Synthesis and Properties of a Dithiiranetrans-1,2-Dioxide, a Three-Memberedvic-Disulfoxide

Abstract

cis- and trans-3-(1-adamantyl)-3-tert-butyldithiirane 1-oxides were oxidized with dimethyldioxirane to give the trans-1,2-dioxide. Thermal decomposition of the 1,2-dioxide yielded the corresponding (E)- and (Z)-sulfines, thioketone, and cis- and trans-dithiirane 1-oxides. In the thermolysis, decomposition to the sulfines and SO was the main path and that to the thioketone and SO(2) was the minor one. The two decomposition processes and epimerization to the cis-1,2-dioxide were analyzed theoretically. SO generated in situ reacted with thioketones as additives to give the corresponding dithiirane 1-oxides.

Preparation of 3,3‐Di‐tert‐butylthiirane trans‐1,2‐Dioxide and Its Reaction with a Platinum(0) Complex To Give a (Disulfenato)platinum(II) Complex: Regioselectivity of the Oxidation of a Related (Sulfenato–thiolato)platinum(II) Complex

“…No formation of 15 and 17 on the decomposition in chloroform at room temperature may indicate that the 1,2-oxygen shift of 8 to the dithiirane 1,1-dioxide requires a larger activation energy than the extrusion of SO to give 16, which is consistent with the theoretical consideration. [9] Platinum Complexes 1,2-Dioxide 8 was treated with [(Ph 3 P) 2 Pt(η 2 -C 2 H 4 )] in dichloromethane at 0°C. The mixture containing the desired (disulfenato)Pt II complex 18, sulfine 16, and 8 was recrystallized from a mixed solvent of hexane and dichloromethane at -20°C to give 18 as a yellow powder in 56 % yield [Equation (6)].…”

“…. The change in regioselectivity as described above was explained by protonation on the sulfinyl oxygen atom with the coexisting carboxylic acid leading to a decrease in the electron density on the sulfinyl-sulfur atom [Equation (9)]. The extent of the decrease in the electron density is dependent on the strength of the acid.…”

“…[6][7][8][9][10] 3-(1-Adamantyl)-3-tert-butyldithiirane trans-1,2-dioxide (4) is the first three-membered vic-disulfoxide synthesized by the oxidation of the corresponding dithiirane 1-oxide 5 with an acetone solution of dimethyldioxirane (DMD) [Equation (1)]. [9] An interesting reaction of 4 is its decomposition in refluxing chloroform as shown in Scheme 1 to give sulfine 6 and sulfur monoxide (SO) by the main path. SO was trapped with thioketone 7, generated from a minor path, to provide dithiirane 1-oxide 5 (Scheme 1).…”

2,7‐Di‐tert‐butylnaphtho[1,8‐cd][1,2]dithiole 1,2‐dioxides: Thermally Stable, Photochemically Active vic‐Disulfoxides

“…[3] More recently, Nakayama, Ishii, and co-workers succeeded in isolating vicsulfoxides 2-7 in the solid state. [4][5][6][7] However vic-disulfoxides 2-7 still undergo further reaction in solution at room temperature or below. Herein, we report two novel diastereomeric vic-disulfoxides that have a significantly higher barrier to thermal rearrangement than 1-7.…”

Sulfur Monoxide Transfer from peri-Substituted Trisulfide-2-oxides to Dienes: Substituent Effects, Mechanistic Studies and Application in Thiophene Synthesis

“…17 The trapping of SO with 2,3-dimethylbutadiene has been used to identify reaction pathways in the oxidation of sulfines 6 and thionosulfite 7, 18,19 and in the thermal degradation of the threemembered-ring vic-disulfoxide 8. 20 More recently, Nakayama has described novel transformations of SO generated from the room temperature breakdown of the bridged bicyclic sulfoxide 9, produced in situ from the DielsÀAlder reaction of 3,4-di-tertbutylthiophene 1-oxide with dimethylacetylenedicarboxylate. 21 Successful in situ trapping of some strained alkenes and alkynes ABSTRACT: Three peri-substituted trisulfide-2-oxides are prepared by treatment of 1,8-naphthalene dithiols with thionyl chloride and pyridine.…”