Phase equilibria and excess properties for binary systems in reactive distillation processes Part I. Methyl acetate synthesis

Isothermal vapor–liquid equilibrium (VLE) and excess enthalpy (H^E) data were measured for binary systems required for the design of reactive distillation processes for the methyl acetate production. The isothermal P–x data were measured with the help of a computer-operated static apparatus. A commercial isothermal flow calorimeter was used for the determination of the heats of mixing. Temperature-dependent interaction parameters for the UNIQUAC model were fitted simultaneously to the experimental data from this work and other authors.     

Cp*(2)TiMe(2): an improved catalyst for the intermolecular addition of n-alkyl- and benzylamines to alkynes

Cp(2)TiMe(2) has been found to be a competent catalyst for the intermolecular addition of sterically less demanding n-alkyl- and benzylamines to internal alkynes. In the presence of 2.0-6.0 mol % of the catalyst, hydroamination reactions between n-propyl-, n-hexyl-, benzyl-, p-methoxybenzyl- or 2-phenylethylamine and diphenylacetylene, 3-hexyne or 4-octyne go to completion within 24 h or less at 114 degrees C (oil bath temperature). After subsequent reduction of the initially formed imines with zinc-modified sodium cyanoborohydride in MeOH at 25 degrees C, the corresponding secondary amines can be isolated in excellent yields (>78%). Hydroamination/reduction sequences employing the unsymmetrically substituted alkyne 1-phenylpropyne give access to mixtures of regioisomeric secondary amines. The observed regioselectivity is low.     

Ni(0)L]-catalyzed cyclodimerization of 1,3-butadiene: a density functional investigation of the influence of electronic and steric factors on the regulation of the selectivity

We present a comprehensive theoretical investigation of the influence of the ligand L on the regulation of the product selectivity for the [Ni(0)L]-catalyzed cyclodimerization of 1,3-butadiene. The investigation was based on density functional theory (DFT) and a combined DFT and molecular mechanics (QM/MM) approach for the real [bis(butadiene)Ni(0)L] catalysts with L = PMe(3), I; PPh(3), II; P((i)Pr)(3), III; and P(OPh)(3), IV. The role of electronic and steric effects has been elucidated for all crucial elementary steps of the entire catalytic cycle. Allylic isomerization, allylic enantioface conversion, as well as oxidative coupling are shown to be influenced to a minor extent by electronic and steric effects. In contrast, the ligand's properties have a distinct influence on the preestablished equilibrium between the eta(3),eta(1)(C(1)) and bis-eta(3) forms 2 and 4, respectively, of the [(octadienediyl)Ni(II)L] complex and on the rate-determining reductive elimination following competing routes for generation of either VCH, cis-1,2-DVCB, or cis,cis-COD. Electronic factors are shown to predominantly determine the position of the kinetically mobile 2 right harpoon over left harpoon 4 equilibrium. 4 is the prevailing species for ligands L that are pi-acceptors (L = P(OPh)(3)) or weak sigma-donors (L = PPh(3)), while stronger sigma-donors (L = PMe(3), P((i)Pr)(3)) displace the equilibrium to the left. Steric bulk on the ligand as well as its pi-acceptor ability act to facilitate the reductive elimination, while sigma-donor abilities serve to retard this process. Electronic and steric factors are found to not influence uniformly the reductive elimination routes with either 2 or 4 involved. The regulation of the product selectivity is elucidated on the basis of both thermodynamic and kinetic considerations.     

Mass density and dielectric constants of quench condensed AuSn-and AgSn-films

The mass density and dielectric constants at λ=632.8 nm of quench condensed AuSn and AgSn films are determined by ellipsometric measurements combined with quartz microbalances. The measurements, which were carried out continuously during the condensation process indicate that the properties of these films are thickness dependent for films thinner than about 30 nm. There is strong evidence that the films have a porous structure which decreases with increasing films have a porous structure which decreases with increasing film thickness asymptotically. The mass density of the films thicker than 30 nm is in the whole concentration range lower than the interpolations of the densities of the pure solid elements assuming a constant atomic volume but it is higher than a corresponding interpolation of the densities of the pure liquid elements. An evaluation of the complex dielectric constant (DC) of the thicker films according to the Drude theory yields a relaxation time of the disordered films, which is distinctly smaller than that of bulk metals. In the case of the thicker films no annealing effects are observed.     

Direct potentiometric immunoelectrodes

Summary The selective binding of 3-indole acetic acid (IAA) alkali phosphatase (AP) to respective antibodies immobilized on pretreated titanium wires as electrodes (40×0.8 mm ø) is studied and the conditions are optimized with respect to selectivity and sensitivity, and the cross-reactivity of some related compounds is determined. Using these experiences, such wires are used as electrodes to detect selectively the methylester of IAA (IAA-Me). They are shown to behave best when the change of the electrode potential is measured against a similar reference electrode, coated with immobilized immuno globulin G (IgG) of the respective pre-immuno serum. A second coating with bovine serum albumin (BSA) is shown to prevent unspecific binding of IAA-Me. The sensitivity goes down to around 100 pmol/ml. Part I: Fresenius J Anal Chem (1992) 343:541     

Crystallization of amorphous metal films within and without magnetic field

Assuming that the conduction electrons of an amorphous metal contribute to the binding, we investigate whether a magnetic field will influence the transition from the amorphous to the crystalline state. Measurements taken on amorphous Bi, Ga and Yb films show no change in the crystallization temperatures within an accuracy of ±0.1 K due to a magnetic field of 18.5 T parallel to the surface of the films.Dedicated to Prof. Dr. W. Buckel on the occasion of his 60th birthday     

2,3,5,6-Tetramethylmorpholine: II—1H n.m.r. structural studies of the isomers of 2,3,5,6-tetramethylmorpholine

The structures of the six isomers of 2,3,5,6-tetramethyl-morpholine have been determined by means of proton nuclear magnetic resonance studies at 100 MHz. The spectra have been analysed in terms of spin–spin coupling constants and population distributions of the possible conformers at low temperatures. Also included in this paper are results from n.m.r. studies on the six 4-benzyl-2,3,5,6-tetramethylmorpholine derivatives, which give information about the stereochemistry of the methyl groups α to the amine group.