluoromethyl sulfinic acid from σ-adducts initially formed by carbanion attack at the 5-position of 4a. Evidence for the high steric requirements of the benzyltriflone anions come from the low value of β; the slope of the linear plot of values of logk5 versus pKa

Novel functional [4]helicenes through a photooxidation pathway. Investigation of the absorption and fluorescence in solution

Novel functional [4]helicenes have been designed and synthesized, in 54%–72% overall yields, through an operational and simple two-step photochemical approach starting from various p-substituted phenylacetonitriles, and were characterized by NMR ($^{1}$H, $^{13}$C, and COSY) and FT-IR spectroscopies. UV–Vis absorption properties of these tetracyclic ${\pi }$-conjugated systems have been experimentally investigated in various solvents and their optical gap energy was estimated to be less than 3.28 eV. The photoluminescence properties of these molecules have been evaluated in solutions and an emission in the blue region of the visible spectrum was noted. The obtained results seem encouraging for the examination of such compounds as promising materials for optoelectronic applications

Novel functional [4]helicenes through a photooxidation pathway. Investigation of the absorption and fluorescence in solution

Novel functional [4]helicenes have been designed and synthesized, in 54%–72% overall yields, through an operational and simple two-step photochemical approach starting from various p-substituted phenylacetonitriles, and were characterized by NMR ($^{1}$H, $^{13}$C, and COSY) and FT-IR spectroscopies. UV–Vis absorption properties of these tetracyclic ${\pi }$-conjugated systems have been experimentally investigated in various solvents and their optical gap energy was estimated to be less than 3.28 eV. The photoluminescence properties of these molecules have been evaluated in solutions and an emission in the blue region of the visible spectrum was noted. The obtained results seem encouraging for the examination of such compounds as promising materials for optoelectronic applications

7-Cyano-15-methoxy[6]helicene through a photochemical pathway and investigation of its chiroptical and photophysical properties

7-Cyano-15-methoxy[6]helicene was synthesized, in 54% overall yield, through a short photochemical procedure including mild conditions and inexpensive reagents. The desired helical hexacyclic framework was characterized by $^{1}\mathrm{H}$ and $^{13}\mathrm{C}$ NMR and mass spectroscopies. Single crystals of the helicene were also obtained and an X-ray diffraction analysis is presented. Enantiomers of the helicene were obtained in 100% $ee$ after separation by chiral HPLC and their chiroptical properties were experimentally investigated from optical rotatory dispersion and electronic circular dichroism (ECD). UV–Vis absorption and fluorescence properties of the helicene were evaluated in solutions and a strong emission was noted in the blue region of the visible spectrum . Its electrochemical behavior was also experimentally examined and HOMO and LUMO energy levels were estimated, showing an electrochemical band gap of 2.11 eV. The results obtained herein are helpful to explain the interest of cyano and methoxy groups in making the new material a good candidate to be used in optoelectronic applications

7-Cyano-15-methoxy[6]helicene through a photochemical pathway and investigation of its chiroptical and photophysical properties

7-Cyano-15-methoxy[6]helicene was synthesized, in 54% overall yield, through a short photochemical procedure including mild conditions and inexpensive reagents. The desired helical hexacyclic framework was characterized by $^{1}\mathrm{H}$ and $^{13}\mathrm{C}$ NMR and mass spectroscopies. Single crystals of the helicene were also obtained and an X-ray diffraction analysis is presented. Enantiomers of the helicene were obtained in 100% $ee$ after separation by chiral HPLC and their chiroptical properties were experimentally investigated from optical rotatory dispersion and electronic circular dichroism (ECD). UV–Vis absorption and fluorescence properties of the helicene were evaluated in solutions and a strong emission was noted in the blue region of the visible spectrum . Its electrochemical behavior was also experimentally examined and HOMO and LUMO energy levels were estimated, showing an electrochemical band gap of 2.11 eV. The results obtained herein are helpful to explain the interest of cyano and methoxy groups in making the new material a good candidate to be used in optoelectronic applications

Study of Kinetics, Equilibrium and the Influence of Steric Effects on Proton-Transfer in the Reactions of 2, 2, 4- and 2, 6- Substituted Anilines with 2-Phenoxy-3,5-dinitropyridine in DMSO

