RESUMEN
Polyazanes (i.e., higher nuclearity homologues of hydrazines) with increasing numbers of bound nitrogen atoms (from 3 to 5), including the first pentazane ever described, were prepared by the addition of lower-order polyazanes to diazo reagents. A structure was obtained. It was shown that the polynitrogen chains adopt a helical conformation. DFT modeling shows that the arrangement persists in solution. Although the polyazanes are all reducing agents, they become less so as the number of nitrogens increases.
RESUMEN
New energetic polymers were synthesized from monomers containing a trans-2-tetrazene unit. In contrast to traditional binders, such as inert hydroxytelechelic polybutadiene or glycidyl azide polymers-in which the energetic features are on the side chains-the energetic groups in the polytetrazenes are incorporated directly in the polymer backbone. Thermal analyses demonstrated that decomposition occurs at approximately 130 °C, regardless of the polymer structure. Glass-transition temperatures ranged from -34.2 to 0.2 °C and could be lowered further (to -61 °C) with the help of a new diazidotetrazene energetic plasticizer. Interestingly, hexafluoroisopropanol (HFIP) enabled complete, room-temperature depolymerization within 1â week. This depolymerization should enable the recycling of unused pyrotechnic compositions based on these new binders.
RESUMEN
The endohedral functionalization of a molecular cage by an azaphosphatrane unit has allowed for the creation of highly engineered catalytic cavities for efficient conversion of CO2 into cyclic carbonates. Strong structure/activity/stability correlations have been demonstrated by careful adjustment of the size, shape, and electronic properties of the hemicryptophane host.
RESUMEN
Three azaphosphatranes were used as organocatalysts for the synthesis of cyclic carbonates from CO2 and epoxides. They proved to be efficient single-component, metal-free catalysts for the reaction of simple or activated epoxides (styrene oxide, epichlorohydrin, glycidyl methyl ether) with CO2 under mild reaction conditions, displaying high stability and productivity over several days of reaction. Substitution patterns on the catalyst were shown to affect activity and stability. Kinetic analysis allowed investigation of the reaction mechanism.
Asunto(s)
Compuestos Aza/química , Dióxido de Carbono/química , Carbonatos/síntesis química , Compuestos Epoxi/química , Compuestos Organofosforados/química , Carbonatos/química , Catálisis , Estructura MolecularRESUMEN
Functionalized hydrazines and bishydrazines are interesting straightforward precursors for accessing higher nitrogenated compounds. They offer structural diversity and promising energetic properties as well, namely for propulsion applications. A novel and scalable synthesis has been developed for a new family of bishydrazines, starting from monomethylhydrazine (MMH). This solvent-free route represents a suitable alternative to the one described in the literature. It was extended to design a new family of unsymmetrical hydrazines bearing various functional groups. A selected series of promising compounds, densified with nitrogenated groups (amino, hydrazino or azido functions), was identified as a class of plausible candidates for liquid propulsion. Indeed, the energetic interest of such hydrazines was demonstrated by computing their heats of formation and specific impulse values in bipropellant systems. This led to theoretical energetic performances comparable to that of the MMH/N2 O4 system already in use today.
RESUMEN
Enantiopure hemicryptophanes designed from the cyclotriveratrylene (CTV) unit display remarkable properties in selective host-guest recognition or as supramolecular catalysts. The unprecedented control of the helical chirality of the CTV unit by remote stereogenic centers of a tren moiety is reported, providing an original access to this highly promising class of host molecules. Although the chiral centers and the CTV unit are separated by more than 10 Å, one single diastereomer is formed; the nature of the diastereoselective process is discussed and the procedure is exemplified using different enantiopure tren derivatives. This work also highlights the influence of the chirality of the CTV unit on the whole cage structure.
Asunto(s)
Modelos Moleculares , Compuestos Policíclicos/química , Catálisis , Cristalografía por Rayos X , Conformación Molecular , Estructura Molecular , Estereoisomerismo , TermodinámicaRESUMEN
The synthesis based on palladium catalytic coupling of 38 new-arylated benzo[b]thiophenes or thiophenes is described in a few steps. We also report the direct arylation of the position 3 of the benzo[b]thiophenic structure, a 'one pot' 2,5-heterodiarylation of thiophenes as well as the synthesis of precursors of amino-acids with a 2-arylated benzo[b]thiophene core. These compounds were evaluated on bacteria strains: most of them did not exhibit any antibiotic activity but were found to selectively inhibit the NorA multidrug transporter of Staphylococcus aureus. As such, they restored the activity of the NorA substrates ciprofloxacin against a resistant S. aureus strain in which this efflux pump is over-expressed.