Conformations, possible hydrogen bonding, and microwave spectrum of 3-buten-2-ol

Smith, Zuzana; Carballo, Norberto; Wilson, Edwin Bidwell; Marstokk, K.-M.; Moellendal, H.

doi:10.1021/ja00293a026

Cited by 40 publications

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“…The quasi 50/50 presence of these two butenol rotamers in the gas phase is experimentally verified by a microwave analysis (Smith, Carballo, Bright Wilson, Marstokk & M~llendal, 1985). The relatively much higher energy of the third rotamer (Rot.…”

Section: Geometry Of An Isolated Butenol Moleculementioning

confidence: 76%

“…In order to analyse the importance of surrounding molecules on the molecular geometry, we first optimized the geometry of an isolated (R)-butenol molecule using Pulay's gradient method, the computer program BRABO (Van Alsenoy, 1988;Van Alsenoy & Peeters, 1993) and the 4-21 G basis set (Pulay, Fogarasi, Pang & Boggs, 1979). The relaxation was considered complete when the residual forces on the separate atoms were smaller than 10pN.…”

Section: Geometry Of An Isolated Butenol Moleculementioning

confidence: 99%

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Solids modelled by crystal field ab initio methods. IX. Stereoselective order–disorder in tri-ortho-thymotide–3-buten-2-ol (2/1) clathrate

Verhulst¹,

Lenstra²,

Alsenoy³

1995

Acta Crystallogr Sect B

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Geometries of 3-buten-2-ol (CH 3 --CHOH CH---CH2) were optimized using standard ab initio ,9]trioxacyclododecin-6,12,18-trione. Excellent agreement is obtained with available microwave and diffraction data. Despite the neglect of orbital overlap between neighbouring molecules, all the significant geometric differences between the gas phase and the solid state are well reproduced. Specifically we note the differences in C~C--CmO torsion angles. The presence of both R and S configurations in the TOTclathrate with a low degree of chiral discrimination has been experimentally verified. From the difference in calculated molecular energy between the two butenol enantiomers that were optimized within the TOTclathrate, the observed enantiomeric excess of 4--6% in favour of (R)-butenol is reproduced.

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Section: Geometry Of An Isolated Butenol Moleculementioning

confidence: 76%

Section: Geometry Of An Isolated Butenol Moleculementioning

confidence: 99%

Solids modelled by crystal field ab initio methods. IX. Stereoselective order–disorder in tri-ortho-thymotide–3-buten-2-ol (2/1) clathrate

Verhulst¹,

Lenstra²,

Alsenoy³

1995

Acta Crystallogr Sect B

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“…The microwave spectrum of 3‐buten‐2‐ol, 1b , shows it to exist as more than two conformers out of a possible nine, with the OH group close to the double bond in the two conformers assigned . In the gas phase, the two most stable conformers are + ac , −sc and sp , −sc in that order, with sp , +sc close behind (Table ).…”

Section: Resultsmentioning

confidence: 99%

GIAO/DFT calculations of relative conformer energies and ¹H NMR shifts of unsaturated alcohols in benzene

Lomas

Maurel

2011

J of Physical Organic Chem

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Density functional theory calculations were performed on alkenols and alkynols at the PBE1PBE/6‐311 + G(d,p) level with the inclusion of solvent (benzene) effects by the integral‐equation‐formalism polarizable continuum model (IEFPCM). For the smaller molecules, conformers in which the OH group is in the vicinity of the double or triple bond are preferred, but this preference falls as the alkyl chain is lengthened. The solvent effect on the relative Gibbs energies of different conformers is irregular, and in only two cases, 3‐buten‐1‐ol and 3‐butyn‐1‐ol, is there marked levelling. Gauge‐including atomic orbital calculations, based on the PBE1PBE/6‐311 + G(d,p) geometries but using a larger basis set, cc‐pVTZ, give nuclear magnetic resonance shifts for all the protons in each conformer. Overall shifts are calculated by weighing these according to the conformer population. Calculated values are well correlated with experimental data from high‐dilution spectra in the same solvent, ranging from about 0.4 to 5.8 ppm, with a slope of 1.09 ± 0.01. Calculations on some alcohols with hetero‐atom substituents confirm that these also prefer gauche (synclinal) conformers in the gas phase, with a less marked preference in benzene. The nuclear magnetic resonance shifts, however, are calculated to be on average over 0.8 ppm higher than observed. Copyright © 2011 John Wiley & Sons, Ltd.

