Synthesis, spectroscopic characterization and crystallographic behavior of ethyl 2-(4-methyl-(2-benzylidenehydrazinyl))thiazole-4-carboxylate: Experimental and theoretical (DFT) studies

Haroon, Muhammad; Akhtar, Tashfeen; Yousuf, Muhammad; Baig, Mirza Wasif; Tahir, Muhammad Nawaz; Rasheed, Lubna

doi:10.1016/j.molstruc.2018.04.083

Cited by 17 publications

(9 citation statements)

References 42 publications

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“…The planarity of the thiazole ring in two most closely related reported crystal structures, one having methyl substituted phenyl ring and second having bromo substituted phenyl ring was obvious by r.m.s. deviation of 0.004 and 0.0072 Å [ 25 ]. The nitro group C (N1/O1/O2) and carboxylate group D (C11/O3/O4) are oriented at a dihedral angle of 26.84 (10)° and 4.6 (5)° with the parent groups A and B, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…The nitro group C (N1/O1/O2) and carboxylate group D (C11/O3/O4) are oriented at a dihedral angle of 26.84 (10)° and 4.6 (5)° with the parent groups A and B, respectively. The C-atoms (C12/C13) are at a distance of -0.003 (11) and 1.329 (13) Å, respectively, from the carboxylate group as compared to their distance of 0.034 (16) and 1.440 (21) Å from the carboxylate group in closely related crystal structure having bromo substituted phenyl ring instead of nitro substituted phenyl ring [ 25 ]. Intramolecular H-bonding of type C–H…N and C–H…O are responsible for stabilization of molecular configuration.…”

Section: Resultsmentioning

confidence: 99%

“…Pre-coated Silica 60 HF 254 Aluminum sheets (Merck, Germany) were used to monitor the reaction with thin layer chromatography (TLC). The melting point determination, functional group identification, NMR chemicals shifts and single crystal analysis were carried out as reported elsewhere [ 25 ]. Dimethyl sulfoxide-deuterated (DMSO- d 6 ) was used to record the proton and carbon NMR (nuclear magnetic resonance), using 300 and 75 MHz frequency, respectively.…”

Section: Methodsmentioning

confidence: 99%

“…The reaction progress assessed by TLC. When the reactants consumed, as shown by TLC, quenching of reaction by adding ice cold water resulted into precipitates, which on filtration and washing with excess of water yielded pure compound [ 25 ].…”

Section: Methodsmentioning

confidence: 99%

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Synthesis, crystal structure, Hirshfeld surface investigation and comparative DFT studies of ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate

et al. 2022

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The ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate (1), a thiazole ester, was synthesized by refluxing 1-(2-nitrobenzylidene)thiosemicarbazide and ethyl bromopyruvate. The compound is characterized by spectrometric, spectroscopic and single crystal (SC-XRD) techniques. Non-covalent interactions that are responsible for crystal packing are explored by Hirshfeld surface analysis. All theoretical calculations were performed by DFT quantum chemical methods using 6-311G(d,p) and cc-pVTZ basis sets and compared. Theoretical harmonic frequencies of ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate (1) were optimized. Confirmation of hydrogen bonding sites was analyzed by molecular electrostatic potential (MEP) and Mulliken population analysis. The vibrational frequencies of characteristic functional groups and chemical shifts were found in good agreement with experimental assignments. Frontier molecular orbital (FMO) revealed relatively small HOMO–LUMO (highest occupied molecular orbital-lowest unoccupied molecular orbital) gape, which speaks off the nearly planar geometry and extended conjugation, as compared to the substituents with no conjugation possible. It has also been observed that –NO2 substituent plays a vital role for this relatively small HOMO–LUMO gape and overall electronic properties when compared with similar thiazole carboxylates (2–6, Table 6). Ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate (1) was also evaluated for its anti-oxidant and anti-microbial activities. Graphical Abstract

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Synthesis, crystal structure, Hirshfeld surface investigation and comparative DFT studies of ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate

et al. 2022

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“…As well as other industrially important activities, including antifouling and anticorrosion effects (25,26) have also been reported for these compounds. Moreover, The imine bond (C = N) in these compounds are useful in the organic synthesis, in particular for the synthesis of many of pharmaceutical and bioactive heterocycles such as, thiazoles (27)(28)(29)(30)(31), 1,3,4-thiadiazoles (32), thiazolidinones (33,34), quinolines (35), naphthyridines (36), oxadiazoles (37,38), pyrimidines (39). Water plays an important role in our life.…”

