Deuterium sulfides

Depending on the linear, branched or cyclic structure of the unsaturated compound, a variety of dialkyl sulfides has been obtained in the reaction with H2S (equations 16-18). The regiochemistry depended markedly on the structure of the diene. For a mechanistic purpose, some experiments have been carried out using deuterium sulfide, D2S. The results have been interpreted in terms similar to those of Nordlander and coworkers9 (vide infra). The thiylation of 1,3-dienes was assumed to start with a regiospecific addition of a proton or a deuteron to one of the two double bonds to form two isomeric ion pairs as in equation 14 which, in the poorly dissociating solvent, collapse into products with equal probability. 

Although the exchange of the hydroxyl hydrogen in methanol with deuterium in various deuterium compounds such as deuterium oxide and deuterium sulfide has been reported 1-3) and the preparation of methanol-d (CH3OD) by the saponification of esters and decomposition of Grignard reagent with deuterium oxide has been described 4 6), the catalytic exchange of deuterium gas with methanol over Adams platinum catalyst has not been previously studied. 

P. G. T. Fogg and C. L. Young, Eds., lUPAC Solubility Data Series, Vol. 32, Hydrogen Sulfide, Deuterium Sulfide, and Hydrogen Selenide, Pergamon Press, Oxford, England, 1988. 

Deuterium sulfide is introduced with shaking into an ice-cooled suspension of Ig in DgO placed in a closed recirculating glass apparatus with all joints melt-sealed. Unconverted DgS is reintroduced into the reaction mixture. The heavy hydriodic acid formed is separated from the precipitated sulfur by filtration (in the absence of air) and separated from the dissolved DsS by prolonged evacuation. 

In the dual-temperature H2O/H2S process (61,62), exchange of deuterium between H20(l) and H2S(g) is carried out at pressures of ca 2 MPa (20 atm). At elevated temperatures deuterium tends to displace hydrogen in the hydrogen sulfide and thus concentrates in the gas. At lower temperatures the driving force is reversed and the deuterium concentrates in H2S in contact with water on the tiquid phase. 

Wafers were prepared, sulfided and evacuated (2 h at 673 K) as described above. The temperature was then set at 423 K and 80 kPa of purified deuterium (Air Liquide, N28) was admitted into the cell. The purification procedure consisted of passing the gas through a moisture filter (Chrompack Gas Clean 7971), an oxygen filter (Chrompack Gas Clean 7970) and a liquid nitrogen trap. 

More recently, a number of reports dealing with 1,3-sulfonyl shifts which proceed by other mechanisms have been published. For example, Baechler and coworkers suggested that the higher activation enthalpy observed for the isomerization of the deuterium labeled methallyl sulfone 72 in nitrobenzene at 150°C as compared to the corresponding sulfide, together with the positive entropy of activation may be taken as evidence for a homolytic dissociation mechanism (equation 44). A similar mechanism has also been suggested by Little and coworkers for the gas-phase thermal rearrangement of deuterium labelled allyl sec-butyl sulfone, which precedes its pyrolysis to alkene and sulfur dioxide. 

Clarke, E.C.W. and D.N. Glew (1971), Aqueous nonelectrolyte solutions, Part VIII. Deuterium and hydrogen sulfides solubilities in deuterium oxide and water, Can. J. Chem., 49, 691-698. Corsi, R.L., S. Birkett, H. Melcer, and J. Bell (1995), Control of VOC emissions from sewers A multi-parameter assessment, Water Sci. Tech, 31(7), 147-157. 

Part VIII. Deuterium and Hydrogen Sulfides Solubilities in Deuterium Oxide and Water," Can. J. Chem., 1971, 49, 691-98. 

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