Self-induced nonequivalence in the 1H-NMR spectra of the (+)- and (-)-isomers of a cannabinoid ketone intermediate.
The 1H-NMR spectra in deuteriochloroform of racemic and optically pure (trans)-6a,7,10,10a-tetrahydro-1-hydroxy-6,6-dimethyl-3-pentyl-6H-dibenz o [b,d]pyran-9(8H)-one (1) are nonsuperimposable, while nonracemic mixtures of the (+)- and (-)-isomers show two sets of signals for the phenolic and aromatic protons in ratios directly proportional to the enantiomeric composition of the mixture. This is a new example of "self-induced nonequivalence" or "diastereomeric solute-solute interaction," a known but seldom reported phenomenon. The magnitude of the chemical shift differences are dependent on the ratios of the two enantiomers while the chemical shift delta values are concentration dependent. The overall effect was clearly observable even at a concentration of 0.01 M. In a practical sense, optical purities of samples of the cannabinoid ketone (1) are readily determined by 1H-NMR without the use of additional chiral shift reagents.
Hui
R A
RA
Roche Diagnostic Systems, Incorporated, Nutley, NJ.
Salamone
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S
Williams
T H
TH
D002186:Cannabinoids / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D013237:Stereoisomerism
D002186:Cannabinoids; C074006:6a,7,10,10a-tetrahydro-1-hydroxy-6,6-dimethyl-3-pentyl-6H-dibenzo(b,d)pyran-9(8H)-one