Novel Reactions of Organomolybdenum and Organotungsten Compounds: Additive–Reductive Carbonyl Dimerization,Spontaneous Transformation of Methyl Ligands into μ-Methylene Ligands,and Selective Carbonylmethylenation

Hitherto there was no reaction known that permits transformations of R¹R²-CO → 0.5 R¹R²R³C–CR¹R²R³ in one step. This type of additive–reductive carbonyl dimerization is now possible using alkoxy(alkyl)tungsten(v) complexes with aromatic, heteroaromatic or α,β-unsaturated aldehydes and ketones. When a corresponding phenyl complex was employed in a test experiment, it was revealed that an aliphatic ketone could be used as the substrate in this reaction. A second interesting type of reaction is the transformation of CH₃ ligands into μ-CH₂ ligands, which occurs during the treatment of MeLi or Me₃Al with molybdenum or tungsten chlorides (oxidation states VI and V, for Mo additionally IV) at low temperatures with liberation of CH₄. Here, the question arises as to whether the intermediate involved has a terminal CH₂ ligand (Schrock carbene complex) or a μ-CH₃ ligand (CH₃ bound by a two-electron three-center bond to two metal atoms). Of all the μ-CH₂ complexes obtained, those which were synthesized by the action of MeLi on molybdenum chlorides can be recommended as reagents for carbonylmethylenation of aldehydes and ketones. They display high selectivity, very low basicity, a surprising resistance to protons, they are readily available, can be easily modified and, as regards their selective behavior, they have been investigated more thoroughly than other readily accessible carbonylmethylenation reagents of comparable selectivity. The results of NMR spectroscopic investigations on the structure of the μ-CH₂ complexes, and associated reaction mechanisms are discussed. A survey of carbonylmethylenation reagents, which have been reported in the literature, permits comparisons to be made with carbonylmethylenating molybdenum and tungsten complexes.     

Selective metal promoted hydrolysis of nitrile groups in the side chain of tetraazamacrocyclic Cu2+-complexes

The metal promoted hydrolysis of nitrile groups in the side chains of tetraazamacrocyclic Cu2+ complexes has been studied by stopped-flow techniques. It is shown that the reaction proceeds by an intramolecular attack of an axially coordinated OH- onto the nitrile group to give the corresponding amide. In alkaline solution the amide then deprotonates and binds to the axial position of the Cu2+ thus preventing further coordination of an OH-. This explains mechanistically that in the Cu2+ complexes of macrocycles carrying two nitrile functions only one is selectively hydrolysed. The nitrile hydrolysis has also been used on a preparative scale to synthesize tetraazamacrocycles with two different side chains. X-Ray diffractions of several products are presented to confirm the structures and the results from the kinetics and equilibria measurements.     

Radiotracer studies on ion-selective membranes based on poly(vinyl chloride) matrices

Radiotracer studies with (45)Ca, (89)Sr and (133)Ba have provided evidence that the permeation of magnesium, strontium and barium ions through PVC membranes containing Orion 92-20-02 liquid ion-exchanger is inhibited by their low affinity for the liquid ion-exchanger sites. Experiments with (7)Be indicate a strong affinity of the membrane for beryllium ions with corresponding inhibition of permeation. When acid is present in the solution on one side of the membrane, preferential permeation by protons may lead to transport of ions against their concentration gradient in order to maintain the balance of charge.     

State of Molecules and Ions in the Structural Channels of Synthetic Beryl with an Ammonium Impurity

The contents of the structural channels of beryl, grown hydrothermally from an ammonium-containing solution, were investigated by IR and EPR spectroscopy. Using IR spectroscopy we found that water molecules, ammonium ions, and a small number of HCl molecules enter the structural channels of beryl in the course of mineral growth. In these beryls, the ammonium ions play the role of alkali cations. The ammonium ions are as rigidly fixed in the lattice as are water molecules; they are eliminated by calcination at high temperatures close to the decomposition temperature. On exposure to radiation at 77 K, the paramagnetic NH ₃ ⁺ and H⁰ radicals are stabilized in the structural channels of beryl. In addition to the known H⁰ radical, other states of atomic hydrogen, interacting with medium protons, are observed as well. For one of the additional radicals, H_b, we suggest the model of atomic hydrogen stabilized at the center of a silicon-oxygen ring with two water molecules in adjacent cavities.     

