Four bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutan-1-yl)oligosulfanes

Abstract

The four oligosulfanes, bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutan-1-yl)disulfane, C(16)H(24)Cl(2)O(2)S(2), (III), 1,3-bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutan-1-yl)trisulfane, C(16)H(24)Cl(2)O(2)S(3), (V), 1,4-bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutan-1-yl)tetrasulfane, C(16)H(24)Cl(2)O(2)S(4), (VII), and 1,6-bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutan-1-yl)hexasulfane, C(16)H(24)Cl(2)O(2)S(6), (VIII), all have similar geometric parameters, with the C-C bond lengths involving the chloro-substituted cyclobutanyl C atom being elongated to about 1.59 A. There are two molecules in the asymmetric units of the tri- and tetrasulfanes, and the molecules in the latter compound have local C(2) symmetry. The molecule of the hexasulfane has crystallographic C(2) symmetry. Most of the cyclobutanyl rings are not perfectly planar and have slight but varying degrees of distortion towards a flattened tetrahedron. The polysulfane chain in each structure has a helical conformation, with each additional S atom in the chain adding approximately one quarter of a turn to the helix.

Reactions of Sulfanyl Chlorides with Thiocamphor and Thiofenchone: WagnerMeerwein Rearrangement of an Intermediate Thiocarbonylium Ion

“…Chromatography on SiO 2 plates led to partial decomposition of the main product, and only a mixture of the known symmetric bis(1-chloro-2,2,4,4-tetramethyl-3-oxocyclobutyl)tri-and -tetrasulfanes 4 (n 3,4) [3] was isolated as a minor fraction.…”

“…), or Bruker DRX-600 instrument (600 and 150.9 MHz, resp. ), in CDCl 3 [4] by treatment of a soln. of the corresponding ketones in MeOH with a mixture of HCl and H 2 S gas in the presence of equal amounts of methyl orthoformate.…”

“…± In a recent report [1], reactions of the sterically crowded 2,2,4,4-tetramethyl-3-thioxocyclobutanone (1) with PCl 5 and SCl 2 to give the stable achlorosulfanyl chloride 2 and a-chlorodisulfanyl chloride 3, respectively, have been described (Scheme 1). These products were shown to add easily to 1 to give symmetrically substituted polysulfanes 4 [2] [3]. On the other hand, 2 and 3 are highly electrophilic reagents, which react smoothly with enolizable thiocarbonyl-functionalized N-heterocycles like 1H-imidazole-2-thiones or thiouracil to give the corresponding di-and trisulfanes of type 5, respectively [2].…”

2,2,4,4-Tetramethylcyclobutane-1-one-3-thione

“…Sulfur dichloride in tetrachloromethane adds easily to 1 to give disulfanyl chloride 4 along with trisulfane 5 as a side product. 8,9 In an analogous reaction, disulfur dichloride and 1 react slowly and tetrasulfane 6 is formed as the exclusive product (eq 3). Reactions with Organometallics.…”

Reactions of Stable α‐Chlorosulfanyl Chlorides with CS‐Functionalized Compounds

“…Compounds 3 and 4 react easily with thioacetic acid to give acetylated disulfanes [1]. Furthermore, they add to 1 and adamantanethione yielding the corresponding a,a'-dichloro-disulfanes [2] [3].…”