Kinetics of equilibrium attainment between molecular glycolaldehyde structures in an aqueous solution

Glushonok, G.K.; Glushonok, T.G.; Шадыро, О. И.

doi:10.1007/bf02754560

Cited by 21 publications

(36 citation statements)

References 7 publications

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“…The NMR and UV results on diluted acetol state that hydroxyaceton is 96% in the carbonyl form and only up to 4% in the hydrated form [20]. The results presented here give evidence of at least two conformers of hydroxyacetone in the carbonyl form exist in the 90 wt.% water solution.…”

Section: Resultsmentioning

confidence: 49%

“…Previous research on glycolaldehyde that employed vibrational sectroscopy includes the work of Michelsen and Klaboe [13], infrared matrix isolation study of Aspiala et al [14], and, more recently, Yaylayan et al studied transformation of glycolaldehyde with temperature and in different solvents [15]. Quite a few NMR studies were done on glycolaldehyde [9], [10], [11], [16], [17], [18] and [19] and one on hydroxyacetone in aqueous solutions [20]. Whereas glycolaldehyde exhibits really complicated behavior in water, methanol and dimethyl sulphoxide, forming several types of open and closed dimers, as well as hydrate and enediol [10] and [15], hydroxyacetone in water seems to remain a monomer [20].…”

Section: Introductionmentioning

confidence: 99%

“…Quite a few NMR studies were done on glycolaldehyde [9], [10], [11], [16], [17], [18] and [19] and one on hydroxyacetone in aqueous solutions [20]. Whereas glycolaldehyde exhibits really complicated behavior in water, methanol and dimethyl sulphoxide, forming several types of open and closed dimers, as well as hydrate and enediol [10] and [15], hydroxyacetone in water seems to remain a monomer [20]. Both free glycoladehyde [21] and [22] and hydroxyacetone [23] exhibit intramolecular hydrogen bonding that establishes planar CSince there were some discrepancies in the vibrational assignment of the glycolaldehyde bands and no assignment has been done for hydroxyacetone so far, semi-empirical normal coordinate analysis was performed with valence force constants transferred from well established force fields of acetone and acetaldehyde [24] and ethylene glycol [25], with very few modifications.…”

Section: Introductionmentioning

confidence: 99%

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Vibrational analysis of hydroxyacetone

Mohaček-Grošev

2005

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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In order to be able to fully understand the vibrational dynamics of monosaccharide sugars, we started with hydroxyacetone CH 2 OHCOCH 3, and glycolaldehyde CH 2 OHCOH, which are among the smallest molecules that contain hydroxyl and carbonyl group on neighboring carbon atoms. This sterical configuration is characteristic for saccharides and determines their biochemical activity. In this work vibrational analysis of hydroxyacetone was undertaken by performing the normal coordinate analysis for glycolaldehyde first, and transferring these force constants to hydroxyacetone. The observed Raman and infrared bands for 90 wt.% solution of hydroxyacetone in water (acetol) were used as a first approximation for the bands of free hydroxyacetone. The number of observed Raman and infrared bands for acetol exceeds the number of calculated values for the most stable hydroxyacetone conformer with C s symmetry, which suggests more than one conformer of hydroxyacetone in water solution. In particular, there are two bands both in infrared (1083 and 1057 cm −1 ) and in Raman spectrum (1086.5 and 1053 cm −1 ) that are assigned to the CO stretching mode and this is one of the indicators of several hydroxyacetone conformers in the solution. Additional information was obtained from low temperature Raman spectra: at 240 K a broad assymmetric band centered around 280 cm −1 appears, suggesting a disorder in the orientation of hydroxyl groups. Glassy state forms at ∼150 K. The broad band at 80 cm −1 is assigned to frozen torsions of hydroxymethyl groups.

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Section: Resultsmentioning

confidence: 49%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Vibrational analysis of hydroxyacetone

Mohaček-Grošev

2005

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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“…Glycolaldehyde in the melt is a rich mixture of monomers, open and closed dimers, some of which include hydroxyl groups simultaneously present in axial and equatorial position in the same molecule [25]. Therefore, determination of the relative stability of two glycolaldehyde dimer forms, one having two hydroxyl groups placed axially, and the other having two OH groups placed equatorially, is not possible in the way it was performed, e.g.…”

Section: Resultsmentioning

confidence: 99%

Glycolaldehyde dimer in the stable crystal phase has axial OH groups: Raman, infrared and X-ray data analysis

Mohaček-Grošev

Prugovečki

Prugovečki³

et al. 2013

Journal of Molecular Structure

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Mohaček-Grošev, V., Prugovečki, B., , ''Glycolaldehyde dimer in the stable crystal phase has axial OH groups: Raman, infrared and X-ray data analysis '', Journal of Molecular Structure, Vol. 1047, pp. 209-215. Glycolaldehyde dimer in the stable crystal phase has axial OH groups:Raman, infrared and X-ray data analysisGraphical abstract AbstractAlthough a small molecule and a simple 1,4-dioxane derivative, 2,5-dihydroxy-1,4-dioxane or glycolaldehyde dimer has a crystal structure that has eluded researchers so far, chief reason lying presumably in substance polymorphism. Here we report for the first time on the stable crystal structure of the glycolaldehyde dimer characterized by the X-ray powder diffraction method at room temperature. It crystallizes in the monoclinic system, space group P2 1 /c, with unit cell parameters a = 5.9473 (1) Mohaček-Grošev, V., Prugovečki, B., Prugovečki, S., Strukan, N. (2013), ''Glycolaldehyde dimer in the stable crystal phase has axial OH groups: Raman, infrared and X-ray data analysis '', Journal of Molecular Structure, Vol. 1047, pp. 209-215. Raman and infrared spectra were re-examined and assigned with the help of ab initio calculation followed by a normal modes analysis modes most sensitive to crystal packing were identified as the C-OH deformations which were assigned to the IR and Raman bands at 1239 and 1237 cm −1 , respectively; the two O-C-O deformation modes, both associated with the Raman and IR bands at 561 and 535 cm −1 and, the two OH torsion modes assigned to the IR bands at 630 and 604 cm −1 .

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“…Studies performed on kinetics of equilibrium attainment for a similar compound, glycolaldehyde, indicate that transformation of the isomeric structures into each other occurs in milliseconds (Glushonok et al 2000). The monomer is the only form with a carbonyl group which can undergo rapid interaction with the amine group of the semicarbazide ligand.…”

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confidence: 99%