Vibrational overtone spectroscopy of jet-cooled methanol from 5000 to 14 000 cm(-1)

Spectra of jet-cooled methanol in the overtone and combination region from 5000 to 14 000 cm(-1) have been obtained by means of infrared laser-assisted photofragment spectroscopy. Many of the observed features are assigned to combination bands of the type nnu(1)+nu(6), nnu(1)+nu(8), and nnu(1)+nu(6)+nu(8) (n=1,2,3), where nu(1) is the OH stretch, nu(6) is the OH bend, and nu(8) is the CO stretch. These bands show sharp torsion-rotation structure with features as narrow as 0.1 cm(-1). We also observe CH stretch overtones that are weaker than the OH containing combination bands and lack distinct torsion-rotation structure above v(CH)=2. The extent of observed structure on these bands allows us to place limits on the intramolecular vibrational energy redistribution decay rates in the upper vibrational states. We report a global fit of the observed band centers to a simple expression involving low-order anharmonicity constants.     

Stereoselective synthesis of the cyclic ether core of (+)-laurenyne

A concise enantioselective synthesis of the cyclic ether core of the marine natural product (+)-laurenyne has been accomplished using ring-closing metathesis for medium-ring construction.     

Characterization of cocoa butters and other vegetable fats by pyrolysis-mass spectrometry

Pyrolysis Mass Spectrometry (Py-MS) was used for the discrimination of cocoa butters from other vegetable fats. Mass spectra ranging from 50 amu to 250 amu were analyzed by principal component analysis (PCA) and with neural nets. The application of neural nets leads to a good discrimination between the two classes. Detailed analysis of the nets revealed that only the first 60 masses were used within the net. The use of PCA requires a careful selection of the number of masses included in the calculation. Canonical variance analysis was applied to determine the significant masses. Optimal performance of PCA was observed only using the first 22 significant masses. Most of these masses were different from the ones used by the neural net. It seems that the mass spectra obtained by Py-MS contain sufficient information for the discrimination of pure cocoa butter from other vegetable fats, but none of the methods seems to be able to extract all information available. Neural net provides a very robust method for this task and no prior data selection was necessary. Received: 13 May 1996 / Revised: 7 August 1996 / Accepted: 7 August 1996     

Improved preparation and new reactions of β -(1-phenylthio) cyclopropyl enones

β-(1-Phenylthio)cyclopropyl enones can be conveniently prepared via reaction of the lithium salts of α-hydroxymethylene ketones with 1-lithio-1-phenylthiocyclopropane and are converted efficiently by treatment with aqueous acid to γ-keto cyclobutanones and less successfully by thermolysis to -γ-keto phenylthiocyclopentenes.     

Inductively coupled plasma mass spectrometry: Application to the determination of arsenic species

The application of ion-pair reversed phase chromatography (HPLC) and inductively coupled plasma mass spectrometry to the determination of six species of arsenic is described: arsenious acid (As^III), arsenic acid (As^V), monomethylarsinic acid (MMA), dimethylarsinic acid (DMA), arsenocholine (AsC) and arsenobetaine (AsB) in marine biota and in natural fresh water. The coupling conditions of HPLC-ICP-MS are given and also the evaluation of the extraction procedure applied to determine these species in marine organisms. The limits of detection are between 6 and 25 g.l^–1.     

ASSESSMENT OF GENOTOXICITY AND MUTAGENICITY OF 1,2-DIOXETANES IN HUMAN CELLS USING A PLASMID SHUTTLE VECTOR

Abstract— 1,2-Dioxetanes are efficient sources of triplet excited carbonyl compounds on thermal decomposition. They cause photochemical and photobiological transformations in the dark. In order to study the genotoxicity and mutagenicity of 1,2-dioxetanes, the replicating shuttle vector pZ189 was damaged with 3,3,4-trimethyl-l,2-dioxetane(TrMD) or 3-hydroxymethyl-3,4,4-trimethyl-l,2-dioxetane (HTMD) in vitro and subsequently transfected into normal human lymphoblasts. We found a dose-dependent increase of genotoxicity (decrease of plasmid survival) and increase of mutation frequency with both dioxetanes. However, TrMD was less mutagenic than HTMD at similar genotoxicity. Sequence analysis of the supF gene revealed more point mutations than deletions. Single base substitutions occurred exclusively at G:C sites: 94.6% of point mutations with TrMD and 100% with HTMD were G:C to T:A and G:C to C:G transversions. These are the typical mutations following 7,8-dihydro-8-oxoguanine (8-oxo-G) formation, the main DNA lesion induced by TrMD and HTMD. Only with TrMD we found 5.4% G:C to A:T transitions, probably reflecting the more pronounced ability of TrMD to form some pyrimidine dimers. Our results indicate that 8-oxo-G is also the most relevant modification in in vivo mutagenesis.