The Reaction of Singlet Oxygen with Adamantylideneadamantane Mediated by Rose Bengal

The photo-oxygenation of adamantylideneadamantane ( 1 ) on siliceous supports using admixed granules of ion-exchange resin fixed to methylene blue (MB) and rose bengal (RB) gave exclusively the corresponding dioxetane derivative 2 for the former sensitizer, while the latter gave 2 and traces of the epoxide 3. RB and the charge-transfer complex produced from N-ethylcarbazole and 2,4,5,6-tetranitrofluoren-9-one both reacted with chemically generated singlet oxygen to give superoxide radical anion. Trapping of the latter with 5,5-dimethyl-1-pyrroline 1-oxide gave an adduct exhibiting a characteristic ESR spectrum. The treatment of 1 in MeOH with 30% aqueous H₂O₂ for 22 h at 60° gave 3 in 100% yield. Repetition of this experiment in the presence of 2,6-di(tert-butyl)-p-cresol caused no significant change. These results indicate that singlet oxygen reacts with 1 , in the presence of RB, by two different processes. The first leads to dioxetane formation. The second process involves conversion of singlet oxygen by RB to superoxide radical anion which subsequently gives H₂O₂ so producing epoxide 3 from 1 .     

Intrinsic folding of small peptide chains: spectroscopic evidence for the formation of beta-turns in the gas phase

Laser desorption of model peptides coupled to laser spectroscopic techniques enables the gas-phase observation of genuine secondary structures of biology. Spectroscopic evidence for the formation of beta-turns in gas-phase peptide chains containing glycine and phenylalanine residues establishes the intrinsic stability of these forms and their ability to compete with other stable structures. The precise characterization of local minima on the potential energy surface from IR spectroscopy constitutes an acute assessment for the state-of-the-art quantum mechanical calculations also presented. The observation of different types of beta-turns depending upon the residue order within the sequence is found to be consistent with the residue propensities in beta-turns of proteins, which suggests that the prevalence of glycine in type II and II' turns stems essentially from an energetic origin, already at play under isolated conditions.     

Scandium-catalyzed allylboration of aldehydes as a practical method for highly diastereo- and enantioselective construction of homoallylic alcohols

A general approach for the allylation of aldehydes using stable, air-tolerant camphor-based chiral allylboronates under Sc(OTf)3 catalysis is described. This practical methodology provides both syn and anti propionate units and other homoallylic alcohols with very high levels of diastereo- and enantioselectivity for several substrates, including functionalized aliphatic aldehydes useful toward the elaboration of complex natural products.     

Spectrophotometric determination of Fe(II) in milligram solid samples

The analytical procedure of determination of Fe(II) in the presence of Fe(III) in milligram samples is proposed. A solid sample is dissolved in hydrochloric acid in argon atmosphere. Subsequently, the pH-value of the solution is fixed and Fe(III) complexed by phosphoric buffer. At the next step Fe(II) is oxidized by -molybdosilicic acid. Finally, the intensity of colouring caused by the reduced form of the acid is measured at the wavelength 770 nm. The proper treatment of the sample during oxidation, and immediately before, is decisive for the accuracy of the analysis. The method was verified by means of the analysis of synthetic magnetite. The theoretical content of Fe(II) was 24.12%, the determined one was 24.02 ± 0.10%. The method was applied to the determination of the homogeneity of an iron catalyst for ammonia synthesis.     

Reactions SRN1 en serie heterocyclique: I - reactivite de sels de nitro-5 tetrahydrooxazines-1,3

Heterocyclic nitronate anions prepared from 3-ethyl-5-hydroxymethyl-5-nitrotetra-hydro-1,3-oxazine are found to be suitable nucleophiles for S_RN1 reactions. Base-promoted nitrous acid elimination from C-alkylation product gives rise to new tetrahydro-1,3 oxazines with a trisubstituted ethylenic double bond in the 5 position.     

Synthesis of new thienocyclopenta[3,2-d]-oxazole and thiazole derivatives

Synthesis of thieno[2′,3′:5,4]cyclopenta[3,2-d]oxazole and thiazole derivatives are achieved by insertion of carbon dioxide and disulfide into 4-amino-5-chloro-5,6-dihydro-4H-cyclopenta[b]thiophen-6-one.     

On the Correlation between Ionization Potentials and Excitation Energies,part III: Pyrazine

A recently suggested scheme for relating ionisation potentials (IP) to excitation energies (E) has been applied to pyrazine and 2,6-dimethylpyrazine. The results indicate that in these systems the energy gap (ΔE) between the two lowest lying ¹n,π*-states is significantly smaller than that (ΔIP) between the corresponding ²n-states of the parent radical cations. The values estimated for ΔE on the basis of ΔIP, measurable by photoelectron spectroscopy, disagree with those calculated theoretically but seem to be supported by the experimental evidence available. Since ΔE = ΔIP would normally be expected, the relationship ΔE < ΔIP actually present in these systems is discussed and related to the different shape of the n-MO's involved in the ionization and excitation processes.     

Note sur le mécanisme réactionnel de la transposition de Dimroth. Une étude ab initio

An ab initio study of the Dimorth rerarrangement of the -amino-1,2,3,4-tetrazole leads to the conclusion teht in vapour phase the rate determining step is not the ring-chain isomerism, but is either the Z-E iomerism around the C?N double bond or the 1,3-sigmatropic shift of the proton.     

Automatic sugar analysis in the beet industry. Part I: Parameter optimization of a reversed phase HPLC carbohydrate determination

An evaluation of the most commonly used HPLC system (reversed phase octadecyl sillica gel) was undertaken in order to determine the level of certain carbohydrates in molasses produced in the refining of sugar beet. Chromatographic parameters and purification operations prior to analysis are discussed in order to develop an analytical method permitting automation of sugar determination. A Zorbax ODS column (250 × 9.4 mm), water elution, and light scattering detection allow easy determination of glucose + fructose, sucrose, and raffinose in molasses using an internal standard (maltose).