Adducts of Rh2[MTPA]4 with some phosphine chalcogenides: nature of binding and ligand exchange

Adducts of four phosphine chalcogenides with the chiral dirhodium complex ([Rh-Rh]) were investigated by variable-temperature 1H and 31P NMR spectroscopy in order to compare their properties as axial ligands. Whereas the selenide (1) and the sulfide (2) are strong ligands with electrostatic attraction and, in addition, a significant orbital (HOMO-LUMO) interaction, the phosphine oxide compounds (P=O) bind primarily via electrostatic attraction and are relatively weak donors. Moreover, the overall bond strength in these adducts depends on steric congestion around the P=O group.     

Moclobemide-selective membrane electrode and its pharmaceutical applications

A liquid membrane electrode prepared with moclobemide-dipicrylamine ion-pair complex, dissolved in nitrobenzene as solvent, was studied for analytical performance. The linear response covers the range 10(-3)-10(-6) M moclobemide solution, with a slope of 50.7 mV decade(-1) (pH range 3.5-8). The detection limit is 3 x 10(-7) M. The electrode shows stability, good reproducibility and fast response. The selectivity of the electrode is good. There are two important interfering ions: mianserin and thiamine (Vitamin B(1)). The compression excipients (such as Mg(2+), starch, talcum powder) do not interfere. These characteristics of the electrode enabled it to be used for the determination of moclobemide in drugs and as an active substance, via indirect and direct potentiometric methods. Via an indirect potentiometric method moclobemide, as an active substance, can be determined with an average recovery of 99.96% and a relative standard deviation of 0.85%, and this method can also be used for its determination in drugs with a relative standard deviation of < 2%. The electrode is useful for the determination of the dissolution rate of moclobemide tablets. The physical processes are numerically simulated by typical equations. The apparent first-order rate constants for disintegration and dissolution were calculated.     

Versuche zur Totalsynthese von Brefeldin A

Preliminary results leading towards the total synthesis of Brefeldin A are presented.