An investigation of the electronic structure of some 3-monosubstituted-2-methylpropenes through computational chemistry and photoelectron spectroscopy

Schuquel, Ivânia T.A.; Ducati, Lucas C.; Custódio, Rogério; Rittner, Roberto; Klapstein, Dieter

doi:10.1016/j.chemphys.2008.02.052

Cited by 3 publications

(1 citation statement)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A recent review drew attention to the importance of unconventional, weak hydrogen bonds, CH/ n , CH/π and XH/π (X = O, S, Se), in determining the conformations of organic compounds and bioconjugates . Early infrared (IR) spectroscopic studies of small unsaturated alcohols are confirmed by work which in many cases combines IR and/or microwave (MW) spectroscopy, and gas electron diffraction (GED) measurements and photoelectron spectroscopy, with ab initio calculations, to identify the preferred conformers. These studies of the conformational equilibria show them to be dominated by OH/π interactions, and the proximity of putative donors and acceptors is frequently taken as demonstrating that intramolecular hydrogen bonding (IHB) occurs.…”

Section: Introductionmentioning

confidence: 99%

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

Lomas

2011

J of Physical Organic Chem

View full text Add to dashboard Cite

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.

show abstract