Continuous flow hydroformylation of alkenes in supercritical fluid-ionic liquid biphasic systems

A process for the hydroformylation of relatively low volatility alkenes (demonstrated for 1-dodecene) in a continuous flow system is described. The catalyst is dissolved in an ionic liquid while the substrate and gaseous reagents are transported into the reactor dissolved in supercritical CO(2), which simultaneously acts as a transport vector for aldehyde products. Decompression of the fluid mixture downstream yields products which are free of both reaction solvent and catalyst. The use of rhodium complexes of triaryl phosphites leads to ligand degradation through reaction of the ionic liquid with water and subsequent attack of the released HF on the phosphite. Sodium salts of sulfonated phosphines are insufficiently soluble in the ionic liquids to obtain acceptable rates, but replacing the sodium by a cation similar to that derived from the ionic liquid, allows good solubility and activity to be obtained. The nature of the ionic liquid is very important in achieving high rates, with 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amides giving the best activity if the alkyl chain is at least C(8). Catalyst turnover frequencies as high as 500 h(-1) have been observed, with the better rates at higher substrate flow rates. Rhodium leaching into the product stream can be as low as 0.012 ppm, except at low partial pressures of CO/H(2), when it is significantly higher. Oxygen impurities in the CO(2) feed can lead to oxidation of the phosphine giving higher rates, lower selectivities to the linear aldehyde, increased alkene isomerization and greater leaching of rhodium. However, it is found that under certain process conditions, the supercritical fluid-ionic liquid (SCF-IL) system can be operated continuously for several weeks without any visible sign of catalyst degradation. Comparisons with commercial hydroformylation processes are provided.     

Continuous flow homogeneous catalysis using supercritical fluids

The continuous flow hydroformylation of 1-octene catalysed by Rh/[RMIM][Ph(2)PC(6)H(4)SO(3)](R = 1-propyl, 1-pentyl or 1-octyl) dissolved only in the steady state reaction mixture and using scCO(2) as a transport vector for both substrates and products gives rates up to 160-240 catalyst turnovers h(-1) with low rhodium leaching over a 12 h period at a total pressure of 125-140 bar.     

The preparation and crystal structure of bis(bis(diphenyl-phosphino)ethane)carbonylformylosmium(II) hexafluoroantimonatedichloromethane (1/1)

Reaction of trans[Os(CO)₂(dppe)₂]²⁺ with [KHB(OPrⁱ)₃] gives the formyl complex trans[Os(CHO)(CO)(dppe)₂][SbF₆] which is thermally very stable; the crystal structure shows it to have trans stereochemistry and a long Os-C bond.     

Highly selective formation of linear esters from terminal and internal alkenes catalysed by palladium complexes of bis-(di-tert-butylphosphinomethyl)benzene

The methoxycarbonylation of terminal or internal alkenes catalysed by palladium complexes of bis-(di-tert-butylphosphinomethyl)benzene under mild conditions leads to linear esters in 99% selectivity via a hydride mechanism.     

Studies of prereactions during MOVPE growth of wide band-gap II/VI semiconductors: the effect of pyridine upon the gas-phase reactions between H2S and Me2Zn

The effect of pyridine addition upon the gas-phase reactions of hydrogen sulphide (H₂S) with dimethylzinc (Me₂Zn) in the presence of pyridine has been investigated and compared with results from reactions of H₂S with Me₂Cd. The deposits of ZnS which form have been analysed and consist of particles in the nanocrystalline size range of mainly the hexagonal phase. The average particle size within the deposits depends on both the concentration of pyridine in the gas phase and the temperature at which the reactants are mixed. Pyridine may bind through the lone pair of the nitrogen to surface metal atoms of growing particles, inhibiting further growth of the particle.     

Synthesis of hybrid dendritic molecules with diazaphospholidine oxide grafted at the surface of octavinylsilsesquioxane (OVS)

A range of dendritic molecules was made using the monodentate SEMI-ESPHOS phosphine oxide ligand, which was derivatised with a series of functional groups including bromide, vinyl, allyl and terminal alkyne. Several methods to attach the resulting precursors onto octavinylsilsesquioxane (OVS), ranging from hydrosilylation, Suzuki, Heck, Grubbs or Sonogashira coupling reactions, have been investigated. Cross-metathesis of SEMI-ESPHOS oxide dendrons containing vinyl end groups with OVS catalyzed by Grubbs' catalyst was proven to be effective in the formation of precursors for dendritic molecules based on OVS.     

Vectorial Approach to Fast Correlation Attacks

A new, vectorial approach to fast correlation attacks on binary memoryless combiners is proposed. Instead of individual input sequences or their linear combinations, the new attack is targeting subsets of input sequences as a whole thus exploiting the full correlation between the chosen subset and the output sequence. In particular, the set of all the input sequences can be chosen as the target. The attack is based on a novel iterative probabilistic algorithm which is also applicable to general memoryless combiners over finite fields or finite rings. To illustrate the effectiveness of the introduced approach, experimental results obtained for random balanced combining functions are presentedMost of this work was done while he was with Rome CryptoDesign Center, Gemplus, Italy     

On the Motion of a Dynamic System with Minimal Dissipation

The motion of a holonomic scleronomic non-conservative mechanicalsystem with minimal dissipation is considered. As applicationsof the theory several problems are studied in detail.