Selective 1,4-diacetoxylation of conjugated dienes with tellurium (IV) oxide

Oxidation of several linear conjugated dienes with tellurium (IV) oxide and lithium bromide in acetic acid affords an isomeric mixture of the corresponding diacetoxyalkenes (1,2- and 1,4-addition products), 1,4-isomer being highly selectively produced when the ratio of LiBr/TeO₂, is 5–10.     

A new simple synthesis of 1,4-benzodiazepines

A convenient synthesis of 1,4-benzodiazepines starting from secondary-2-aminobenzhydrols, which are easily obtained from secondary anilines and benzaldehydes, is described. 7-Nitro-1-methyl-1,4-benzodiazepine 1d can be formed from 5-nitro-2-methylaminomethylacylaminobenzo-phenone 10b and c by using ammonium carbonate instead of ammonia, which gives only the Smiles-rearranged product 11 .     

DNA damage by fasicularin

Fasicularin is a structurally novel thiocyanate-containing alkaloid isolated from the ascidian Nephteis fasicularis. Early biological experiments suggested that this compound's cytotoxic properties may stem from its ability to damage cellular DNA. Sequence gel analysis reveals that treatment of a 5'-32P-labeled DNA duplex with fasicularin in pH 7.0 buffer causes strand cleavage selectively at guanine residues. Further experiments indicate that production of these base-labile lesions in DNA involves alkylation of guanine residues by a fasicularin-derived aziridinium ion. This work reveals fasicularin as the first natural product found to generate a DNA-alkylating aziridinium ion via a mechanism analogous to the clinically used anticancer drugs mechlorethamine, melphalan, and chlorambucil.     

Experimental and theoretical study on gas-phase ion/molecule reactions of silver trimer cation, Ag3+, with 12-crown-4

The reaction mechanisms of silver trimer cation, Ag3+, with 12-crown-4 (12C4) were studied experimentally and theoretically. Using a cylindrical ion trap time-of-flight mass spectrometer, gas-phase ion/molecule reactions of Ag3+ with 12C4 were observed. Metal-ligand complexes of [Ag(12C4)]+, [Ag3(12C4)]+ and [Ag3(12C4)2]+, and of [Ag(12C4)2]+ and [Ag3(12C4)3]+, were observed as the reaction intermediates and terminal products, respectively. The formations of the [Ag12C4]+ and [Ag(12C4)2]+ complexes indicated that the neutral dimer (Ag2) had been eliminated from the trimer cation. From the results of ab initio calculations at the HF/LanL2DZ level of theory and the experiments, it is suggested that three 12C4 molecules can attach to Ag3+ through consecutive reactions and that neutral Ag2 can be easily eliminated from [Ag3(12C4)]+.     

Palladium-catalyzed allylic oxidation of olefins by t-butyl hydroperoxide and tellurium(IV) oxide

Treatment of several cyclic olefins, β-pinene, allylbenzene, and estragole with palladium(II) salt in acetic acid in the presence of t-butyl hydroperoxide and tellurium(IV) oxide afforded mainly the corresponding allylic acetates. The reaction proceeded catalytically with palladium(II) salt, t-BuOOH working as a reoxidizing agent.     

Retarded transverse current-current response functions of a two-dimensional electron gas

The retarded transverse current-current response functions of an ideal two-dimensional electron gas at zero temperature are calculated. Introducing a new approximation scheme which allows one to take account of the reaction of the electromagnetic field to the induced current, i.e. the influence of the electronic induced current on the dynamics of the electromagnetic field, within the framework of the conventional linear response theory in a self-consistent way, a possible form of the dispersion relation for the transverse plasmon in the system is obtained. It is found that the energy of the transverse plasmon has a gap at k=0, if the thickness of the system is finite, in contrast to the longitudinal case.     

Ru-catalyzed ring-opening and substitution reactions of heteroaromatic compounds using propargylic carboxylates as precursors of vinylcarbenoids

[reaction: see text] The reaction of heteroaromatic compounds with propargylic carboxylates in the presence of a catalytic amount of [RuCl(2)(CO)(3)](2) or PtCl(2) gives trienes in good yields. The key intermediate is an electrophilic (1-acetoxylvinyl)carbene complex generated from the activated propargylic acetates with transition metals.     

Determination of selenium in sediment by isotope-dilution inductively coupled plasma mass spectrometry with an octapole reaction cell

A method is described for determination of selenium in sediment by isotope-dilution inductively coupled plasma mass spectrometry with an octapole reaction cell (ID–ICP–ORCMS). Sediment samples were digested with HNO₃, HClO₄, and HF, and the digestion included an elaborate evaporation process to remove bromine from the digested solution. Simple strong cation-exchange disk filtration was used to remove rare earth elements (REE) from the digested solution, because REE²⁺ seriously interfere with Se isotopes (i.e. ¹⁵⁶Gd²⁺ with ⁷⁸Se⁺, ¹⁶⁰Gd²⁺ with ⁸⁰Se⁺). Addition of acetic acid to the filtrate was examined to improve the sensitivity of ICP–ORCMS measurement of Se⁺ by means of a carbon-enhancement effect. The interfering for selenium isotopes were almost eliminated by use of H₂ as reaction gas. Interference from BrH⁺ formed in the reaction cell was negligible because the Br was removed in the evaporation process. Approximately 99.5% of REE were removed by cation-exchange disk filtration yet more than 99% of Se remained in the filtrate solution. The intensity for Se⁺ was enhanced approximately fourfold by addition of 5% (v/v) of acetic acid whereas that for was barely enhanced. Measured ⁸⁰Se/⁷⁸Se ratios in unspiked digested solutions of the sample were in good agreement with that for an Se standard solution. The analytical results for Se in the certified reference materials MESS-3 and PACS-1 were in good agreement with their certified values, with small uncertainties.