Conformational behaviour of medium-sized rings. Part 10. Dithiosalicylides and trithiosalicylides

Study on the Solubilities of Mononitro-Substituted Products of Nitration of m-Toluic Acid in Several Solvents at Temperatures between 297.65 and 351.75 K

“…The common nitrating agents are nitric acid, − urea nitrate, , nitrourea, , guanidine nitrate, nitroguanidine, and N 2 O 5 . This reaction needs to be run for a relatively long time at relatively low temperatures.…”

Cyclophanes in Host-Guest Chemistry

“…77 Because of the substituent s on the benzene rings, 10 is not coplanar and exists in enantiomeric forms that are related to each other as right-and left-handed three-bladed propellers. 75 Among the analogous hosts investigated, 80 only 18 possessed both of the properties exhibited by 10: crystalline inclusion complex formation and spontaneous optical resolution. Thus, although the crystalline complex is a racemate as a whole, optical resolution takes place in every single crystal.…”

Synthesis and Structure of Functionalized Derivatives of the Cleft-Shaped Molecule Dithiosalicylide

“…Conformationally rigid molecules whose structures define cavities and clefts have potential uses as receptors, − catalysts, , and as molecular building blocks in the construction of new materials , NMR 7 and X-ray crystallographic 8 studies have shown that dithiosalicylide ( 1 ) adopts a boat conformation where the aromatic rings form a shallow “v-shaped” pocket in which the dihedral angle between the aromatic rings is approximately 65 ° . Although dithiosalicylides are not conformationally locked, as is the case for the structurally related Kagan's ether 1,2 and Troeger's base 3 compounds, the inversion barrier between the enantiomeric boat conformations is quite high (∼25 kcal/mol) …”

“…7,8 NMR 7 and X-ray crystallographic 8 studies have shown that dithiosalicylide (1) adopts a boat conformation where the aromatic rings form a shallow "vshaped" pocket in which the dihedral angle between the aromatic rings is approximately 65 °.8 Although dithiosalicylides are not conformationally locked, as is the case for the structurally related Kagan's ether 1,2 and Troeger's base 3 compounds, the inversion barrier between the enantiomeric boat conformations is quite high (∼25 kcal/ mol). 7 As part of investigations [9][10][11] into the chemistry of 3H-1,2-benzodithiol-3-one 1-oxide and related compounds, we recently developed a simple preparation of dithiosalicylide from 3H-1,2-benzodithiol-3-one (2). 12,13 Treatment of 2 with triphenylphosphine provides good yields of 1, presumably via dimerization of a benzothietan-2-one (3) or ketene (4) intermediate (Scheme 1).…”