Determination of TBT in water and sediment samples along the Argentine Atlantic coast.

Cases of imposex have been reported for some organisms living in areas of the Argentine Atlantic coast. Since this is one of the known effects of the anti-fouling agent tributyltin (TBT), quantitative determinations of organotins in samples of water and sediments collected from sites along the Argentine coast were carried out. Severe cases of imposex were first reported for two gastropod species living in the Mar del Plata area, and determinations of TBT in samples collected from this site gave extremely high values and showed a close correlation between the degree of imposex and TBT concentration. Recent investigations in the area have shown a significant decrease. Surveys were also conducted in sites that exhibit highly irregular coastal profiles to examine the relevance of physical environments. Alarming concentrations of TBT were determined in most of the sites where heavy boat traffic and/or marine activities occur, demonstrating the urgent need for regulations to avoid further input of TBT. Reports from other sites in South America reveal that this should be a subject of regional concern in order to avoid severe damage to the biodiversity of regional marine organisms.

Acid hydrolysis of diazepam. Kinetic study of the reactions of 2-(N-methylamino)-5-chlorobenzophenone, with HCl in MeOH-H2O.

In the acid hydrolysis of diazepam (1), several unusual products, apart from 2-(N-methylamino)-5-chlorobenzophenone (2) and glycine, were isolated. On the assumption that some of those products could arise from further degradation of 2, the reaction of this compound with 0.5-2 M HCl was studied, in 1:1 MeOH-H2O, at 60 and 80 degrees C. Several unexpected products were isolated from the reaction of 2 with HCl, namely, 2-amino-5-chlorobenzophenone (3), 2-(N,N-dimethylamino)-5-chlorobenzophenone (4), 2-(N-methylamino)-3,5-dichlorobenzophenone (5), 2-amino-3,5-dichlorobenzophenone (6), 2,4-dichloro-10-methyl-9,10- acridinone (7), and 2,4-dichloro-9,10-acridinone (8). The methyl transfers, the chlorination, and the cyclization reactions that give rise to products 3-8 are unexpected under the present reaction conditions. The rate of reaction of 2, as well as the rate of formation of compounds 3-6, was measured at several HCl concentrations.

Isolation and structure elucidation of novel products of the acidic degradation of diazepam.

The acidic degradation of diazepam in methanolic aqueous solution has been investigated. Apart from the known degradation products, 2-(N-methylamino)-5-chlorobenzophenone and glycine, produced by the hydrolytic cleavage of the benzodiazepinone ring, five novel products were isolated and fully characterized by their spectroscopic features and independent synthesis. Substituted 2-amino-3,5-dichlorobenzophenones and 2,4-dichloroacridinones were found, the formation of which in the reaction media is mechanistically intriguing. The role of these unexpected products in accelerated studies of diazepam stability is discussed.