John D. Payzant

Sulfides in petroleum

Abstract The homologous series of terpenoid sulfides previously reported to be present in Athabasca bitumen have been detected in a variety of petroleums from the Western Hemisphere. All 22 samples examined, ranging in age from Devonoan to Cretaceous, contained the terpenoid sulfides. A method is described for the isolation of sulfides from petroleums based on the selective oxidation of sulfides to more polar sulfoxides which are easily removed from the mixture and their subsequent reduction to sulfides. The sulfide content in the petroleum maltenes examined ranged from 0.3 to 16.1% w/w. In addition to the bicyclic and tetracyclic terpenoid sulfides a new series of tricyclic terpenoid sulfides has been identified, and the details of the isoprenoid side chain have been elucidated for all three homologous series. The distributions by carbon number of the bicyclic and tetracyclic homologous series of terpenoid sulfides show pronounced variations which are attributed to thermal maturity and degree of water washing of the petroleum, thus the ability to identify terpenoid sulfides should provide a useful tool for oil-oil and oil-source rock correlation studies. The bicyclic and tricyclic terpenoid sulfides have the same carbon framework as the carotenoids which suggest that these sulfides were accessory pigments in photosynthesis.

Novel terpenoid sulfoxides and sulfides in petroleum

Abstract Homologous series of novel and unexpected biological markers, bicyclic and tetracyclic terpenoid sulfoxides and sulfides, have been identified in the Athabasca bitumen.

A homologous series of novel hopane sulfides in petroleum

Abstract A homologous series of hexacyclic sulfides ranging from C 30 to C 35 and containing the 17α(H), 21β (H) hopane carbon skeleton, III , have been identified in the heavy oils of Northern Alberta.

The identification of homologous series of thiolanes and thianes possessing a linear carbon framework from petroleums and their interconversion under simulated geological conditions

Abstract Several homologous series of monocyclic thiolanes and thianes possessing a linear carbon framework have been identified in a variety of petroleums. Of the 20 petroleums examined, none of the five biodegraded petroleums contained significant amounts of sulfides having a linear carbon framework, while all of the non-biodegraded petroleums which contained sulfides (11 out of 15 samples) did contain sulfides possessing a linear carbon framework. The distribution by carbon number of these homologous series of thiolanes and thianes extends from at least C 8 to C 30 and they may be separated from the terpenoid sulfides and other complex polycyclic sulfides by adduction with thiourea. The structures of several of the homologous series of thiolanes and thianes were determined by comparison with synthetic compounds. Raney nickel reduction of the sulfides from Bellshill Lake, an Alberta petroleum, afforded saturate hydrocarbons dominated by a series of n -alkanes which have a distribution by carbon number very similar to that of the naturally-occurring saturate hydrocarbons of this petroleum. The behaviour of several sulfides possessing a linear carbon framework under geological conditions was simulated by heating synthetic sulfides in the presence of calcium carbonate. If the sulfur atom was initially present at the end of the linear chain it tended to remain there with the formation of the five-membered thiolane ring favoured over the six-membered thiane ring. However, if the sulfur atom was initially positioned one carbon atom away from the terminal carbon, then it tended to hop further along the chain in a three-carbon-atom step. Repetition of this isomerization process could generate the variety of mid-chain isomeric sulfides observed in petroleum. Aromatization of the thiolane to the corresponding thiophene was also observed to take place on pyrolysis. An improved procedure for the isolation of sulfides from petroleum is described, the key step of which is the oxidation of the sulfides to the corresponding sulfoxides using tetrabutylammonium periodate in toluene/methanol. The method is rapid, near quantitative and does not distinguish between thiolanes and thianes but does distinguish between sulfides and thiophenes.

The synthesis of 1β(H), 6β(Me)-2,2,6-trimethyl-8-ethylbicyclo-[4,3,0]-7-thianonane and the structure of the isomeric bicyclic-terpenoid sulfides occurring in petroleum.

Abstract The synthesis of the title compound is described. Comparison of ms and nmr data with those of the isomeric bicyclic terpenoid sulfide of petroleum shows that the latter has the structure of 1α(H), 6β(H)-2,2-dimethyl-9-ethylbicyclo-[4,4,0]-8-thiadecane.

The identification of 9-n-alkyl fluorene-9-ols in the Alberta oil sands

Abstract Homologous series of 9- n -alkyl fluorene-9-ols and their nuclear methylated derivatives have been detected in the Alberta oil sands and their structure identified by infrared, field ionization and capillary gas chromatography-mass spectrometry and by comparison with synthetic standards.