Synthesis, Characterization and Antimicrobial and Anticancer Evaluations of Some Novel Heteroannulated Difuro[3,2-c:3',2'-g]Chromenes.

The goal of this study was directed to synthesize a novel class of annulated compounds containing difuro[3,2-c:3',2'-g]chromene. Friedländer condensation of o-aminoacetyl derivative 3 was performed with some active methylene ketones, namely, 1,3-cyclohexanediones, pyrazolones, 1,3-thiazolidinones and barbituric acids, furnished furochromenofuroquinolines (4,5), furochromenofuropyrazolopyridines (6-8), furochromenofurothiazolopyridines (9,10) and furochromenofuropyridopyrimidines (11, 12), respectively. Also, condensation of substrate 3 with 5-amine-3-methyl-1H-pyrazole and 6-amino-1,3-dimethyluracil, as cyclic enamines, resulted in polyfused systems 13 and 14, respectively. In vitro antimicrobial efficiency of the prepared heterocycles against microbial strains exhibited variable inhibition action, where compound 3 was the most effective against all kinds of microorganisms. A significant cytotoxic activity was seen upon the annulation of the starting compound with thiazolopyridine (9 and 10) as well as pyridopyrimidine moieties (11, 12 and 14). The spectroscopic and analytical results were used to infer the structures of the novel synthesized compounds.

TD-DFT calculations, dipole moments, and solvatochromic properties of 2-aminochromone-3-carboxaldehyde and its hydrazone derivatives.

2-Aminochromone-3-carboxaldehyde (ACC) and its hydrazones (ACMHCA and ACMNPHTCA) with semicarbazide hydrochloride and N-phenylthiosemicarbazide were synthesized and characterized by elemental analysis and spectral studies. The solvatochromic behavior of the title compounds in various solvents showed distinct bathochromic shifts on going from nonpolar to polar solvents, suggesting intramolecular-charge-transfer (ICT) solute-solvent interactions. The ground and excited state dipole moments of ACC, ACMHCA, and ACMNPHTCA were determined experimentally by the solvatochromic shift method using the Bilot-Kawski, Lippert-Mataga, Bakhshiev, Kawski-Chamma-Viallet functions, and a microscopic Reichardt's solvent polarity parameter (ENT). All the investigated molecules showed a substantial increase in the dipole moment upon excitation to the emitting state. The experimental results were generally consistent with the values obtained by the TD-DFT, B3LYP/6-311G++(d,p) method. Molecular electrostatic potential (MEP) mapping and natural charge and natural bonding orbital (NBO) analysis were performed and the results were discussed. The 1H NMR chemical shifts of the prepared compounds were simulated by the gage independent atomic orbital (GIAO) method and compared with their experimental chemical shift values. The biological activity data were correlated with the frontier molecular orbitals. The photovoltaic behavior of the title compounds showed there was sufficient electron injection.

Synthesis, spectral analysis, quantum studies, NLO, and thermodynamic properties of the novel 5-(6-hydroxy-4-methoxy-1-benzofuran-5-ylcarbonyl)-6-amino-3-methyl-1H-pyrazolo[3,4-b] pyridine (HMBPP).

Ring opening followed by ring closure reactions of 4-methoxy-5-oxo-5H-furo[3,2-g] chromene-6-carbonitrile (1) with 5-amino-3-methyl-1H-pyrazole (2) afforded the novel 5-(6-hydroxy-4-methoxy-1-benzofuran-5-ylcarbonyl)-6-amino-3-methyl-1H-pyrazolo[3,4-b] pyridine (3, HMBPP). The chemical structure of the synthesized compound was established based on elemental analysis and spectral data. The chemical calculations were performed using the Becke3-Lee-Yang-Parr (B3LYP) and Coulomb Attenuating Method (CAM-B3LYP)/6-311++G(d,p) basis sets at the DFT level of theory. The Coulomb-attenuating method (CAM-B3LYP) and Corrected Linear Response Polarizable Continuum Model (CLR) PCM were used to obtain the theoretical electronic absorption spectra in the gas phase, methanol, and cyclohexane, respectively, indicating good agreement with the observed spectra. The local reactivity descriptors supported the high reactivity of C7 for nucleophilic attack. The computed total energy and thermodynamic parameters at the same level of calculations confirmed the high stability of structure 3 (HMBPP) as compared with the other expected structure 4. The 1H and 13C chemical shift values, as well as vibrational wavenumber values, were theoretically determined and exhibited a high correlation with the experimental data. Natural bond orbital analysis (NBO) was used to investigate hyper conjugative interactions. The first static hyperpolarizability, second hyperpolarizability, polarizability, and electric dipole moment have been determined. At different temperatures, the thermodynamic properties of the compounds were calculated.