Section: Introductionmentioning

confidence: 99%

Transalkylidation reaction: green, catalyst-free synthesis of thiosemicarbazones and solving the NMR conflict between their acyclic structure and intramolecular cycloaddition products

El‐Atawy

Omar

Hagar

et al. 2019

Green Chemistry Letters and Reviews

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A series of arylidene thiosemicarbazides have been prepared by a new method, which was titled as transalkylidation. This method is an effective, fast, green and clean method. The mechanism of this reaction has been discussed. Moreover, we clarified the divergences of the structural assignments reported in the literature for the reaction of thiosemicarbazide and aldehydes or ketones in the presence of different catalysts. Where 1,2,4-triazolidine-3-thiones were incorrectly reported as sole product of such reaction, based on occurance of intramolecular cycloaddition of thiosemicarbazones formed in situ. Our findings proved that the reaction stops at earlier stage of thiosemicarbazone and neither cyclization to 1,2,4-triazolidine-3-thiones nor 2-amino-1,3,4-thiadiazoline take place. We have removed the confusion of the NMR interpretation of thiosemicarbazone and their cycloaddition product by carrying out 1 H-NMR, 13 C-NMR, 15 N-NMR and 1 H-15 N HSQC experiments with temperature gradient. Furthermore, DFT-NMR calculations have been done to make structural distinguish between the three possible structural isomers for this reaction, namely, 1,2,4triazolidene-3-thione, 2-amino-1,3,4-thiadiazoline and thiosemicarbazone.

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Synthesis of Thiazole‐Chalcone Hybrid Molecules: Antioxidant, Alpha(α)‐Amylase Inhibition and Docking Studies

Iqbal

Akhtar

Haroon

et al. 2023

Chemistry & Biodiversity

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The molecular hybrid approach is very significant to combat various drug-resistant disorders. A simple, convenient, and cost-effective synthesis of thiazole-based chalcones is accomplished, using a molecular hybrid approach, in two steps. The compound 1-(2-phenylthiazol-4-yl)ethanone (3) was used as the main intermediate for the synthesis of 3-(arylidene)-1-(2-phenylthiazol-4-yl)prop-2-en-1-ones (4a-f). Thin layer chromatography was used to testify the formation and purity of all synthesized compounds. Further structural confirmation of all compounds was achieved via different spectroscopic techniques (UV, FT-IR, 1 H-and 13 C-NMR) and elemental analysis. All synthesized compounds were tested for their α-amylase inhibition and antioxidant potential. The cytotoxic property of compounds was also tested with in vitro haemolytic assay. All tested compounds showed moderate to excellent α-amylase inhibition and antioxidant activity. All tested compounds are found safe to use due to their less toxicity when compared to the standard Triton X. The molecular docking simulation study of all synthesized compounds was also conducted to examine the best binding interactions with human pancreatic αamylase (pdb: 4 W93) using AutodockVina. The molecular docking results authenticated the in vitro amylase inhibition results, i.e., 3-(3-Methoxyphenyl)-1-(2-phenylthiazol-4-yl)prop-2-en-1-one (4e) exhibited lowest IC 50 value 54.09 � 0.11 μM with a binding energy of À 7.898 kcal/mol.

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Synthesis, spectroscopic characterization and crystallographic behavior of ethyl 2-(4-methyl-(2-benzylidenehydrazinyl))thiazole-4-carboxylate: Experimental and theoretical (DFT) studies

Cited by 17 publications

References 42 publications

Synthesis, crystal structure, Hirshfeld surface investigation and comparative DFT studies of ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate

Synthesis, crystal structure, Hirshfeld surface investigation and comparative DFT studies of ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate

Transalkylidation reaction: green, catalyst-free synthesis of thiosemicarbazones and solving the NMR conflict between their acyclic structure and intramolecular cycloaddition products

Synthesis of Thiazole‐Chalcone Hybrid Molecules: Antioxidant, Alpha(α)‐Amylase Inhibition and Docking Studies

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