Comparative conformational analysis of 1,3-dioxane and 1,3-dithiane

It was shown by ab initio quantum-chemical approximations HF/6-31G(d) and MP2/6-31G(d)//HF/6-31G(d) that the conformational isomerization of 1,3-dioxane and 1,3-dithiane proceeded along common routes. The potential energy surface of both compounds contains six minima including the chair invertomers and enantiomeric flexible forms. They are separated by several potential barriers. It was established by molecular dynamics method that the flexible conformers at heating and keeping at 295–300 K transformed into each other and in the chair conformer.     

Zur stereochemie S-alkylierter 1,3-dithiane

The steric relationships of some mono- and bis-sulfonium-salts of 1,3-dithianes previously described by us are discussed by NMR-spectroscopic measurements.     

A rapid, efficient and selective conversion of aldehydes and acetals to their 1,3-dithiane derivatives with 2,2-dimethyl-2-sila-1,3-dithiane

Aldehydes and acetals are cleanly and rapidly converted to the corresponding dithianes with 2,2-dimethyl-2-sila-1,3-dithiane and stoichiometric amounts of boron trifluoride etherate even in the presence of ketones, which do not react competitively with the reagent.     

Collision-induced dissociations of substituted benzyl anions: Deprotonated 2-Phenyl-1,3-dithiane

Deprotonated 2-phenyl-1,3-dithiane undergoes competitive losses of H˙, C₃H₆ C₂H₄S, C₃H₄S, C₇H₆S, C₁₀H₁₀ and C₁₀H₁₀S upon collisional activation. The elimination of H occurs from the phenyl ring. The loss of C₃H₆ occurs by simple cleavage of the dithiane ring. All other processes involve specific proton transfer followed by either cleavage or internal nucleophilic displacement.     

Reaction of lithiated 2-trimethylsilyl-1,3-dithiane with (±)-pantolactone

Pantolactone methoxymethyl ether reacted with lithiated 2-trimethylsilyl-1,3-dithiane to give the corresponding ketene dithioacetal and formal monoaddition product of silicon-free 2-lithio-1,3-dithiane at a ratio of 2:1. Possible ways of formation of the latter are discussed.     

New 1,3-dithiane type ionic liquid crystal compounds

New pyridinium type thermotropic ionic liquid crystal materials having a 1,3-dithiane ring in their central core, N -substituted-4-(5-alkyl-1,3-dithian-2-yl)pyridinium bromides ( 8 ), were synthesized. These compounds exhibited a smectic A phase over a very wide temperature range including room temperature.     

Crystal and molecular structures of diastereomeric 2-phosphoryl-, 2-thiophosphoryl-, and 2-selenophosphoryl-substituted 1,3-dithianes

The crystal and molecular structures of five pairs of diastereomeric cis- and trans-2-phosphoryl-, 2-thiophosphoryl-, and 2-selenophosphoryl-5-t-butyl-1,3-dithianes have been determined. For all the examined compounds, all of the basic geometrical parameters, such as bond lengths, bond and torsion angles, and the deformation of a chair conformation of the six-membered heterocyclic rings, have been established. The differences in corresponding bond lengths and valence angles in diastereomeric cis- and trans-2-P-substituted 1,3-dithianes are discussed.     

Calorimetric and computational study of 1,3-dithiacyclohexane 1,1-dioxide (1,3-dithiane sulfone)

The enthalpies of combustion and sublimation of 1,3-dithiacyclohexane 1,1-dioxide (1,3-dithiane sulfone) were measured by a rotating-bomb combustion calorimeter and the Knudsen effusion technique, and the gas-phase enthalpy of formation was determined, Delta(f)H(m)*(g) = -326.3 +/- 2.0 kJ mol(-1). Standard ab initio molecular orbital calculations at the G2(MP2) level were performed, and a theoretical study on molecular and electronic structure of the compound has been carried out. Calculated Delta(f)H(m)*(g) values agree very well with the experimental one. These experimental and theoretical studies support the relevance of the repulsive electrostatic interaction between sulfur atoms in 1,3-dithiane sulfone, that apparently counterbalances any n(S) --> rho(C-SO2)* stabilizing hyperconjugative interaction.