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Structure Determination, Conformational Flexibility, Internal Dynamics, and Chiral Analysis of Pulegone and Its Complex with Water
Author(s) -
Krin Anna,
Pérez Cristóbal,
Pinacho Pablo,
QuesadaMoreno María Mar,
LópezGonzález Juan Jesús,
AvilésMoreno Juan Ramón,
Blanco Susana,
López Juan Carlos,
Schnell Melanie
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201704644
Subject(s) - conformational isomerism , molecule , chemistry , rotational spectroscopy , hydrogen bond , pulegone , enantiomer , crystallography , stereochemistry , computational chemistry , organic chemistry , chromatography , essential oil
In the current work we present a detailed analysis of the chiral molecule pulegone, which is a constituent of essential oils, using broadband rotational spectroscopy. Two conformers are observed under the cold conditions of a molecular jet. We report an accurate experimentally determined structure for the lowest energy conformer. For both conformers, a characteristic splitting pattern is observed in the spectrum, resulting from the internal rotation of the two non‐equivalent methyl groups situated in the isopropylidene side chain. The determined energy barriers are 1.961911(46) kJ mol −1 and 6.3617(12) kJ mol −1 for one conformer, and 1.96094(74) kJ mol −1 and 6.705(44) kJ mol −1 for the other one. Moreover, a cluster of the lowest energy conformer with one water molecule is reported. The water molecule locks one of the methyl groups by means of a hydrogen bond and some secondary interactions, so that we only observe internal rotation splittings from the other methyl group with an internal rotation barrier of 2.01013(38) kJ mol −1 . Additionally, the chirality‐sensitive microwave three‐wave mixing technique is applied for the differentiation between the enantiomers, which can become of further use for the analysis of essential oils.