Use of an ionic liquid in a two-phase system to improve an alcohol dehydrogenase catalysed reduction

Due to favourable partition coefficients the highly enantioselective reduction of 2-octanone, catalysed by an alcohol dehydrogenase from Lactobacillus brevis, is faster in a biphasic system containing buffer and the ionic liquid [BMIM][(CF(3)SO(2))(2)N] compared to the reduction in a biphasic system containing buffer and methyl tert-butyl ether.     

Reversal of diastereoselectivities in intra- and intermolecular reactions of 2-adamantanylidenes primarily caused by electron-donating and electron- withdrawing substituents on C5

[reaction: see text] A reversal of diastereoselectivity was observed for novel 5-(trimethylsilyl)adamantan-2-ylidene (1c) with regard to 5-hydroxyadamantan-2-ylidene (1a). Ostensibly in intermolecular reactions, 5-substituted 2-adamantanylidenes (1) are sterically unbiased. However, inductive effects originating from the pendant group bend the divalent carbon bridge of 1 either toward (ERG's, e.g., -Si(CH(3))(3)) or away from (EWG's, e.g., -OH) the gamma-position. Hence, the more exposed side is more susceptible to intermolecular reaction and the other side concomitantly undergoes intramolecular 1,3-CH insertions more readily.     

Ultrasonic Broadband Spectrometry of Liquids A Research Tool in Pure and Applied Chemistry and Chemical Physics

This review is a survey of the many scientific applications of ultrasonic broadbandspectrometry (absorption and velocity measurements with coherent sound waves)in liquids and liquid systems, covering, at present, a frequency range from nearly10 kHz to 10 GHz. Ultrasonic spectrometry has proved to be an almost universalresearch tool in many laboratories, one that is useful for investigation of variouschemical, biochemical, and physicochemical systems. Sound waves traversingliquids induce periodic perturbations in pressure and temperature, which can shiftequilibria, resulting in characteristic sound absorption and velocity dispersionspectra. An analysis of such spectra yields valuable information about thermodynamic and kinetic parameters of the particular system that is often difficult toobtain by other methods. Since such periodic perturbations imposed on the systemare incremental in nearly all cases, the system can be studied under equilibriumconditions. All nonlinear effects (heating, nonconstant fluid compressibility, andothers) are negligible, permitting, for instance, the application of linearized rateequations. In this review, various examples of measured broadband spectra arepresented. Related elementary processes are discussed. Among these are ionicand molecular reactions, including mechanisms of association and complexation,proton transfer, solvation, isomerization, interconversion, side-group rotation,hydrogen-bonding, as well as stacking processes and micelle formation. Specialattention will be given to the extensive research on chemical relaxation.Fundamental early and recent publications are cited and discussed. Many referencesare included with particular emphasis on less well known research and publicationsfrom countries of the former USSR. This review aims at a demonstration of thewidespread applications of modern ultrasonic techniques in many fields ofliquid-state research.     

Tetrakis(2-hydroxyphenyl)ethene and derivatives. A structurally preorganized tetradentate ligand system for polymetallic coordination chemistry and catalysis

A topologically unique, conformationally constrained tetradentate ligand system for polymetallic coordination chemistry has been developed: tetrakis(2-hydroxyphenyl)ethene (1a) and substituted derivatives. The design exploits the planarity of the tetraphenylethylene core to impart rigidity to the roughly square oxygen binding array, while maintaining a degree of conformational mobility associated with rotation about the aryl-ethylene carbon-carbon bonds. Tetrakis(2-hydroxyphenyl)ethene derivatives are designed to promote multiple metal bridging over chelating coordination modes. The ligand is synthesized from anisole or 4-tert-butylanisole in four steps via the 2,2'-dimethoxybenzophenone hydrazones 4a,b. The sterically hindered ortho-substituted tetraphenylethylene core is produced in high yield by acid-catalyzed decomposition of the corresponding diaryl diazomethane prepared in situ by oxidation of the hydrazone using nickel peroxide. Deprotection of the methyl ethers using boron tribromide gives tetrakis(2-hydroxyphenyl)ethene (1a), characterized by X-ray crystallography, and tetrakis(5-tert-butyl-2-hydroxyphenyl)ethene (1b). Sterically isolating substituents in the 3-position can be installed via Claisen rearrangement/hydrogenation, providing tetrakis(3-n-propyl-2-hydroxyphenyl)ethene (6) efficiently. To illustrate potential applications of this unprecedented ligand class, two coordination complexes are reported, including tetrakis(2-diethylaluminoxyphenyl)ethene (8), a structurally robust eight-membered-ring aluminum/oxygen crown complex characterized both in solution and in the solid state.     

The chemistry of the azanonaborane cluster RNH2---B8H11NHR

The preparation and properties of the R¹R²NH---B₈H₁₁NHR cluster are described. The cluster is stable to aqueous solutions and can be made water-soluble by the introduction of a few hydrophilic groups. This makes the cluster a good candidate as the boron moiety in compounds for boron neutron capture therapy. The chemistry of the cluster preparation, the stability of the cluster, and conditions for reactions of the organic moieties are reviewed. Pyridine derivatives of the cluster show electronic interaction between the cluster and the pyridine.     

Capillary Electrophoresis Coupled On-Line with Nitrogen-Selective Thermionic Detection Using an Eluent-Jet Interface

The on-line coupling of capillary electrophoresis (CE) with a thermionic detector (TID) originally developed for gas chromatography (GC) is reported for the first time. An eluent-jet interface previously used to combine micro-liquid chromatography and mass spectrometry can now be used to couple CE and TID. Preliminary results demonstrate the possibility of performing direct nitrogen-selective detection, even for less volatile compounds. Detection limits of 4–12 pg N/s were obtained for the four tested compounds piperidine, dimethylformamide, tetra-n-butylammonium hydroxide, and nicotinic acid. Optimization of both the TID and the eluent-jet interface can be performed independently; optimum TID parameters agree rather closely with the detector specifications under GC conditions. The nitrogen-selective TID proved to be linear over more than three orders of magnitude with acceptable repeatability. The on-line coupling of CE and TID may well become an interesting approach for the rapid and direct analysis of ionic and high-molecular-mass N-containing compounds.     

Thermolysis of 1-(1-aryl-1-bromomethyl)cyclopropyl bromides: a reinvestigation

Two compounds, the (Z)- and (E)-isomers of 2,4-dibromo-1-p-tolyl-1-butene 2a and 3a, respectively, were isolated in 65% total yield when 1-(1-bromo-1-p-tolylmethyl)cyclopropyl bromide (1a) was heated at 150 degrees C for 1 h. 1,1-Dibromo-2-p-tolylcyclobutane (4a), previously reported to be the only product in this reaction, was not detected. The phenyl analogue of 1a reacted similarly and gave the (Z)- and (E)-isomers of 2,4-dibromo-1-phenyl-1-butene 2b and 3b, respectively, in 60% yield. A rationale for the reaction is presented.