Thioozonide decomposition: sulfur and oxygen atom transfer. Evidence for the formation of a carbonyl O-sulfide intermediate

Journal Article · Wed May 14 00:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00270a058· OSTI ID:5455769

Matturro, M G; Reynolds, R P; Kastrup, R V; Pictroski, C F

The chemistry of ozonides is of considerable interest from a practical and theoretical viewpoint. Thioozonide 1, formally the monosulfur-substituted ozonide of dimethylcyclobutadiene, has been proposed as an intermediate in the room temperature photooxidation of 2,5-dimethylthiophene. Subsequent low-temperature studies confirmed this structural assignment. When 1 is allowed to warm to room temperature, it rearranges to a mixture of sulfine 2 and cis- and trans-3-hexene-2,5-diones (3c and 3t). Recent examination of the thermal decomposition of 1 has led to a proposed mechanism involving a carbonyl sulfide 4 as an intermediate along the sulfur expulsion pathway to 3c; however, no experimental support for this hypothesis was given. Carbonyl O-sulfides have also been implicated as intermediates from the photolysis of oxathiiranes. The authors report evidence for the formation of 4 during the decomposition of 1 and that elemental sulfur (S/sub 8/) is formed during the reaction by concatenation of sulfur atoms or fragments (S/sub 2/, S/sub 3/, etc.).

• Research Organization: Exxon Research and Engineering Co., Annandale, NJ
• OSTI ID: 5455769
• Journal Information: J. Am. Chem. Soc.; (United States), Vol. 108:10
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
CHEMICAL PREPARATION
DIENES
DECOMPOSITION
OXYGEN COMPOUNDS
SULFIDES
SULFUR COMPOUNDS
EXPERIMENTAL DATA
CHALCOGENIDES
CHEMICAL REACTIONS
DATA
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYENES
SYNTHESIS
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)