Structural characterization and keto-enol tautomerization of 4-substituted pyrazolone derivatives with DFT approach.

The synthesis of two pyrazolone derivative compounds, PYR-I(4-Acetyl-1-(4-chlorophenyl)-3-isopropyl-1H-pyrazol-5(4H)-one) and PYR-II1-(4-Chlorophenyl))-3-isopropyl-5-oxo-4,5-5-dihydro-1H-pyrazole-4-carbaldehyde, their characterization by FT-IR, NMR, UV-Vis and GC-MS techniques, and the evaluation of the keto-enol tautomerization process of the structures along with the DFT approach and spectral data were reported in this paper. Spectral findings indicated that PYR-I was stable at the keto state. The IR spectrum recorded in solid form showed that the PYR-II structure was stable in the enol state, while the NMR spectrum in the solution medium showed that it was stable in the keto state. DFT-based analyses were realized with the B3LYP hybrid functional and the 6-311++G(d,p) basis set. The modelled keto, transition and enol state molecular geometries of structures were optimized in the gas phase and different solvent media and the total energy and dipole moment values were investigated at the specified theoretical level. The possible keto-enol tautomerism mechanism of the structures was evaluated through some thermodynamic parameters such as the difference in free Gibbs energy (ΔG), enthalpy (ΔH), entropy (ΔS), and predictive tautomeric equilibrium constants (Keq), acidity constants (pKa) and percentages of tautomers at 298.15 K and 1 atm pressure. The results of these analyses based on the DFT approach indicated that the keto-enol tautomer equilibrium heavily favours the keto form for PYR-I and the enol form for PYR-II in all cases. Moreover, natural bond orbital (NBO) analysis was performed for the tautomers, and the chemical reactivity profiles of the most stable tautomers were examined with the values of frontier molecular orbital energy and some reactivity descriptors.

Bioactive Properties and Phytochemical Screening of Mad Honey Bee Pollen.

INTRODUCTION: Mad honey is widely used in folk medicine in the Black Sea region of Turkey for its medicinal properties, but its pollen is not collected by mad honey producers and its benefits are unknown. METHODS: In this study, water and ethanol extracts of mad honey bee pollen from four different plateaus in the Black Sea region of Turkey were researched for their antioxidant and antimicrobial properties. Phytochemical analyses were carried out and the data were supported with UV-Vis spectrophotometry. Antimicrobial activity was researched against four Gram-positive and four Gram-negative bacteria, one fungus, and one yeast. The results were compared with standard antioxidants and antibiotics. RESULTS: The ethanol extracts of the samples from Sinop (P5), Giresun (P7), and Trabzon (P8) were the most active samples as antioxidants, and almost all the extracts of R. ponticum bee pollen were effective on the tested microorganisms. However, P5-8 showed better values for B. cereus, E. feacalis, E. coli, and P. aeruginosa. CONCLUSION: It has been proven that mad honey bee pollen is a natural product with previously unknown medicinal properties and rich phytochemical content. Future research and clinical trials are important to scientifically support its benefits in complementary medicine.

A Multidisciplinary Approach to Coronavirus Disease (COVID-19).

Since December 2019, humanity has faced an important global threat. Many studies have been published on the origin, structure, and mechanism of action of the SARS-CoV-2 virus and the treatment of its disease. The priority of scientists all over the world has been to direct their time to research this subject. In this review, we highlight chemical studies and therapeutic approaches to overcome COVID-19 with seven different sections. These sections are the structure and mechanism of action of SARS-CoV-2, immunotherapy and vaccine, computer-aided drug design, repurposing therapeutics for COVID-19, synthesis of new molecular structures against COVID-19, food safety/security and functional food components, and potential natural products against COVID-19. In this work, we aimed to screen all the newly synthesized compounds, repurposing chemicals covering antiviral, anti-inflammatory, antibacterial, antiparasitic, anticancer, antipsychotic, and antihistamine compounds against COVID-19. We also highlight computer-aided approaches to develop an anti-COVID-19 molecule. We explain that some phytochemicals and dietary supplements have been identified as antiviral bioproducts, which have almost been successfully tested against COVID-19. In addition, we present immunotherapy types, targets, immunotherapy and inflammation/mutations of the virus, immune response, and vaccine issues.

Photophysical Properties of New Pyrazolone Based Azo- Compounds.

New 5-pyrazolone based azo- dyes (2-5) and a bisazo- dye (6) were synthesized via diazo- coupling reaction with substituted aryl amines. All azo-5-pyrazolone compounds were characterized with the aid of FTIR, UV-Vis., 1H NMR, 13C NMR-APT and, GC-MS or ESI(+)-MS spectroscopic techniques. NMR studies showed that all azo- and bisazo- compounds, are in hydrazo-keto form except compound 5 which is in enol-azo form in solution. FTIR(ATR) studies indicated that compounds 2 and 4 are in azo-keto form, compounds 3 and 6 are in hydrazo-keto form and compound 5 is in enol-azo form in the solid state. All newly synthesized compounds were investigated for their absorption and emission characteristics. Photophysical properties of the solvent polarity effect and acid/base effect on the absorption and emission spectra were evaluated for an azo- (2) and a bisazo- compound (6). All azo-5-pyrazolone compounds showed fluorescence properties and the solvents with different polarities gave rise to shifts in the absorption and emission spectra of 2 and 6. The base addition did not affect the emission spectra while changing the absorption properties of the azo- and bisazo- compounds. Thermal work of 2 and 6 were carried out with TG/DTG technique and the results showed that compound 2 had adequate stability for industrial applications as a fluorescent material.

Regio- and stereoselective aminopentadienylation of carbonyl compounds.

A simple and robust protocol is detailed for the preparation of enantioenriched α-substituted (1,4-pentadien-3-yl)amine derivatives. The methodology involves the addition of an in situ formed pentadienyl indium reagent to chiral tert-butylsulfinimines, previously formed in the same pot. The addition takes place with excellent γ-regio- and diastereoselectivity for a wide range of carbonyl compounds, including α-unsubstituted aldehydes and methyl alkyl ketones. The catalytic hydrogenation of the sulfinamines obtained provides a convenient access to chiral α-substituted (3-pentyl)amines. The hydroboration-oxidation of the α-(1,4-pentadien-3-yl)amine derivatives, followed by a cyclization under Mitsunobu conditions, takes place with an excellent diastereoselectivity governed by the chiral sulfinyl group.

Synthesis of new pyrazolothiazole derivatives from 4-thiazolidinones.

The synthesis of new 2,3,5,6-aryl substituted tetrahydro-2H-pyrazolo[3,4-d]- thiazoles 4a-j as potential biologically active compounds by the cyclocondensation of phenyl hydrazine with new 5-arylidene derivatives 2a-j of 2,3-disubstituted-1,3- thiazolidin-4-ones 1a-e is reported.

Epibatidine alkaloid chemistry: 5. Domino-Heck reactions of azabicyclic and tricyclic systems.

Palladium-catalyzed hydroarylations and additional domino reactions of aza-bicyclic and tricyclic norbornene derivatives were investigated and a series of new epibatidine analogues were synthesized.