Straightforward green synthesis of indeno-furan carboxylates from ninhydrin and β-ketoesters: X-Ray crystal structure, Hirshfeld and DFT investigations

Boraei, Ahmed T. A.; Soliman, Saied M.; Haukka, Matti; Salama, Eid E.; Sopaih, Manar; Barakat, Assem; Sarhan, Ahmed A. M.

doi:10.1016/j.molstruc.2022.132433

Cited by 7 publications

(3 citation statements)

References 28 publications

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“…The authors revised their structures with the help of GIAO NMR calculations. Sarhan et al 64 reported on green synthesis of indeno-furan carboxylates, discussed their crystal structure and performed GIAO NMR calculations to support experimental spectra in solution. Cardoso and Colherinhas 65 studied fullerene C60 dynamics in ionic liquid and water and the solute-solvent interactions using molecular dynamic methods and GIAO NMR calculations.…”

Section: Dft Studies Of Nuclear Shieldingmentioning

confidence: 99%

Theory and computation of nuclear shielding

2023

Nuclear Magnetic Resonance

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This chapter continues earlier reviews of essential works on theoretical issues of nuclear magnetic shieldings published from 1 January to 31 December 2022. As previously, the chapter concentrates on theoretical calculations of nuclear shielding parameters and/or chemical shifts in case of free molecules in the gas phase and solution, and in some cases in the solid state using a periodic formulation. The nuclear shieldings in solution are mainly calculated using inexpensive polarizable continuum model of solvent (PCM). The use of discrete solvent molecules (in particular water and other polar solvents), which is essential for correct description of hydrogen bonding, is often omitted by numerous authors. Most calculations use a relatively simple and fast, but reliable density functional theory (DFT) combined with gauge-including atomic orbital (GIAO) approach. On the other hand, reports on prediction of nuclear magnetic shielding parameters using high level theoretical methods combined with large and flexible basis sets are not so common due to the enormous computational cost. In addition, correction of raw theoretical nuclear magnetic shieldings due to ro-vibration (zero-point vibration correction, ZPVC) and temperature corrections (TC), as well as implicit and explicit solvent effects and relativistic corrections are not often reported.

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Section: Dft Studies Of Nuclear Shieldingmentioning

confidence: 99%

Theory and computation of nuclear shielding

2023

Nuclear Magnetic Resonance

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“…The reaction of hydrazine hydrate with ethyl 3-formyl-1H-indole-2-carboxylate (i.e., ester 1) in ethanol afforded 3,5-dihydro-4H-pyridazino [4,5-b]indol-4-one (i.e., substance 2). Thionation of substance 2 to a thione (i.e., compound 3) was conducted using P 2 S 5 in pyridine [34,35]. The structure of compound 3 was deduced from 1 H and 13 C NMR spectra, which showed an indole NH signal at 12.54 ppm and a pyridazine NH signal at 14.47 ppm.…”

Section: Chemistrymentioning

confidence: 99%

Synthesis, X-ray Single-Crystal Analysis, and Anticancer Activity Evaluation of New Alkylsulfanyl-Pyridazino[4,5-b]indole Compounds as Multitarget Inhibitors of EGFR and Its Downstream PI3K-AKT Pathway

et al. 2022

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The alkylation of 3,5-dihydro-4H-pyridazino[4,5-b]indole-4-thione with benzyl bromide, ethyl chloroacetate, and allyl bromide in the presence of potassium carbonate (K2CO3) yielded new alkylsulfanylpyridazino[4,5-b]indole derivatives (i.e., compounds 4–6). Hydrazinolysis of ester 6 resulted in hydrazide 7. The structure of compound 6 was verified by X-ray single-crystal analysis. Among the synthesized compounds, compound 6 exhibited the most promising cytotoxicity toward MCF-7 cells with an IC50 value of 12 µM. It showed potential inhibition activity toward EGFR, PI3K, and AKT in MCF-7 cells, with 0.26-, 0.49-, and 0.31-fold reductions in concentration compared to an untreated control. Additionally, it showed apoptosis-inducing activity in MCF-7 cells (47.98-fold); overall apoptosis increased to 38.87% compared to 0.81% in the untreated control, which disrupted the cell cycle at pre-G1 and S phases. Moreover, compound 6 exhibited good binding affinities toward the tested proteins (EGFR, PI3K, and AKT) and had binding energies ranging from −15.87 to −24.87 Kcal/mol. It also formed good interactions with essential amino acids inside the binding sites. Hence, compound 6 is recommended as an anti-breast cancer chemotherapeutic due to its effects on the EGFR-PI3K-AKT pathway.

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“…Additionally, this process can be used to create benzo[c] [2,6]naphthyridines and chromeno [4,3-c]pyridines in mild yields [30]. Recent research by Boraei et al has shown a simple and sustainable approach to the creation of tatraazafluoranthenones by using β-ketoesters such as ethyl acetoacetate and ethyl benzoylacetate with ninhydrin in green solvents such as water [31][32][33].…”

Section: Introductionmentioning

confidence: 99%

4-Methyl/Phenyl-1,2,5,6-tetraazafluoranthen-3(2H)-ones Synthesis: Mechanistic Pathway Study and Single-Crystal X-ray Analysis of the Intermediates

Sarhan,

Haukka,

Barakat

et al. 2023

Crystals

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The synthesis of 4-methyl/phenyl-1,2,5,6-tetraazafluoranthen-3(2H)-one 4 and 7 has been reported with ninhydrin via a reaction first with ethyl acetoacetate or ethyl benzoylacetate and then a reaction of the resultant esters with hydrazine hydrate. The mechanism of hydrazinolysis and cyclization to obtain tetraazafluoranthen-3(2H)-ones is ambiguous, and the previously proposed mechanism was not based on facts because the actual intermediates were not isolated. Herein, the important intermediates involved in the hydrazinolysis–cyclization mechanistic pathway were isolated and characterized using NMR and X-ray single-crystal analysis. The intermediates demonstrate that the reaction carried out via two hydrazinolysis–cyclization reactions, the first of which includes the condensation of one hydrazine molecule with two ketone groups and the second of which includes the reaction of another hydrazine molecule with the ester and then condensation with the other ketone group. The stability of hydrazide 11 enabled the hydrazine to reduce the carbonyl of the ketone group to form 12 via a Wolff–Kishner-like reduction. The structure of the three intermediates was confirmed using X-ray crystallographic analysis. It was found that the three fused ring systems deviated from planarity to different extents, with their deviation from being coplanar reaching up to 5.3°. The possible non-covalent interactions which control the molecular packing of these intermediates were elucidated with the aid of Hirshfeld analysis.

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Straightforward green synthesis of indeno-furan carboxylates from ninhydrin and β-ketoesters: X-Ray crystal structure, Hirshfeld and DFT investigations

Cited by 7 publications

References 28 publications

Theory and computation of nuclear shielding

Theory and computation of nuclear shielding

Synthesis, X-ray Single-Crystal Analysis, and Anticancer Activity Evaluation of New Alkylsulfanyl-Pyridazino[4,5-b]indole Compounds as Multitarget Inhibitors of EGFR and Its Downstream PI3K-AKT Pathway

4-Methyl/Phenyl-1,2,5,6-tetraazafluoranthen-3(2H)-ones Synthesis: Mechanistic Pathway Study and Single-Crystal X-ray Analysis of the Intermediates

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