Kinetic and equilibrium results for the reactions of 2-phenoxy-3,5-dinitropyridine (1), with a series of 2, 2, 4- and 2, 6- substituted anilines (2a-f), in the presence of DABCO in DMSO are reported. The reactions yield the 2-anilino derivatives (5), without the accumulation of intermediates. Kinetics studies are compatible with a two-step mechanism involving initial nucleophilic attack by amine at the ring carbon substituted by phenoxy group followed by either base-catalyzed or uncatalyzed conversion to the product. The base-catalyzed pathway is likely to involve rate-limiting proton-transfer from the zwitterionic intermediate to base. This work indicates a steric effect to proton transfer in reactions involving 2, 6-disubstituted anilines. The results were compared with those for reactions of 1, 3, 5-trinitrobenzene with anilines

Kinetic, mechanistic, and spectroscopic studies of permanganate oxidation of azinylformamidines in acidic medium, with autocatalytic behavior of manganese(II)

The kinetics of permanganate oxidation of two substituted azinylformamidines (Azn-Fs), namely N,N-dimethyl-N′-(pyridin-2-yl)formamidine (Py) and N,N-dimethyl-N′-(pyrimidin-2-yl)formamidine (Pym), in sulfuric acid were investigated using conventional spectrophotometry. Kinetic evidence for the formation of 1:1 intermediate complexes between the oxidant and substrates was obtained. The reactions of both substrates with permanganate showed similar kinetics, i.e. first order in [MnO4−]0 and fractional-first-order with respect to both [Azn-F]0 and [H+]. The initial product, Mn2+, was found to autocatalyze the oxidation process. Changes in the ionic strength and dielectric constant of the medium had no significant effect on the rate. The final oxidation products of Py and Pym were identified as 2-aminopyridine and 2-aminopyrimidine, respectively, in addition to dimethylamine and carbon dioxide. A plausible reaction mechanism is suggested and the reaction constants involved in the mechanism were evaluated

Copper(II) catalysis for oxidation of l-tryptophan by hexacyanoferrate(III) in alkaline medium: A kinetic and mechanistic approach

The catalytic effect of copper(II) catalyst on the oxidation of l-tryptophan (Trp) by hexacyanoferrate(III) (HCF), has been investigated spectrophotometrically in an aqueous alkaline medium at a constant ionic strength of 0.5 mol dmâ3 and at 25 °C. The stoichiometry for both the uncatalyzed and catalyzed reactions was 1:2 (Trp:HCF). The reactions exhibited first order kinetics with respect to [HCF] and less than unit orders with respect to [Trp] and [OHâ]. The catalyzed reaction exhibited fractional-first order kinetics with respect to [CuII]. The reaction rates were found to increase as the ionic strength and dielectric constant of the reaction medium increase. The effect of temperature on the rates of reactions has also been studied, and the activation parameters associated with the rate-determining steps of the reactions have been evaluated and discussed. Addition of the reaction product HCF(II) to the reaction mixture did not affect the rates. Plausible mechanistic schemes for uncatalyzed and catalyzed reactions explaining all of the observed kinetic results have been proposed. In both cases, the final oxidation products are identified as indole-3-acetaldehyde, ammonia, and carbon dioxide. The rate laws associated with the reactionsâ mechanisms are derived. The rate constants of the slow steps of the reactions along with the equilibrium constants are also calculated. Keywords: Oxidation, Kinetics, l-Tryptophan, Hexacyanoferrate(III), Copper(II), Catalysi

Synthesis, anticancer activity, and molecular docking of new pyrazolo[1,5-a]pyrimidine derivatives

The reaction of 3-aminopyrzoles with dimethylamino-acrylonitrile derivatives was utilized for the production of new functionalized pyrazolopyrimidine compounds 4a-c and 6a-c. The structures of the obtained pyrazolopyrimidines were characterized by the different spectroscopic measurements (IR, NMR, and mass analyses). The DFT quantum chemical calculations were applied to the determination of the HOMO-LUMO energies and Mulliken atomic charges. The investigated derivatives exhibited a low HOMO-LUMO energy gap, ranging from 2.70 to 2.34 eV, 4c and both 4b and 6b, respectively. Furthermore, the anticancer activities of the synthesized compounds have also been investigated against four cancer cells as well as normal cells (WI38). The investigated compounds demonstrated an impressive cytotoxic effect on MCF-7 and Hep-2 cells. On comparison with 5-fluorouracil, pyrazolopyrimidines 6a–c showed promising cytotoxic action against MCF-7 and Hep-2, with IC50 values of 18.31–26.51 and 24.15–27.16 μM, respectively. Molecular docking of the prepared pyrazolopyrimidines 4 and 6 with the crystal structure of the KDM5A protein, obtained from the PDB, revealed the types of the protein's binding sites