Gas chromatographic and mass spectrometric characterization of isomeric alkylthiophenes (C20) and their occurrence in deep sea sediments

Six isomeric C₂₀ alkylthiophenes were synthesized in order to prove the occurrence of such compounds in various deep sea sediments. As expected from the analogy with the corresponding saturated hydrocarbons, 2- and 3-heptadecylthiophene have considerably longer relative retention times than the isomeric isoprenoid compounds, i.e. 2- and 3-(4,8,12-trimethyltridecyl)thiophene and 3- and 4-methyl-2-(3,7,11-trimethyldodecyl)thiophene. Covats retention indices for all compounds were determined by isothermal analysis at 190°C on two different silicone-coated capillary columns. The mass spectra of the monoalkylated thiophenes show a base peak at m/z 98 corresponding to a Mcafferty rearrangement product in the case of the 3-substituted isomers, whereas a simple benzylic cleavage dominates in the mass spectra of 2-alkylthiophenes. 4-Methyl-2-(3,7,11-trimethylodecy)thiophene is an exception from this simple rule because also shows the McLafferty rearrangement as dominant fragmentation. Two of the isoprenoid thiophenes are prominent compounds in various deep sea sediments.