Phase behaviour and molecular dynamics in the binary system of sodium perchlorate and 1,2-propanediamine

The phase and glass transition behaviour in a binary mixture of sodium perchlorate and 1,2-propanediamine {(NaClO₄)_x(12PDA)_1?x, x < 0.40} was investigated by differential scanning calorimetry and Raman scattering measurements. A eutectic point and a peritectic point were found at x = 0.17 and 0.19, respectively. The phase diagram indicates the existence of solvated compounds of (NaClO₄)₁(12PDA)₄ and (NaClO₄)₂(12PDA)₅. The concentration dependence of the glass transition point shows a sigmoid curve implying an underlying anomaly.     

A novel one-pot synthesis of carbazole-1,4-quinones through Pd-catalyzed cyclocarbonylation,desilylation and oxidation processes from 3-iodo-2-propenylindoles

A novel one-pot synthesis of carbazole-1,4-quinone by consecutive Pd-catalyzed cyclocarbonylation, desilylation, and oxidation reactions is described. We propose a possible mechanism of the cyclocarbonylation reaction between 3-iodo-2-propenylindole and CO (1 atm) in the presence of a tributyl(vinyl)tin and Pd-catalyst and the resulting acylpalladium species was directly coupled with a terminal alkene to produce the carbazole-1,4-quinone. To our knowledge, this is the first example of this type of reaction. A new formal total synthesis of a carbazole-1,4-quinone alkaloid, murrayaquinone A was established using this reaction.     

Rhodium(I)-catalyzed direct carboxylation of arenes with CO2 via chelation-assisted C-H bond activation

Rh-catalyzed direct carboxylation of unactivated aryl C-H bond under atmospheric pressure of carbon dioxide was realized via chelation-assisted C-H activation for the first time. Variously substituted and functionalized 2-arylpyridines and 1-arylpyrazoles underwent the carboxylation in the presence of the rhodium catalyst and a stoichiometric methylating reagent, AlMe(2)(OMe), to give carboxylated products in good yields. The catalysis is proposed to consist of methylrhodium(I) species as the key intermediate, which undergoes C-H activation to afford rhodium(III), followed by reductive elimination of methane to give nucleophilic arylrhodium(I). This approach demonstrates promising application of C-H bond activation strategy in the field of carbon dioxide fixation.     

Excess resistance in the superconducting transition of a mesoscopic Al disk

We report resistance measurements on a mesoscopic Al disk whose size is comparable to the superconducting coherence length. As the magnetic field increases, resistance peaks successively appear and some of the peak resistances are larger than the normal state value R_N. These peaks are ascribed to the transitions between different vortex states in the superconducting Al disk. The experimental results suggest that some anomalous energy dissipation is caused by the dynamics of the vortices in the confined geometry.