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“…It was shown that equilibria exist between conformations in which the O H proton is associated with the .rr system and those in which it is free. The relative abundances of these conformations differ appreciably from those found in the vapour state (14)(15)(16)(17)(18)(19)(20)(21)(22). The O H stretching frequencies and relative intensities of the O H bands are dependent upon the conformations, which in turn are influenced by substitution in the vicinity of the carbinol and olefinic carbons.…”

Section: Introductionmentioning

confidence: 81%

The identification of structural fragments of enolic monoterpenes, enolic pheromones, and related natural products, from OH stretching vibration frequencies and relative intensities

Bacon¹,

Maas²

1989

Can. J. Chem.

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Can. J. Chem. 67, 250 (1989). The OH stretching frequency has proved to be a powerful tool for structural investigations of enolic natural products containing diverse structural elements. The position of unsaturation can in many cases be determined directly from frequency measurements. Primary, secondary, and tertiary a-p and P-y unsaturation can unambiguously be identified due to the possession of OH bands arising from an interaction of the OH proton with the .rr system. Frequently, unsaturation further removed than the y position can be identified, particularly when a double bond is present, intermediate between the distal .rr system and the OH group. The identification of long-range OH-.rr system interactions relies on the observation that an intermediate double bond reduces the rotational freedom of the molecule. This reduction in entropy is assumed to be responsible for a significant population of the conformation in which the OH group is associated with the .rr system.Key words: infrared, conformation, natural products, alcohols, molecular structure. 250 (1989). La frequence de la vibration dlClongation OH s'avkre un outil puissant dans les etudes de structures des produits naturels tnoliques comportant divers elements de structure. Dans plusieurs cas, les mesures de frkquence permettent de determiner directement la position de l'insaturation. En se basant sur la presence de bandes OH provenant d'une interaction entre le proton du OH et le systkme .rr, on peut identifier sans ambigui'tks les insaturations a-p ainsi que P-y, tant primaire que secondaire ou tertiaire. On peut friquemment identifier des insaturations dont la position est plus tloignte que la position y ; cette affirmation est particulikrement vraie lorsqu'il existe une double liaison entre le systkme .rr tloigni et le groupement OH. L'identification des interactions OH-.rr B distance est bake sur l'observation qu'une double liaison intermediaire rtduit la liberte de rotation de la molCcule. On fait l'hypothkse que cette reduction de I'entropie est responsable de la presence d'une population importante de la conformation dans laquelle le groupement OH est associC avec le systkrne .rr.

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Conformations, possible hydrogen bonding, and microwave spectrum of 3-buten-2-ol

Cited by 40 publications

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Solids modelled by crystal field ab initio methods. IX. Stereoselective order–disorder in tri-ortho-thymotide–3-buten-2-ol (2/1) clathrate

Solids modelled by crystal field ab initio methods. IX. Stereoselective order–disorder in tri-ortho-thymotide–3-buten-2-ol (2/1) clathrate

GIAO/DFT calculations of relative conformer energies and ¹H NMR shifts of unsaturated alcohols in benzene

The identification of structural fragments of enolic monoterpenes, enolic pheromones, and related natural products, from OH stretching vibration frequencies and relative intensities

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Conformations, possible hydrogen bonding, and microwave spectrum of 3-buten-2-ol

Cited by 40 publications

References 0 publications

Solids modelled by crystal field ab initio methods. IX. Stereoselective order–disorder in tri-ortho-thymotide–3-buten-2-ol (2/1) clathrate

Solids modelled by crystal field ab initio methods. IX. Stereoselective order–disorder in tri-ortho-thymotide–3-buten-2-ol (2/1) clathrate

GIAO/DFT calculations of relative conformer energies and 1H NMR shifts of unsaturated alcohols in benzene

The identification of structural fragments of enolic monoterpenes, enolic pheromones, and related natural products, from OH stretching vibration frequencies and relative intensities

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GIAO/DFT calculations of relative conformer energies and ¹H NMR shifts of unsaturated alcohols in benzene