The conformations of allylic alcohols in solution from FT-i.r. OH stretching vibration measurements

Bacon, J.; Maas, J.H. van der

doi:10.1016/0584-8539(88)80164-8

Cited by 14 publications

(13 citation statements)

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“…The purpose of this paper is to show that measurement of the O H stretching frequency, alone, is capable of giving detailed information regarding the nature 'Author to whom correspondence may be addressed. W e recently described the influence of structural changes on the O H stretching vibrations of allylic and P-y enols in dilute solution in CC14 (12,13). 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.…”

Section: Introductionmentioning

confidence: 99%

“…CApproximated from limited data available. dRelative intensity of rotamer bands depends upon degree of substitution at the carbinol and olefinic carbons (12). 'The secondary alcohols exhibit no bands that can be attributed to conformations in which the OH is free, except in the case of severe steric interactions in the eclipsed (E) conformation (13).…”

Section: Introductionmentioning

confidence: 99%

“…Recent advances in the study of the O H stretching frequency in dilute solution, using FT-IR, have allowed structural correlation with band position to be made with great accuracy (12)(13)(14)23), and structural elucidations of certain natural products have been made (1 1). The purpose of this paper is to show that measurement of the O H stretching frequency, alone, is capable of giving detailed information regarding the nature 'Author to whom correspondence may be addressed.…”

Section: Introductionmentioning

confidence: 99%

“…Figure 2 shows the typical intramolecularly hydrogen bonded conformation for allylic alcohols. Thus the allylic alcohols usually exhibit a composed O H stretching vibration band, which can be resolved into two bands by bandsplitting techniques (13). Typical O H stretching vibration frequencies are given in Table 1.…”

Section: Introductionmentioning

confidence: 99%

“…3), which are mutually exclusive. Substitution at the P carbon atom determines which conformation is adopted (12).…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…3), which are mutually exclusive. Substitution at the P carbon atom determines which conformation is adopted (12).…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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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¹H NMR study of the hetero‐association of unsaturated alcohols with pyridine

Lomas

2011

J of Physical Organic Chem

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The 1H NMR titration method is used to investigate the association of some unsaturated alcohols with pyridine in benzene. The association constant for allyl alcohol (2‐propen‐1‐ol) is slightly higher than for alkanols, but putting one methylene group between the OH and vinyl group completely eliminates this enhancement. In alkynols both the OH and ≡CH protons associate with pyridine. Here, the effects of chain‐lengthening on the association constant are irregular. Values for alkynols and some alcohols with hetero‐atom substituents are lower than expected on the basis of a Taft polar constant (σ*) correlation of alkanol association constants and of a correlation with the pKa’s of the corresponding carboxylic acids. It is suggested that stabilization of the ground state by OH/π interactions is responsible for these low association constants. Small increases in the NMR shifts of the OH protons in the 3‐carbon and 4‐carbon alkenols and alkynols can also be attributed to OH/π interactions, but the 5‐carbon analogues have shifts as low as alkanols. Copyright © 2011 John Wiley & Sons, Ltd.

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Fourier transform—infrared study of hydrogen-bonding between an OH-donor and a vicinal oxygen acceptor

Singelenberg

Maas

1990

Journal of Molecular Structure

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The conformations of allylic alcohols in solution from FT-i.r. OH stretching vibration measurements

Cited by 14 publications

References 11 publications

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

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

¹H NMR study of the hetero‐association of unsaturated alcohols with pyridine

Fourier transform—infrared study of hydrogen-bonding between an OH-donor and a vicinal oxygen acceptor

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The conformations of allylic alcohols in solution from FT-i.r. OH stretching vibration measurements

Cited by 14 publications

References 11 publications

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

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

1H NMR study of the hetero‐association of unsaturated alcohols with pyridine

Fourier transform—infrared study of hydrogen-bonding between an OH-donor and a vicinal oxygen acceptor

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¹H NMR study of the hetero‐association of unsaturated alcohols with pyridine