Reactivity of di-iodine toward thiol: Desulfuration reaction of 5-nitro-2-mercapto-benzimidazole upon reaction with di-iodine

Corban, G. J., Antoniadis, C. D., Hadjikakou, S. K., Kourkoumelis, N., Tyurin, V. Yu., Dolgano, A., Milaeva, E. R., Kubicki, M., Bernhardt, P. V., Tiekink, E. R. T., Skoulika, S. and Hadjiliadis, N. (2012) Reactivity of di-iodine toward thiol: Desulfuration reaction of 5-nitro-2-mercapto-benzimidazole upon reaction with di-iodine. Heteroatom Chemistry, 23 5: 498-511. doi:10.1002/hc.21042


Author Corban, G. J.
Antoniadis, C. D.
Hadjikakou, S. K.
Kourkoumelis, N.
Tyurin, V. Yu.
Dolgano, A.
Milaeva, E. R.
Kubicki, M.
Bernhardt, P. V.
Tiekink, E. R. T.
Skoulika, S.
Hadjiliadis, N.
Title Reactivity of di-iodine toward thiol: Desulfuration reaction of 5-nitro-2-mercapto-benzimidazole upon reaction with di-iodine
Journal name Heteroatom Chemistry   Check publisher's open access policy
ISSN 1042-7163
1098-1071
Publication date 2012-01-01
Sub-type Article (original research)
DOI 10.1002/hc.21042
Open Access Status Not Open Access
Volume 23
Issue 5
Start page 498
End page 511
Total pages 14
Place of publication Hoboken, NJ, United States
Publisher John Wiley & Sons
Subject 1600 Chemistry
Abstract The reaction of 2-mercapto-benzoic acid (H 2MBA), 2-mercato-nicotinic acid (H 2MNA), and 2-mercapto-pyrimidine (PMTH) with a twofold molar amount of di-iodine (I 2) results in the isolation of crystals of the neutral disulfides of formulae: {(HMBA) 2·1/2(CH 3CN)} (1), {(HMNA) 2· (H 2O)} (2), and (PMT) 2 (3), respectively, when dichloromethane/acetonitrile/methanol (1) or dichloromethane (2,3) were used as solvents. The reaction of di-iodine with thethiol PMTH and 2-mercapto- benzothiazole (MBZTH) yields the disulfide (PMT) 2 (3), and the di-iodine adduct of formula {[MBZTH-I 2]·[MBZTH] 2} (4), respectively. The reaction of di-iodine with 5-nitro-2-mercapto- benzimidazole (O 2N-MBZIMH) (5) in the presence of ferric trichloride hydrate (FeCl 3·6H 2O), in a 6:3:1 (I 2:thiol:FeCl 3·6H 2O) molar ratio, results in cocrystal (6), which contain the desulfurated hydroxyl derivative O 2N-BZIMOH (6a) and unreacted O 2N-MBZIMH (6b) in a 3:1 molar ratio. The compounds were characterized by elemental analysis, FT-IR, and 1H NMR spectroscopy. The crystal structures of compounds 1-6 were also determined by X-ray crystallography. Cyclic voltammetry measurements showed that thiols with low oxidation potentials (< 1.0 V) mainly form disulfides upon a reaction with di-iodine, whereas those with higher oxidation potential form charge transfer (CT), resulting in desulfurated products, MBZIMH. However, in the case of O 2N-MBZIMH a desulfurated species was isolated. The formation of the final product also requires the presence of FeCl 3. Copyright
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Non HERDC
School of Chemistry and Molecular Biosciences
 
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