Cyclohexanethiol

Abstract: 1,6-Anhydro derivatives of D-glucopyranose, maltose, and maltotriose reacted at room temperature with trimethylsilylated benzenethiol (2) and cyclohexanethiol (3) in the presence of zinc iodide (Znl2) or trimethylsilyl triflate (TMSOTf), giving the corresponding thioglycosides with predominance of one anomer in high yield. 1,6-Anhydro-2,3,4-tri-O-benzyl-β-D-glucopyranose (1) condensed with a more complex thiol derivative, methyl 2,3,6-tri-O-benzyl-4-thio-4-S-trimethylsilyl-α-D-glucopyranoside (19), to give the 4-thiomaltose derivative (20), whereas no condensation took place between the 1,6-anhydro disaccharide homologue (21) and thiol derivative (19). The difference in reactivity between 1,6-anhydro mono- and di-saccharides was utilized for a specific cross-coupling reaction.

Abstract: Statistical thermodynamic treatments were made of the conformational energetics of the cyclohexanethiol and 2,4‐dimethyl−3‐thiapentane molecules. For cyclohexanethiol, there are 24 conformations that arise from the chair—skew‐boat and equatorial—axial equilibria of the frame and different orientations of the thiol group. The equatorial‐chair conformation is the most stable; the axial‐chair conformation has about 1.1 kcal/mole greater energy. For 2,4‐dimethyl−3‐thiapentane, six conformations could arise from different orientations of the isopropyl groups; however, only a d—l pair that involves no methyl—methyl interaction between the isopropyl groups has appreciable stability. Vibrational assignments needed for each compound were obtained by interpreting the molecular spectra for the vapor, liquid, and crystal states with the guidance of force‐constant calculations. Tables of the chemical thermodynamic properties were compiled.