Industrial & Engineering Chemistry Research, Vol.49, No.19, 9349-9354, 2010
Environmentally Benign Chiral Resolution of trans-1,2-Cyclohexanediol by Two-Step Supercritical Fluid Extraction
A racemic mixture of trans-1,2-cyclohexanediol (CHD) is reacted with S,S- or R,R-tartaric acid in ethanol with a 0.5 or higher molar ratio of resolving agent to racemic CHD. The tartaric acid (TA) forms a diastereomeric cocrystal with only one of the enantiomers; the other enantiomer remains unreacted at any molar ratio. The unreacted mixture of enantiomers is recovered from the sample by supercritical fluid extraction at 20 MPa and 33 degrees C. A subsequent extraction is then performed at 20 MPa and at least 73 degrees C. During this second extraction step, the diastereomeric cocrystal is decomposed in situ. Both enantiomers are recovered in nearly 50-50% yield with enantiomeric excess values of 65-90%. The mixtures of enantiomerss rich in S,S-CHD and R,R-CHD are then reacted with S,S-TA and R,R-TA, respectively, and the procedure is repeated. In two resolution steps, both enantiomers of CHD were produced in quantitative yields in a purity of ee > 99%.