Synthesis, X-ray, NMR, FT-IR, UV/vis, DFT and TD-DFT studies of N-(4-chlorobutanoyl)-N′-(2-, 3- and 4-methylphenyl)thiourea derivatives

Hamza M. Abosadiya, El Hassane Anouar, Siti Aishah Hasbullah, Bohari Mohd. Yamin

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

A new isomers of thiourea derivatives, namely N-(4-chlorobutanoyl)-N′-(2-methylphenyl)-thiourea (1a), N-(4-chlorobutanoyl)-N′-(3-methylphenyl)thiourea (1b) and N-(4-chlorobutanoyl)-N′-(4-methylphenyl)thiourea (1c) have been synthesized by refluxing mixture of equimolar amounts of 4-chlorobutanoylisothiocyanate with 2, 3 or 4-toluidine, respectively. The three isomers were characterized by spectroscopic (UV/vis, FT-IR and NMR) and X-ray crystallography techniques. To investigate the isomerization effect on spectroscopic data, DFT and TD-DFT calculations have been carried out using five hybrid functionals (B3LYP, B3P86, CAM-B3LYP, M06-2X and PBE0) to predict UV/vis absorption bands (n → π<sup>∗</sup> and π → π<sup>∗</sup>), <sup>1</sup>H and <sup>13</sup>C NMR chemical shifts, FT-IR vibration modes and X-ray parameters (bonds, bond angles and torsion angles) for 1a, 1b and 1c isomers. The results showed that the isomerization effect is significant on λ<inf>MAX</inf> absorption bands, while for IR and NMR the effect is negligible. In accordance with previous studies, B3LYP, B3P86 and PBE0 gave the most reliable to predict the excitation energies of thiourea derivatives.

Original languageEnglish
Pages (from-to)115-124
Number of pages10
JournalSpectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
Volume144
DOIs
Publication statusPublished - 5 Jun 2015

Fingerprint

Thiourea
Thioureas
thioureas
Discrete Fourier transforms
Nuclear magnetic resonance
Derivatives
X rays
nuclear magnetic resonance
Isomers
synthesis
2-toluidine
isomers
Isomerization
x rays
isomerization
Absorption spectra
absorption spectra
computer aided manufacturing
Excitation energy
X ray crystallography

Keywords

  • DFT
  • N-(4-chlorobutanoyl)-N′-(2-methylphenyl)-thiourea
  • NMR
  • TD-DFT
  • Thiourea derivatives
  • X-ray

ASJC Scopus subject areas

  • Instrumentation
  • Atomic and Molecular Physics, and Optics
  • Analytical Chemistry
  • Spectroscopy

Cite this

Synthesis, X-ray, NMR, FT-IR, UV/vis, DFT and TD-DFT studies of N-(4-chlorobutanoyl)-N′-(2-, 3- and 4-methylphenyl)thiourea derivatives. / Abosadiya, Hamza M.; Anouar, El Hassane; Hasbullah, Siti Aishah; Mohd. Yamin, Bohari.

In: Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, Vol. 144, 05.06.2015, p. 115-124.

Research output: Contribution to journalArticle

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abstract = "A new isomers of thiourea derivatives, namely N-(4-chlorobutanoyl)-N′-(2-methylphenyl)-thiourea (1a), N-(4-chlorobutanoyl)-N′-(3-methylphenyl)thiourea (1b) and N-(4-chlorobutanoyl)-N′-(4-methylphenyl)thiourea (1c) have been synthesized by refluxing mixture of equimolar amounts of 4-chlorobutanoylisothiocyanate with 2, 3 or 4-toluidine, respectively. The three isomers were characterized by spectroscopic (UV/vis, FT-IR and NMR) and X-ray crystallography techniques. To investigate the isomerization effect on spectroscopic data, DFT and TD-DFT calculations have been carried out using five hybrid functionals (B3LYP, B3P86, CAM-B3LYP, M06-2X and PBE0) to predict UV/vis absorption bands (n → π∗ and π → π∗), 1H and 13C NMR chemical shifts, FT-IR vibration modes and X-ray parameters (bonds, bond angles and torsion angles) for 1a, 1b and 1c isomers. The results showed that the isomerization effect is significant on λMAX absorption bands, while for IR and NMR the effect is negligible. In accordance with previous studies, B3LYP, B3P86 and PBE0 gave the most reliable to predict the excitation energies of thiourea derivatives.",
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T1 - Synthesis, X-ray, NMR, FT-IR, UV/vis, DFT and TD-DFT studies of N-(4-chlorobutanoyl)-N′-(2-, 3- and 4-methylphenyl)thiourea derivatives

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AU - Anouar, El Hassane

AU - Hasbullah, Siti Aishah

AU - Mohd. Yamin, Bohari

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AB - A new isomers of thiourea derivatives, namely N-(4-chlorobutanoyl)-N′-(2-methylphenyl)-thiourea (1a), N-(4-chlorobutanoyl)-N′-(3-methylphenyl)thiourea (1b) and N-(4-chlorobutanoyl)-N′-(4-methylphenyl)thiourea (1c) have been synthesized by refluxing mixture of equimolar amounts of 4-chlorobutanoylisothiocyanate with 2, 3 or 4-toluidine, respectively. The three isomers were characterized by spectroscopic (UV/vis, FT-IR and NMR) and X-ray crystallography techniques. To investigate the isomerization effect on spectroscopic data, DFT and TD-DFT calculations have been carried out using five hybrid functionals (B3LYP, B3P86, CAM-B3LYP, M06-2X and PBE0) to predict UV/vis absorption bands (n → π∗ and π → π∗), 1H and 13C NMR chemical shifts, FT-IR vibration modes and X-ray parameters (bonds, bond angles and torsion angles) for 1a, 1b and 1c isomers. The results showed that the isomerization effect is significant on λMAX absorption bands, while for IR and NMR the effect is negligible. In accordance with previous studies, B3LYP, B3P86 and PBE0 gave the most reliable to predict the excitation energies of thiourea derivatives.

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