Synthesis of a new class of chiral 1,5-diphosphanylferrocene ligands and their use in enantioselective hydrogenation

A new family of ferrocenylphosphane ligands has been prepared. Their flexible synthesis allows many structural modifications. The asymmetric induction of these ligands was examined in the hydrogenation of functionalized C=C, C=O, and C=N bonds. The enantioselectivity of the reaction was strongly dependent on the substituent R at the position alpha to the ferrocene moiety. In many cases, both enantiomeric beta-hydroxyesters of the reduction product can be obtained by simply replacing a dimethylamino group in the ligand with a methyl group.     

Trace analysis of rare earth elements and other impurities in high purity scandium by inductively coupled plasma mass spectrometry after liquid-liquid extraction of the matrix

Bis(2-ethyl hexyl)-orthophosphoric acid in toluene has been used to extract scandium selectively from an aqueous phase containing nearly thirty elements at various concentrations. The trace elements (Li, Mg, Al, Mn, Co, Ni, Cu, Zn, Ga, Sr, Y, Cd, In, Sb, Ba, REE, Hf, Pt, Tl, Pb, Bi and u) have been determined quantitatively in the aqueous phase using inductively coupled plasma mass spectrometry (ICP-MS). The recoveries have been quantitative for most of the analytes studied and ICP-MS has been found suitable for the determination of trace quantities of these elements in the aqueous extract. The procedure has been applied to the quantitative ultra-trace analysis of rare earth elements (REE) and other trace impurities in high purity scandium metal (4N) using ICP-MS and ID-ICP-MS techniques.Presented in part at the 2nd Regensburger Symposium Massenspektrometrische Verfahren der Elementspurenanalyse, 6.-8.10.93, Regensburg, Germany     

High-performance liquid chromatography of non-polar retinoid isomers

Normal-phase high-performance liquid chromatograms of retinal, retinol and retinyl palmitate isomers using n-heptane-tert.-butyl methyl ether as mobile phase are presented. Methods for the synthesis of various isomers of these retinoids are described. This enables one to produce standard chromatograms and to select various isomers for cochromatography and the identification of the various peaks under study. Assignment of the peaks is based on chromatograms published previously in this journal. For the main isomers it is possible to get baseline separation of the commonly occurring isomeric forms in a reasonably short analysis time.     

Selective modification of the 2-position of pyridoxol

Pyridoxol, protected by acetylation of the hydroxyl groups, has been converted to its N-oxide which upon reaction with perfluoroacetie anhydride yields a 2-nor-2-hydroxymethylpyridoxol derivative as an intermediate. This compound undergoes acyl migration from the 3-position. Protection of the pyridoxol hydroxyls by benzylalion followed by the same treatment yields the unrearranged α²-hydroxy derivative. This compound has been converted to a series of α²-substituted pyridoxols (X = -Cl, -Br, -OCOCH₃, -OCH₃, -OC₂H₅).     

Novel fluorinated block copolymer architectures fuelled by atom transfer radical polymerization

Block copolymers based on poly(pentafluorostyrene), PFS, in various numbers and of different lengths, and polystyrene are prepared by atom transfer radical polymerization (ATRP). Di- and triblock copolymers with varying amounts of PFS were synthesized employing either 1-phenylethylbromide or 1,4-dibromoxylene as initiators for ATRP. Diverse bromo(ester) (macro)initiators were also devised and involved in the formulation of fluorinated pentablock as well as amphiphilic triblock copolymers with a central polyether segment. Amphiphilic star-shaped fluoropolymers, hydrophobic fluorinated nanoparticles, or segmented fluorinated star-shaped block copolymers are further designed by use of different multifunctional initiators. The composition of the novel materials with PFS is determined by combination of SEC and ¹H NMR. Glass transition temperatures and thermal stabilities of the hydrophobic star-shaped PFSs on a six arm dipentaerythritol core are investigated in a wide range of molecular masses and further discussed.     

Kinetic and mechanistic study of the quasiliving cationic polymerization of styrene with the 2-phenyl-2-propanol/AlCl3 · OBu2 initiating system

The cationic polymerization of styrene with the 2-phenyl-2-propanol (CumOH)/AlCl₃ · OBu₂ initiating system at various dibutyl ether concentrations in a mixture of 1,2-dichloroethane and n-hexane (55:45 v/v) at −15 °C was investigated. The experimental results showed that an increase in dibutyl ether concentration leads to a noticeable decrease in the polymerization rate as well as to the more controlled polymerization in terms of molecular weight (M_n) and molecular weight distribution (MWD) evolutions. The kinetic investigation revealed that the polymerization proceeds in two stages. The first stage is characterized by high polymerization rate and slow initiation relative to propagation. During this stage molecular weight decreases or does not change and MWD increases with conversion. In the second stage considerably slower quasiliving polymerization of styrene occurs. The quasiliving nature of the styrene polymerization by the CumOH/AlCl₃ · OBu₂ system is proved and mechanistic scheme of the polymerization is proposed.