Sulfur-sulfur bond cleavage processes. Selective desulfurization of trisulfides

Journal Article · Wed Nov 03 04:00:00 EST 1982 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00386a034· OSTI ID:6449001

Harpp, D N; Smith, R A

The selectivity of sulfur removal in the desulfurization of trisulfides by tertiary phosphorus compounds has been investigated in detail. A mechanistic rationalization is proposed to account for central/terminal sulfur extrusion variation as a function of substrate structure and solvent polarity.Conclusions drawn from this study are that the interaction of phosphine with a trisulfide is a complex process, where the transition states of the two reaction steps in ionic desulfurization are of similar free energy, and that variations in phosphine type and reaction solvent may affect these transition states to alter the kinetically important step. For desulfurization without inversion at an ..cap alpha..-carbon, triphenylphosphine is quite effective as it removes almost exclusively the central sulfur atom. However, for less reactive trisulfides, a tris(dialkylamino)phosphine would be required for a rapid desulfurization. In this case, desulfurization in benzene or ether provides a disulfide with predominant inversion at one ..cap alpha..-carbon (via terminal sulfur removal), while in acetonitrile, a disulfide having predominantly retained stereochemistry at both ..cap alpha..-carbons (via central sulfur removal) is obtained.

• Research Organization: McGill Univ., Montreal, Canada
• OSTI ID: 6449001
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 104:22; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DAYS LIVING RADIOISOTOPES
DESULFURIZATION
EVEN-ODD NUCLEI
ISOTOPE APPLICATIONS
ISOTOPES
KINETICS
LABELLING
LIGHT NUCLEI
NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
RADIOISOTOPES
REACTION KINETICS
SULFIDES
SULFUR 35
SULFUR COMPOUNDS
SULFUR ISOTOPES
TRACER TECHNIQUES