Synthesis, spectrophotometric characterization and DFT computational study of a novel quinoline derivative, 2-amino-4-(2,4,6-trinitrophenylamino)-quinoline-3-carbonitrile

doi:10.1016/j.molliq.2017.11.071

Journal of Molecular Liquids

Volume 249, January 2018, Pages 501-510

https://doi.org/10.1016/j.molliq.2017.11.071 Get rights and content

Highlights

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New quinoline derivative has been synthesized (ATQC).
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The stoichiometry of solid ATCQ is 1:1 (DAQC:PA).
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The solid ACTQ is studied by different spectral techniques.
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DFT computations confirmed the high stability of ATQC.
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The ATQC stability is based on existence intramolecular charge transfer.

Abstract

A novel quinoline derivative, 2-amino-4-(2,4,6-trinitrophenylamino)-quinoline-3-carbonitrile (ATQC) has been synthesized through condensation reaction between 2,4-diaminoquinoline-4-carbonitrile (DAQC) with picric acid (PA) in methanol. It has been proven by elemental analysis that the reaction proceeded based on 1:1 stioichiometric ratio (DAQC:PA). Infrared spectra assert the formation of the investigated compound; its stability is based on the formation of hydrogen bonding NH single bond O beside charge transfer interaction. In addition, both ¹H NMR and ¹³C NMR spectra reconfirmed the formation of the new compound, including both charge and hydrogen bonding. The investigated reaction has been carried out in acetonitrile (AN), methanol (MeOH) and ethanol (EtOH) where it has been proceeded through 1:1 stoichiometric ratio concordant with elemental analysis. It recorded high stability constant from Bensie-Hildebrand equation in methanol relative to acetonitrile or ethanol. Computational analysis using density functional theory (DFT) at B3LYP/6-31G (d, p) basis set using Gaussian 09 W software also, asserted the high stability of the new compound based on the formation of strong hydrogen bonding between NH and neighboring nitro group. Furthermore, the optimization energy, geometrical structures, orbital energies, energy gap were determined. Quantum chemical reactivity parameters, including electronegativity, hardness, softness, electrophilicity index and chemical potential were determined from HOMO and LUMO energies. Molecular electrostatic potential were computed where a charge transfer was evidenced from DAQC towards PA and the LUMO are located at the nitro groups of PA moiety. This situation was found to go in harmony with Mullikan atomic charges calculated at the same level of theory. A complete analysis of the experimental spectra (FT-IR, ¹H NMR and UV–Vis) have been given with TD-DFT at the same basis set. A good consistency between experimental and theoretical calculations was found confirming that the applied basis set is the suitable one for the system under investigation.

Graphical abstract

Introduction

Quinoline nucleus occurs in several natural compounds as Cinchona Alkaloids and also, pharma-cologically active substances displaying a broad range of biological activity. Chloroquine, primaquine, pamaquine, and bulaquine show good examples of the drugs containing the quinoline scaffold that are used for the treatment of malaria [1], [2], [3]. Fluoroquinolones [4], [5] are known to display anti-TB activity. Quinoline-based well-known drug mefloquine is widely used for the prophylaxis of chloroquine-resistant Plasmodium falciparum malaria [6], [7].

Recently, we have described and characterized many systems including charge and hydrogen bonding interactions alones and together, the produced complexes exhibited high stability as can be proven from electronic, infrared and nuclear magnetic resonance spectroscopy. Furthermore, the structures of these complexes were complemented using density functional theory as well as time dependent density functional theory TD-DFT which add more information's about the stability of these complexes in presence of charge and proton transfers interactions [8], [9], [10], [11], [12], [13], [14], [15], [16], [17], [18], [19], [20], [21], [22].

