Aerosol formation and reaction pathways of atmospheric oxidation of dimethylsulfide

This paper concerns with three series of experiments about dimethylsulfide gas phase oxidation, carried out at increasing NOx level (< 20 ppb, 1 ppm, 10 ppm) to show the relation between the amounts of nitrogen oxides and the molar yields of sulfur containing products. DMSO, DMSO2, HCHO, HCOOH and SO2 were found as main reaction products. From these experiments and from preceding studies, a sensitive decrease in the quantity of total sulfur products in aerosol phase is underlined. This result derives from the reaction of NOx with CH3S(O)O2 and CH3S(O)OO radicals, which leads to stable intermediates as methylsulphonylperoxynitrate, MSPN, with a characteristic PAN-like structure.     

An investigation of tautomeric equilibria by means of mass spectrometry

Changes in the mass spectra with inlet temperature were used in this work to demonstrate the dependence of keto-enol tautomerism of acetylacetone, 3-methyl acetylacetone and 3-allyl acetylacetone on temperature. The largest dependence of temperature were shown by the ion [M ? 42]^+. arising from a McLafferty type rearrangement and by the ion [M ? Me]⁺ resulting from simple α-cleavage. The ion [M ? 42]^+. peak increases with the temperature of the inlet system while the ion [M ? Me]⁺ peak decreases. By assuming that the ion [M ? 42]^+. represents the keto form and that the ion [M ? Me]⁺ represents the cis-enol form (stabilized by the hydrogen bond) one sees that the direction of the intensity variation of these peaks with temperature is in accord with the expected change of keto-enol tautomerism with temperature. A quantitative correlation on the basis of the above assumptions is also approached. Recording of the mass spectra of these three β-diketones at different energies of the incident electrons enables us to estimate whether or not the particular ions present in the mass spectra result from energetically favourable processes. The variation of the intensities of the peaks with the temperature of the inlet at different electron energies is also discussed.     

N-labelling studies of the reaction of 2,6-di-t-butyl-4-methyl-4-nitrocyclohexa-2,5-dienone with nitrogen dioxide; A revised mechanism

Reaction of the ¹⁵N-4-nitrodienone (1) with excess nitrogen dioxide in benzene for 16 h gives the 4,5,6-trinitro ketone (2), labelled (¹⁵NO₂) at C6 but not at C4, and recovered 4-nitrodienone (1) in which extensive loss of ¹⁵NO₂ has occurred. The mechanistic implications of these and related results are discussed.     

Palladium-catalyzed regioselective arylation of imidazo[1,2-a]pyrimidine

Imidazo[1,2-a]pyrimidine can be arylated at the 3-position with aryl bromides in the presence of base and a catalytic amount of palladium. This provides an efficient one-step synthesis of 3-arylimidazo[1,2-a]pyrimidines from the unsubstituted heterocycle. [reaction: see text]     

The molecular structure of beryllocene, (C5H5)2Be. A reinvestigation by gas phase electron diffraction

The electron scattering pattern of gaseous dicyclopentadienylberyllium, Cp₂Be, has been recorded from s = 2.00 to 39.00 Å⁻¹ with a nozzle temperature of about 120°C. Molecular models of D_5d symmetry or models containing one π-bonded and one σ-bonded Cp ring are not compatible with the data. The possibility the gaseous Cp₂Be consists fo a mixture D_5d and π-Cp, σ-Cp conformers is considered and rejected. A model of C_5v symmetry can be brought into satisfactory agreement with the data. It is also found that a slip sandwich model obtained from the C_5v model by moving sideways the ring which is at the greatest distance from Be, while keeping the two rings essentially parallel is compatible with the electron diffraction data. The best fit between experimental and calculated intensity curves is obtained with a model with a sideways slip of 0.8(1) Å. This model is similar to that indicated by the X-ray diffraction investigations by Wong and coworkers [4,5]. It is suggested that the potential energy of the molecule does not change much as the magnitude of the slip changes and that the molecule thus undergoes large amplitude vibration.     

Palladium catalysts for aerobic oxidative kinetic resolution of secondary alcohols based on mechanistic insight

The oxidative kinetic resolution of secondary alcohols has been accomplished using 1:1 complexes of PdCl(2) and N-heterocyclic carbenes. In these reactions, both achiral and chiral carbene ligands are used in conjunction with the chiral base (-)-sparteine. A general synthesis of 1:1 PdCl(2)-carbene complexes has been developed and is amenable to a wide range of carbene ligands. The potential of these complexes in aerobic oxidations is highlighted by the use of a chiral Pd(II) complex and the chiral base (-)-sparteine to enhance the kinetic resolution of a racemic alcohol. [reaction--see text]     

Investigation of the metabolic fate of 2-, 3- and 4-bromobenzoic acids in bile-duct-cannulated rats by inductively coupled plasma mass spectrometry and high-performance liquid chromatography/inductively coupled plasma mass spectrometry/electrospray mass spectrometry

Inductively coupled plasma mass spectrometry (ICPMS) has been used to determine the rate and routes of excretion of bromine following the intraperitoneal administration (50 mg kg(-1)) of 2-, 3- and 4-bromobenzoic acids to male bile-duct-cannulated rats. Analysis of urine and bile for (79/81)Br using ICPMS showed that all three bromobenzoic acids were rapidly excreted (82-98%) within 48 h of dosing, primarily via the urine. High-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICPMS) was then used to obtain metabolite profiles for bile and urine. These profiles revealed that extensive metabolism had taken place, with the unchanged bromobenzoic acids forming a minor part of the total of compound-related material detected. Concomitant MS studies, supplemented by alkaline hydrolysis, enabled the identification of the major metabolite of all three of the bromobenzoic acids as a glycine conjugate. Ester glucuronide conjugates were also identified, but formed only a small proportion of total.