From dipivaloylketene to tetraoxaadamantanes
Dipivaloylketene (2) is obtained by flash vacuum pyrolysis of furan-2,3-dione 6 and dimerizes to 1,3-dioxin-4-one 3, which is a stable but reactive ketene. The transannular addition and rearrangement of enols formed by the addition of nucleophiles to the ketene function in 3 generates axially chiral 2,6,9-trioxabicyclo[3.3.1]nonadienes (bisdioxines) 4. When arylamines are used as the nucleophiles under neutral conditions, decarboxylation occurs during the formation of bisdioxines 8. However, when water or alcohols are added to 3 under acidic conditions, bisdioxine-carboxylic acids and esters 10 and 11 are obtained. Acid hydrolysis of the bisdioxines proceeds through the addition of water to a C=C double bond and results in a second transannular oxa-Michael-type reaction and generation of tetraoxaadamantanes 5. This reaction is decarboxylative when free carboxylic acid functions are present in the bisdioxines, thus forming 21 and 22, but carboxylic acid derivatives are preserved to yield compounds 20, 23, 25, 28, and 29. A hydrogenolysis of the dibenzyl ester 23 yields the free dicarboxylic acid 24. The tetraoxaadamantanes are formed in high yields (65–95%) in most cases, but the addition of water to the concave inside of the bisdioxines becomes severely hindered in cyclic derivatives, so that the 38-membered ring compound 32 requires microwave heating at 170 °C to form tetraoxaadamantane 33, and the catenated compound 36 and calix[6]arene derivative 37 did not form tetraoxaadamantanes. The reaction mechanisms of bisdioxine and tetraoxaadamantane formation are discussed.
Dimerization and condensation of pentane-2,4-dione by MOCl4[M = Mo or W]
Tungsten(VI) oxide tetrachloride reacts with pentane-2,4-dione to form a salt whose single crystal X-ray structure shows a dichloro-dioxopentane-2,4-dionato-tungsten(VI) anion and a 2,4,6-trimethyl-3-acetyl-pyrylium cation; the analogus reaction with molybdenum(VI) oxide tetrachloride yields 1,3,5,7-tetramethyl-2,4,6,8-tetraoxa-adamantane.
Heavy metal adsorption from industrial wastewater by PAMAM/TiO2 nanohybrid: Preparation, characterization and adsorption studies
Abstract This study investigates the removal of heavy metals from industrial wastewater using TiO 2 nanoparticles modified with poly-amidoamine dendrimer (PAMAM, G 4 ). The metal ions Cu 2 + , Pb 2 + , and Cd 2 + were selected as model pollutants. FTIR, SEM, BET surface area and Zeta potential measurements, and Dispersion Observing methods have been employed for characterizing the synthetic nanohybrid and these techniques indicated that the PAMAM loaded on to TiO 2 have been favorably synthesized. The effects of several parameters including initial metal ion concentration, temperature, pH solution, the nanohybrid dosage and contact time were studied. The experimental data were analyzed using equilibrium isotherm and kinetics models. The adsorption process was studied using isotherm, kinetics, and thermodynamics models. The analysis shows that the Langmuir isotherm and pseudo-second-order kinetics are appropriate models for the adsorption process. The thermodynamic parameters illustrate that the absorption is endothermic and spontaneous. The findings suggest that the nanohybrid is a good super absorbent for the removal of heavy metals from industrial effluents.