Structure, Thermochemistry and Reactivity of Protonated Glycolaldehyde

Bouchoux, Guy; Penaud–Berruyer, Florence; Bertrand, William

doi:10.1255/ejms.445

Cited by 15 publications

(21 citation statements)

References 17 publications

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“…Although having similar chemical composition, glycolaldehyde and hydroxyacetone have rather different equipotential energy surface judging by the ones calculated by ab initio methods [14], [27] and [28]. We define as τ 1 the CH 2 O torsional angle around C 1 -C 2 bond, and as τ 2 the OH torsional angle around C 1 -O 3 bond.…”

Section: Resultsmentioning

confidence: 99%

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: 99%

Vibrational analysis of hydroxyacetone

Mohaček-Grošev

2005

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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“…A series of α‐, β‐, and γ‐ketoalcohols and ketoethers (Scheme ) have been studied by HPMS and FT‐ICR mass spectrometry and quantum chemistry calculations in order to determine their protonation thermochemistry and structures (Bouchoux, Berruyer‐Penaud, & Bertrand, , Bouchoux et al, , , ). The major results are presented in Table .…”

Section: Aldehydes and Ketonesmentioning

confidence: 99%

“…(a) kJ mol −1 ; (b) J K −1 mol −1 ; (c) HPMS (Bouchoux et al, ); (d) FT‐ICR (Bouchoux et al, ); (e) (Bouchoux et al, , 2006); (f) (Bouchoux, Berruyer‐Penaud, & Bertrand, ). (g) G3 calculations (Bouchoux et al, ).…”

Section: Aldehydes and Ketonesunclassified

Gas-phase basicities of polyfunctional molecules. Part 4: Carbonyl groups as basic sites

Bouchoux

2014

Mass Spec Rev

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This article constitutes the fourth part of a general review of the gas-phase protonation thermochemistry of polyfunctional molecules (Part 1: Theory and methods, Mass Spectrom Rev 2007, 26:775-835, Part 2: Saturated basic sites, Mass Spectrom Rev 2012, 31:353-390, Part 3: Amino acids, Mass Spectrom Rev 2012, 31:391-435). This fourth part is devoted to carbonyl containing polyfunctional molecules. After a short reminder of the methods of determination of gas-phase basicity and the underlying physicochemical concepts, specific examples are examined under two major chapters. In the first one, aliphatic and unsaturated (conjugated and cyclic) ketones, diketones, ketoalcohols, and ketoethers are considered. A second chapter describes the protonation energetic of gaseous acids and derivatives including diacids, diesters, diamides, anhydrides, imides, ureas, carbamates, amino acid derivatives, and peptides. Experimental data were re-evaluated according to the presently adopted basicity scale. Structural and energetic information given by G3 and G4 quantum chemistry computations on typical systems are presented.

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“…The fact that it is the first sacharide found in the interstellar space [1] and the role it plays in the energy metabolism in humans [2], has motivated microwave [3] and conformational studies [4], [5], [6] and [7], electron beam radiation experiments [8], as well as infrared spectroscopic studies of molecules isolated in noble gases [9] or parahydrogen matrix [10]. In the solid state, pure glycolaldehyde exists in the form of a dimer [11] and [12].…”

Section: Introductionmentioning

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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Structure, Thermochemistry and Reactivity of Protonated Glycolaldehyde

Cited by 15 publications

References 17 publications

Vibrational analysis of hydroxyacetone

Vibrational analysis of hydroxyacetone

Gas-phase basicities of polyfunctional molecules. Part 4: Carbonyl groups as basic sites

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

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