Approaches to control selectivity and activity in the catalytic reductive amination of butyraldehyde with ammonia over carbon supported noble metal catalysts (Ru, Rh, Pd, and Pt) were explored. Detailed analysis of the reaction network shows that the Schiff base N-[butylidene]butan-1-amine is the most prominent initial product and, only after nearly all butyraldehyde had been converted to N-[butylidene]butan-1-amine, amines are detected in the product mixture. From this intermediate, good hydrogenolysis catalysts (Ru, Rh) produce mostly butylamine, while catalysts less active in hydrogenolysis (Pd, Pt) lead to the hydrogenation of N-[butylidene]butan-1-amine to mostly dibutylamine.

This article describes the synthesis and characterization of polyisobutylene (PIB) carrying one primary hydroxyl head group and a tertiary chloride end group, [PhC(CH3)(CH2OH)–PIB–CH2C(CH3)2Cl] prepared with direct functionalization via initiation. The polymerization of isobutylene was initiated with the α‐methylstyrene epoxide/titanium tetrachloride system. Living conditions were obtained from −75 to −50 °C (198–223 K). Low molecular weight samples (number‐average molecular weight ∼ 4000 g/mol) were prepared under suitable conditions and characterized by Fourier transform infrared and 1H NMR spectroscopy. The presence of primary hydroxyl head groups in PIB was verified by both methods. Quantitative Fourier transform infrared with 2‐phenyl‐1‐propanol calibration and 1H NMR performed on both the hydroxyl‐functionalized PIB and its reaction product with trimethylchlorosilane showed that each polymer chain carried one primary hydroxyl head group. The synthetic methodology presented here is an effective and simple route for the direct functionalization of PIB. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1005–1015, 2002

First direct spectroscopic evidence for the existence of Bransted acid sites in AIP04-5 (AFI) single crystal molecular sieves substituted with divalent metal cations is reported. Ammonia and pyridine were used as probe molecules. Compared with unsubstituted AlPOd-single crystals, the metal substituted samples exhibit well-developed bands of isolated hydroxyl groups and a broad absorption band indicating the existence of hydrogen bonded OH groups. Upon adsorption of pyridine on the metal substituted samples the formation of a new, relatively free vibrating hydroxyl group (vOH = 3690-3694 cm-') was observed, giving evidence for a strong Lewis type interaction leading to the cleavage of a metal-oxygen bond close or at the position of the substituting metal cation. 0 1997 Elsevier Science B.V.