Synthesis, FT-IR, structural, thermochemical, electronic absorption spectral, and NLO analysis of the novel 10-methoxy-10H-furo[3,2-g]chromeno[2,3-b][1,3]thiazolo[5,4-e]pyridine-2,10(3H)-dione (MFCTP): a DFT/TD-DFT study.

Chemical transformation of 4-methoxy-5-oxo-5H-furo[3,2-g]chromene-6-carbonitrile (1) with 1,3-thiazolidine-2,4-dione (2) in boiling ethanol containing piperidine afforded the novel 10-methoxy-10H-furo[3,2-g]chromeno[2,3-b][1,3]thiazole[5,4-e]pyridine-2,10(3H)-dione (3, MFCTP). The chemical structure of the synthesized compound was established via elemental analysis and spectral data. FT-IR spectroscopy was performed in the range of 400-4000 cm-1 for the vibrational spectral analysis of MFCTP. The GIAO method was employed to calculate the values of 1H and 13C NMR chemical shifts theoretically, which were consistent with the experimental chemical shifts. The molecule (3, MFCTP) has two stable structures, as determined from the potential energy curve. The S1 structure is the most stable conformer of (3, MFCTP) according to the computational results. The density functional theory (DFT) and ab initio HF calculations and different basis set combinations based on the structure optimizations and normal coordinate force field were interpreted with the aid of the molecular structure, fundamental vibrational frequencies, and intensities of the vibrational bands. The potential energy distribution (PED) was determined based on the complete vibrational wavenumber assignments. The calculated spectra of the title compound were in agreement with the observed spectra. The scaled B3LYP/6-311++G(d,p) results exhibited better agreement with the experimental values compared to the other method used. The time-dependent density functional theory (TD-DFT) was employed to calculate the energy and oscillator strength and supplement the experimental findings. Also, it was performed and the results interpreted the molecular electrostatic potential, nonlinear optical and thermodynamic properties, and Mulliken and natural charges of the title compound. DFT calculations were performed to study the structure-activity relationship (SAR) and compared with the experimental antimicrobial results for compound (3, MFCTP).

Synthesis, molecular, electronic structure, linear and non-linear optical and phototransient properties of 8-methyl-1,2-dihydro-4H-chromeno[2,3-b]quinoline-4,6(3H)-dione (MDCQD): Experimental and DFT investigations.

Base catalysed ring opening ring closure (RORC) reaction of 6-methylchromone-3­carbonitrile (1) with 1,3-cyclohexanedione afforded 8-methyl-1,2-dihydro-4H-chromeno[2,3-b]quinoline-4,6(3H)-dione (MDCQD). Theoretical calculations by Density Functional Theory (DFT) at the B3LYP/6-311G (d,p) level of theory was utilized to illustrate the equilibrium geometries of MDCQD. Also, the nonlinear optical properties, simple harmonic vibrational frequencies, thermo-chemical parameters and Mullikan atomic charges were calculated. In addition, the electronic absorption spectra in polar and non polar solvents were discussed on the basis of TD-DFT calculations. A nanofiber-like structure with high aggregation was resolved by using scanning electron microscopy images and its particle sizes were measured by particle size analyzer. The spectroscopic characteristics of the prepared thin film of MDCQD were studied in a wide spectral range of 200-2500nm. The analysis of the absorption edges affords two direct optical band gaps with energies of 1.00 and 2.76eV. A characteristic emission peak of photoluminescence spectrum in the visible region was detected and has a red-shift as a result of solvent polarity. The MDCQD film based heterojunction showed rectification behavior and diode-like characteristics. The photovoltaic characteristics under illumination of 100mW/cm2 were studied. The open-circuit voltage and short-circuit current were found to be 0.22V and 4.25×10-7A/cm2, respectively. Moreover, the prepared heterojunction showed remarkable phototransient characteristics which afford the probability for the operation as a photodiode.