Combinatorial approach to flavor analysis. 1. Preparation and characterization of a S-methyl thioester library

A new method for the "one-pot" synthesis of S-methyl thioesters has been developed by reacting methyl chlorothiolformate with carboxylic acids. The resulting "flavor library" contained all the intended thioesters and a single major impurity, identified by GC-MS as S, S-dimethyldithiocarbonate. Quantification of individual compounds present in the library was performed by GC analysis using two independent methods of detection, SCD and FID. It was shown that apart from S-methyl thioacetate (0.8 mol %), molar concentrations of other thioesters varied in a relatively narrow range from 4.2 mol % for S-methyl thiopropionate to 14.1 mol % for S-methyl thiohexanoate. In general, medium chain S-methyl thioesters were present in slightly higher molar concentrations than those prepared from short or long chain carboxylic acids. This variation was attributed to partial loss of the most volatile components during extraction and the lower reactivity of higher homologues. The library was used for the characterization of some physicochemical parameters of thioesters. In particular, lipophilicity coefficients (log k(w)) and thioester retention in 10, 20, and 33% triolein (used as a model lipid phase) were determined directly by reverse-phase HPLC and extrapolated from the respective data. This analysis illustrates that substantial information can be generated using a library containing a relatively large number of compounds in effectively the same way as is necessary for the analysis of a single sample.