Keeping in view the pharmaceutical and biological importance of quinolines and in continuation of our experts on proton and charge transfer reactions. We will synthesize and characterize a new quinoline derivative (ATCQ) from the condensation reaction of 2,4-diamino quinoline-3-carbonitrile with picric acid in methanol. The produced (ATCQ) will be characterized using elemental analysis, vibrational, nuclear magnetic resonance as well as UV–Vis spectroscopies. Density functional theory based on Gaussian computations will be applied to compliment the experimental work of the novel compound through computing optimization energy, geometric parameters, Mullikan atomic charges and molecular electrostatic potential of the optimized Structures of reactants and product at DFT/B3LYB/6-31G (d, p) level of the theory. Furthermore, complete analysis of the experimental spectroscopic results will be given at DFT and TD-DFT methods. A comparison between theoretical and experimental results will be carried out to check the validity of the applied basis set for the present computations.

Section snippets

Materials, instrumentation and physical measurements

All chemical used were of analytical grade. Picric acid was supplied by Aldrich (Cambridge, UK). Spectroscopic grade solvents were used without further purification. The infrared spectra of the reactants and prepared solid complex were measured as KBr disks on Perkin-Elmer model Frontier (USA). ¹H NMR (600 and 850 MHz) and ¹³C NMR (150 and 217.5 MHz) spectra were measured on a Bruker DPX spectrometers using 10 mg of the sample in dimethysulfoxide (DMSO-d₆) as solvent and tetramethylsilane as an

DFT computations

The reactants (PA and DAQC) and the product (ATCQ) were calculated using B3LYP at 6-31G (d, p) as basis set [24]. The optimization processing was carried out by the aid of Gaussian 09 W package [25]. No imaginary frequency has been recorded during the optimization process and we have not applied any constrains during the optimization. Gauss View 5.0 and Chemcraft programs [26] have been used to extract the computation results and to visualize the optimization structures as well as to draw the

Infrared spectra

The infrared spectrum of the formed ATCQ is presented in Fig.1 as KBr pellet. An interesting observation from Fig.1, is the disappearance of the stretching frequency of picric acid hydroxyl group at 3103 cm^− 1 and the appearance of ν_S (NH₂) and ν_as (NH₂) for one amino group at 3536 and 3427 cm^− 1 compared with two amino group at (3397, 3390 cm^− 1) and (3318, 3312 cm^− 1) for free DAQC. The situation strongly confirms the involvement of one amino group in chemical reaction with hydroxyl group of picric

Conclusion

New quinoline derivative 2-amino-4-(2,4,6-trinitrophenylamino)-quinoline-3-arbonitrile (ATQC) had been synthesized by condensation reaction between 2,4-diamino-3-quinoline-3-carbonitrile with picric acid in methanol. The new compound had been characterized experimentally and theoretically using various tools. Elemental analysis showed that the stoichiometric ratio is 1:1 (DAQC:PA). Infrared, NMR and UV–Vis spectroscopy asserted the formation of the new compound from the appearance of new peaks

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Citation Excerpt :
This frequency value shows good harmony with the computed one, observed at 1626 cm−1. The characteristic aromatic CC stretching vibrations arises in the 1610–1450 cm−1 [47]. In the theoretical funding spectrum, the obtained bands at 1556, 1530, 1518 and 1483 cm−1 were assigned to CC vibrations and the experimental frequencies of CC stretching are showed at 1570 and 1510 cm−1 in the FT-IR spectrum of RS.
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Synthesis, spectrophotometric characterization and DFT computational study of a novel quinoline derivative, 2-amino-4-(2,4,6-trinitrophenylamino)-quinoline-3-carbonitrile

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials, instrumentation and physical measurements

DFT computations

Infrared spectra

Conclusion

Curr. Opin. Microbiol.

Spectrochim. Acta A

J. Mol. Liq.

J. Mol. Struct.

Spectrochim. Acta A

J. Pharm. Anal.

Spectrochim. Acta

Spectrochim. Acta A

J. Mol. Struct.

J. Mol. Liq.

J. Mol. Liq.

J. Mol. Struct.

Chem. Phys. Lett.

Phys. Lett.

Spectrochim. Acta

Turk. J. Chem.

Bioorg. Med. Chem.

Pharmacology

Drugs