Synthesis and dynamic NMR studies of novel hydantoin and thiohydantoin derivatives. Crystal structure of diethyl 2-(4,4-diaryl-2,5-dioxoimidazolidin-1-yl) fumarate and diethyl 2-(4,4-diaryl-2-mercapto-5-oxo-4,5-dihydro-1H-imidazol-1-yl)fumarate

Mohammad M. Ghanbari, Marzieh Jamali, G. Batta, A. Bényei

Research output: Contribution to journalArticle

Abstract

The reaction of stoichiometric amounts of dialkyl acetylenedicarboxylates with triphenylphosphine in the presence of hydantoins or thiohydantoins afforded stable crystalline phosphorus ylides. These compounds undergo smooth elimination of PPh3 to produce dialkyl 2-(4,4-diaryl-2,5-dioxoimidazolidin-1-yl)fumarate, 4 or dialkyl 2-(4,4-diaryl-2-mercapto-5-oxo-4,5-dihydro-1H-imidazol-1-yl)fumarate, 7. Single crystal X-ray diffraction study on 4b and 7b proved the structures unambiguously with C=O and SH functionality at the 2-position of the imidazole ring, respectively. Dynamic effects were observed in the NMR spectra of these compounds and were attributed to restricted rotation around the carbon-nitrogen single bonds. Rotational energy barrier (ΔG#) for their interconversion process of rotational isomers equals to (53.6 and 17.2) ± 2 kcal mol-1.

Original languageEnglish
Pages (from-to)309-313
Number of pages5
JournalJournal of Chemical Research
Volume41
Issue number5
DOIs
Publication statusPublished - May 1 2017

Fingerprint

Thiohydantoins
Hydantoins
Fumarates
Crystal structure
Nuclear magnetic resonance
Derivatives
Energy barriers
Isomers
Phosphorus
Nitrogen
Carbon
Single crystals
Crystalline materials
X ray diffraction
diethyl fumarate
2-imidazoline

Keywords

  • Dynamic 1H NMR
  • Hydantoin
  • Phosphorus ylides
  • Thiohydantoin
  • X-ray diffraction

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Synthesis and dynamic NMR studies of novel hydantoin and thiohydantoin derivatives. Crystal structure of diethyl 2-(4,4-diaryl-2,5-dioxoimidazolidin-1-yl) fumarate and diethyl 2-(4,4-diaryl-2-mercapto-5-oxo-4,5-dihydro-1H-imidazol-1-yl)fumarate",
abstract = "The reaction of stoichiometric amounts of dialkyl acetylenedicarboxylates with triphenylphosphine in the presence of hydantoins or thiohydantoins afforded stable crystalline phosphorus ylides. These compounds undergo smooth elimination of PPh3 to produce dialkyl 2-(4,4-diaryl-2,5-dioxoimidazolidin-1-yl)fumarate, 4 or dialkyl 2-(4,4-diaryl-2-mercapto-5-oxo-4,5-dihydro-1H-imidazol-1-yl)fumarate, 7. Single crystal X-ray diffraction study on 4b and 7b proved the structures unambiguously with C=O and SH functionality at the 2-position of the imidazole ring, respectively. Dynamic effects were observed in the NMR spectra of these compounds and were attributed to restricted rotation around the carbon-nitrogen single bonds. Rotational energy barrier (ΔG#) for their interconversion process of rotational isomers equals to (53.6 and 17.2) ± 2 kcal mol-1.",
keywords = "Dynamic 1H NMR, Hydantoin, Phosphorus ylides, Thiohydantoin, X-ray diffraction",
author = "Ghanbari, {Mohammad M.} and Marzieh Jamali and G. Batta and A. B{\'e}nyei",
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T1 - Synthesis and dynamic NMR studies of novel hydantoin and thiohydantoin derivatives. Crystal structure of diethyl 2-(4,4-diaryl-2,5-dioxoimidazolidin-1-yl) fumarate and diethyl 2-(4,4-diaryl-2-mercapto-5-oxo-4,5-dihydro-1H-imidazol-1-yl)fumarate

AU - Ghanbari, Mohammad M.

AU - Jamali, Marzieh

AU - Batta, G.

AU - Bényei, A.

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N2 - The reaction of stoichiometric amounts of dialkyl acetylenedicarboxylates with triphenylphosphine in the presence of hydantoins or thiohydantoins afforded stable crystalline phosphorus ylides. These compounds undergo smooth elimination of PPh3 to produce dialkyl 2-(4,4-diaryl-2,5-dioxoimidazolidin-1-yl)fumarate, 4 or dialkyl 2-(4,4-diaryl-2-mercapto-5-oxo-4,5-dihydro-1H-imidazol-1-yl)fumarate, 7. Single crystal X-ray diffraction study on 4b and 7b proved the structures unambiguously with C=O and SH functionality at the 2-position of the imidazole ring, respectively. Dynamic effects were observed in the NMR spectra of these compounds and were attributed to restricted rotation around the carbon-nitrogen single bonds. Rotational energy barrier (ΔG#) for their interconversion process of rotational isomers equals to (53.6 and 17.2) ± 2 kcal mol-1.

AB - The reaction of stoichiometric amounts of dialkyl acetylenedicarboxylates with triphenylphosphine in the presence of hydantoins or thiohydantoins afforded stable crystalline phosphorus ylides. These compounds undergo smooth elimination of PPh3 to produce dialkyl 2-(4,4-diaryl-2,5-dioxoimidazolidin-1-yl)fumarate, 4 or dialkyl 2-(4,4-diaryl-2-mercapto-5-oxo-4,5-dihydro-1H-imidazol-1-yl)fumarate, 7. Single crystal X-ray diffraction study on 4b and 7b proved the structures unambiguously with C=O and SH functionality at the 2-position of the imidazole ring, respectively. Dynamic effects were observed in the NMR spectra of these compounds and were attributed to restricted rotation around the carbon-nitrogen single bonds. Rotational energy barrier (ΔG#) for their interconversion process of rotational isomers equals to (53.6 and 17.2) ± 2 kcal mol-1.

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