18655-88-4Relevant articles and documents
An S-oxide of 6-tert-butyl-6-phenylpentathiane. Structure in the crystalline state and in solution and thermal decomposition
Ishii, Akihiko,Oshida, Hideaki,Nakayama, Juzo
, p. 3117 - 3119 (2007/10/03)
Oxidation of 6-tert-butyl-6-phenylpentathiane with trifluoroperacetic acid gave the pentathiane 3-oxide mainly as the monooxide. The 3-oxide takes a twist conformation both in the crystalline state and in solution. Thermal decomposition of the 3-oxide in the presence of 2,3-dimethyl-1,3-butadiene yielded both S2O- and S2-transferred products.
Sulfenyl chloride chemistry. New precursors for diatomic sulfur transfer
Abu-Yousef, Imad A.,Harpp, David N.
, p. 8654 - 8660 (2007/10/03)
When triphenylmethanesulfenyl chloride (1) (or its thio homologue 2) are treated with various bicycles, norbornene (5), or bicyclo[2.2.2]octene (6), dithio adducts 7 and 8 were produced in good isolated yields. Final products were obtained via an episulfide intermediate. The stereochemistry of addition has been determined by X-ray analysis. Treatment of thiosulfenyl chloride 2 (or its dithio homologue 3) with other olefins, cyclopentene (10), cyclohexene (11), or 1,4-dioxene (12), leads to the formation of disulfides (13-15 from 2) and trisulfides (16 and 17 from 3) in high isolated yields (ca. 92%). The structures of 7, 8, and 13-17 were established by 1H and 13C NMR and elemental analysis as well as by X-ray determination. When these adducts are warmed with a 1,3-diene 42, they deliver diatomic sulfur- trapped derivatives, cyclic di-49 and tetrasulfide adducts 46. A variety of solvents, temperatures, times, and concentrations were employed to optimize the yield of 46 and 49. The tetrasulfide adduct 46 is quantitatively converted to disulfide 49 with triphenylphosphine; this affords cyclic disulfides in > 50% isolated yield from the diene. In addition, evidence has been obtained implicating dithietane intermediate 4.
SYNTHESE ET REACTIVITE DE DITHIAPHOSPHADIGERMINANE ET -GERMINANE NOUVEAUX DITHIAPHOSPHONATES GERMANIES CYCLIQUES
Barrau, J.,Rima, G.,Satge, J.
, p. 99 - 106 (2007/10/03)
The synthesis of the six membered heterocycles (1) and (2) are described.Thermolysis of 1 generates the germylated heterocycles (3), (4), (5) and (AnPS2)3,4.These results are explained by a mechanism involving expulsion of and decomposition of the resulting transient thiadigermetane with formation of and .Exchange reactions between 1 and various chlorides are described.With metal 14 chlorides Σ2MCl2 the reactions lead to transient and metallathiones ; while with SCl2 the reaction leads to and singlet sulfur . - Key words: Germylated and phosphorylated heterocycles, transient species, germathione, singlet sulfur.
Does diatomic sulfur (S2) react as a free species?
Steliou, Kosta,Salama, Paul,Yu, Xiaoping
, p. 1456 - 1462 (2007/10/02)
A detailed study into the design and synthesis of stable 1,2-dithietane derivatives for the generation of diatomic sulfur (S2) was undertaken. Computer-aided evaluation of enthalpic differences was used to direct the synthesis of target compounds and, although all of the compounds calculated to afford S2 that were prepared did yield diatomic sulfur, an isolable 1,2-dithietane other than dithiatopazine failed to materialize. The results of this study provide convincing evidence that the computational procedure outlined can be successfully used to predict the course of S2 extrusion pathways from potential dithionocarbonylated derivatives. To determine if the disulfide moiety found in the Diels-Alder adduct derived from the addition of diatomic sulfur to conjugated 1,3-dienes is due to a transference mechanism involving the transient 1,2-dithietane intermediate, a chiral nonracemic binaphthyl source of S2 was prepared. Reactions of S2 from this source with chiral nonracemic and prochiral conjugated 1,3-dienes indicate that the added disulfide moiety would be inconsistent with a transference mechanism and that a "free" acting S2 unit is more likely to be involved.
