Influence of steric factors on the direction of reactions

Russian Journal of Organic Chemistry -     

Pressure-driven "molecular metal" to "atomic metal" transition in crystalline Ga

We present the ultrasonic study of gallium (Ga I) under high pressure up to 1.7 GPa, including the measurements of the density and elastic properties during phase transitions to Ga II and to a liquid state. The observed large drop of both bulk and shear moduli (by 30% and 55%, correspondingly) during the phase transition to Ga II, as well as the increase of the Poisson's ratio from typically "covalent" ( approximately 0.22) to "metallic" ( approximately 0.32) values, experimentally testifies to the coexistence of a molecular and metallic behavior in Ga I and to the disappearance of the "covalency" during the transition to Ga II. A high value of the pressure derivative of the bulk modulus for Ga I and the increase in the Poisson's ratio can be associated with the weakening of the covalency in compressed Ga I and considered as a precursor of the transition to normal metal.     

5,5-dimethyl-1,3-dioxan-4-ol as orthogonally protected equivalent of 2,2-dimethyl-3-hydroxypropanal

Condensation of isobutyraldehyde with aqueous formaldehyde in the presence of Ba(OH)2 gave a new gem-dimethyl-substituted building block.     

Synthesis of the northern fragment of an epothilone D analogue from (−)-carvone

A simple and effective synthesis of the chiral thiazole-containing fragment of an epothilone D analogue from (?)-carvone is described.     

Ultrasonic study of the phase diagram of methanol

The phase diagram of methanol is studied by an ultrasonic technique over the temperature range 90–290 K at pressures up to 1.2 GPa. The pressure and temperature dependence of the velocity of longitudinal ultrasonic waves and the density of crystalline and liquid phases has been determined. Weak anomalies in the velocity of ultrasound in the liquid phase of methanol and the corresponding anomalous additional compression of the liquid at 230–250 K and 0.2–0.6 GPa have been found, and they are likely attributable to structural changes in the liquid phase.     

Elastic properties of crystalline and liquid gallium at high pressures

The elastic properties of gallium, such as the bulk modulus B, the shear modulus G, and the Poisson’s ratio σ, are investigated and the relative change in the volume is determined in the stability regions of the Ga I, Ga II, and liquid phases at pressures of up to 1.7 GPa. The observed lines of the Ga I-Ga II phase transition and the melting curves of the Ga I and Ga II phases are in good agreement with the known phase diagram of gallium; in this case, the coordinates of the Ga I-Ga II-melt triple point are determined to be 1.24 ± 0.40 GPa and 277 ± 2 K. It is shown that the Ga I-Ga II phase transition is accompanied by a considerable decrease in the moduli B (by 30%) and G (by 55%) and an increase in the density by 5.7%. The Poisson’s ratio exhibits a jump from typically covalent values of approximately 0.22–0.25 to values of approximately 0.32–0.33, which are characteristic of metals. The observed behavior of the elastic characteristics is described in the framework of the model of the phase transition from a “quasi-molecular” (partially covalent) metal state to a “normal” metal state. An increase in the Poisson’s ratio in the Ga I phase from 0.22 to 0.25 with an increase in the pressure can be interpreted as a decrease in the degree of covalence, i.e., the degree of spatial anisotropy of the electron density along the bonds, whereas the large value of the pressure derivative of the bulk modulus (equal to approximately 8) observed up to the transition to the Ga II phase or the melt is associated not only with the quasicovalent nature of the Ga I phase but also with the structural features. In view of the presence of seven neighbors for each gallium atom in the Ga I phase, the gallium lattice can be treated as a structure intermediate between typical open-packed and close-packed structures. Premelting effects, such as a flattening of the isothermal dependence of the shear modulus G(p) with increasing pressure and an increase in the slope of the isobaric dependences G(T) with increasing temperature, are revealed in the vicinity of the melting curve. The bulk modulus of liquid gallium near the melting curve proves to be rather close to the corresponding values for the normal metal Ga II.