Oxidation of prochiral sulfides with chiral dioxirane

Dioxirane generated in situ by reaction of chiral 1,2:4,5-di-O-isopropylidene-D-erythro-hexo-2,4-diulo-2,6-pyranose with Oxone oxidizes prochiral sulfides to the corresponding sulfoxides with an enantiomeric excess of 2 to 25%.     

Electrochemical Reduction and Oxidation of 3,4-Disubstituted 1,2,5-Thiadiazoles

The electron-acceptor nitrogen and sulfur atoms in 3,4-disubstituted 1,2,5-thiadiazoles are responsible for much decreased reduction potentials and much increased oxidation potentials of these compounds compared with the corresponding carbocyclic derivatives. The thiadiazole ring is resistant to oxidation, and the reversible electron transfer gives rise to fairly stable radical cations. Reductive stability of the heterocycle depends on the nature of its substituents and on the medium: When nucleofuge substituents are present, two-electron transfer in aprotic media results in heteroring opening with iminonitrile formation, whereas in the presence of two readily leaving groups, the electron transfer induces cleavage of the complete heteroring into inorganic anions.     

Crystallization of chiral compounds. 1. Spectroscopic,thermochemical, and crystallographic investigation of homochiral and racemic glycidyl p-toluenesulfonate

Crystalline specimens of homochiral and racemic glycidyl p-toluenesulfonate were studied by IR spectroscopy, differential scanning calorimetry, and X-ray diffraction analysis. The melting phase diagram of glycidyl p-toluenesulfonate was constructed. The stacking effect in the crystals of the racemic sulfonate is responsible for a more dense molecular packing, with the result that a heterochiral type of crystallization becomes more favorable.     

New approach to nonracemic 1-alkylamino-3-aryloxypropan-2-ols belonging to β-blockers via cyclic sulfites

Nonracemic -blockers, viz., (S)-propranolol and (S)-timolol, were prepared from (S)-glycidol in three steps consisting in the reaction with SOCl₂ followed by the reaction of the resulting (4S)-4-chloromethyl-2-oxo-1,3,2-dioxathiolanes with the corresponding phenol and the final cleavage of (4R)-aryloxymethyl sulfites under the action of amines in DMF.     

Polarity,polarizability, and structure of esters. 6. Conformations of para-substituted phenyl chloroformates in solutions

The ellipsoid of polarizability of the chloroformate fragment ClC(O)O has principle semiaxes b₁=3.64, b₂=5.34, b₃=3.81 Å₃; the angle between b₁ and the C=0 bond is 24.5°. Aromatic chloroformates in solutions exist in conformations with cisoid position of the C=O and O-R bonds and the phenoxyl fragment in aromatic chloroformates deviates from the plane of the molecule.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2704–2708, December, 1989.The authors wish to thank S. G. Vul'fson for assistance in measuring the depolarization of Rayleigh light scattering.     

Photoelectron spectra of alkoxyacetylenes: n, π-interactions with simultaneous participation of both oxygen unshared pairs

Experimental photoelectron spectra in the series HCC-O-Alk have been studied using correlation analysis and have been compared with the results of nonempirical and semiempirical quantum-chemical calculations. Assignments have been made for the upper MOs in this series. The overlap integrals of the unshared pairs on the oxygen atoms with the-orbitals of the acetylene fragment have been evaluated from the photoelectron spectra and found to be similar in value.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1789–1793, August, 1991.The author is deeply grateful to V. L. Polushina for assistance with the synthesis of the model compounds, to N. V. and Ya. Ya. Villein for recording the photoelectron spectra, and to I. S. Ignat'ev and L. Radom for making available the nonempirical calculations.     

Acoustic nonlinearity of granite: Comparison of data of field and laboratory experiments

The paper presents the results of laboratory measurements of the acoustic nonlinearity parameter for a granite sample from the site of a conducted field experiment. This made it possible to completely confirm the results of the field experiment and explain the occurrence of a large scatter of values for the nonlinearity parameter in the field measurements. The size of the quadratic linearity parameter in granite rocks was determined, normalized to the volumetric concentration of fractures, which can be used for remote estimation of the fracture concentration.     

Synthesis and crystal structure of (S)-pindolol

Racemic 3-(4-indolyloxy)-1,2-propanediol 2 has been effectively resolved into (S)- and (R)-enantiomers by a preferential crystallization procedure. Non-racemic (S)-2 was converted into (S)-4-(2,3-epoxypropoxy)-1H-indole (S)-4 via a Mitsunobu reaction and then into (S)-pindolol (S)-1. The crystalline (S)-1 was studied by single crystal X-ray diffraction. A large number of symmetry independent molecules (Z′ = 6) led to a weakening of the system of strong intermolecular hydrogen bonds, which combined with a loose packing (PI = 64.6%), may be the cause of the abnormally low melting point of (S)-1 as compared with rac-1.