Co-catalysis of rhodium/phosphoramidite catalyst and ZSM-35(10) for the tandem hydroformylation-acetalization of olefins.

The Rh/BINAPa and ZSM-35(10) co-catalyzed tandem hydroformylation-acetalization of olefins has been developed. A series of olefins with various alcohols performed well in the process, affording the corresponding acetals with high regioselectivities (l/b ≥ 30.5) and excellent catalytic activities (TON of the Rh catalyst up to 4.3 × 104). Control experiments and DFT calculations indicated that the Rh/L11-catalyzed hydroformylation occurred in the solvent outside the molecular sieve, while the acetalization of intermediate aldehydes with alcohols takes place mainly in the interior of the molecular sieve.

Synthesis and promising properties of a new family of high-nitrogen compounds: polyazido- and polyamino-substituted N,N'-azo-1,2,4-triazoles.

A new family of high-nitrogen compounds, that is, polyazido- and polyamino-substituted N,N'-azo-1,2,4-triazoles, were synthesized in a safe and convenient manner and fully characterized. The structures of 3,3',5,5'-tetra(azido)-4,4'-azo-1,2,4-triazole (15) and 3,3',5,5'-tetra(amino)-4,4'-azo-1,2,4-triazole (23) were also confirmed by X-ray diffraction. Differential scanning calorimetry (DSC) was performed to determine their thermal stability. Their heats of formation and density, which were calculated by using Gaussian 03, were used to determine the detonation performances of the related compounds (EXPLO 5.05). The heats of formation of the polyazido compounds were also derived by using an additive method. Compound 15 has the highest heat of formation (6933 kJ kg(-1)) reported so far for energetic compounds and a detonation performance that is comparable to that of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), while compound 23 has a decomposition temperature of up to 290 °C.