A novel acid-catalyzed rearrangement of n-aryl-n′-aryloxyureas to biphenyl derivatives. A [5,5]-rearrangement involving three heteroatoms.

In the presence of trifluoroacetic acid, N-phenyl-N′-phenoxyurea (1a) rearranges to N-(4′-hydroxy-2-biphenylyl)urea (2a) and N-carbamoyl-2-hydroxy-diphenylamine (3a). The rearrangement is an intramolecular reaction, and the transition state of the breakage of the N-O bond is deduced to be polarized in the form N^δ- --- O^δ+. The reaction is entirely new and constitutes a fundamental aromatic rearrangement.     

Aromatic polyesters obtained directly from hydroxybenzoic acids by hexachlorocyclotriphosphatriazene (PNC) in pyridine

Polyaryl esters of moderate molecular weights were prepared by the direct polycondensation reaction of hydroxybenzoic acids and its derivatives with hexachlorocyclotriphosphatriazene (also known as phosphonitrilic chloride trimer, PNC) as a condensing agent in pyridine. Copolymerization of p-hydroxybenzoic acid with several hydroxybenzic acid derivatives was carried out to improve the processability of the polymer of p-hydroxybenzoic acid, which yields fusible and soluble copolymers of high inherent viscosities. Polymer solubility and thermal behavior were examined.     

Determination of Arsenic Species in Fish Oil After Acid Digestion

Arsenic speciation is of increasing interest to the food industry, as concerns about high total arsenic concentrations in food can often be alleviated to a great extent if the ratio of toxic, less toxic and non-toxic arsenic compounds in the sample is known. The lipid matrix of fish oil is a challenge in the determination of arsenic species, as current methods for this type of analysis require the analyte to be water-soluble. In this study, two sample preparation techniques were applied. One the one hand water-soluble species were extracted with methanol/water, on the other, acid digestion was applied to release lipid-soluble arsenic compounds into the aqueous phase. Ion chromatography – inductively coupled plasma mass spectrometry (IC-ICP-MS) was used for separation and sensitive element-specific detection of arsenic compounds. Additional experiments, including alkaline hydrolysis, were carried out to find out more about the type of lipids arsenic is bound to in fish oil. Up to eight different arsenic species were detected and quantified in fish oil with dimethylarsinate being the major compound both in the aqueous extract and in the acid digest. No inorganic arsenic was detected in the aqueous extract, and the maximum concentration of arsenate determined in the acid digest was 0.05 μg g⁻¹. The total arsenic concentration determined by ICP-MS ranged from <0.1 to 5 μg g⁻¹. With regard to the mass balance, approximately 1% of the total arsenic content was extractable with methanol/water, whereas the sum of arsenic species quantified after acid digestion yielded 85–100% of the total arsenic content. It was confirmed that the large fraction of arsenic in fish oil not extractable on an aqueous basis consists of organoarsenic compounds. This new approach in sample preparation makes the complete characterization of the arsenic content in the sample possible with regard to the respective species, providing necessary information required for risk assessment.     

Facile radical trifluoromethylation of lithium enolates

[reaction: see text] Highly basic lithium enolates are shown to be applicable to radical trifluoromethylation. The reaction is extremely fast, and the minimum reaction time is approximately 1 s.     

Determination and regulation of the migration window in electrokinetic chromatography

The determination of the velocities of the mobile and the pseudostationary phases (the migration (time) window) is mandatory for the determination of physicochemical properties by electrokinetic chromatography (EKC). This review offers a detailed discussion on the definition, the importance, the determination and the regulation of the migration (time) window in EKC. An overview on the theoretical treatment of chromatographic processes in EKC is given defining EKC in comparison to the term capillary electrophoresis. Methods to determine and influence the migration window are discussed with emphasis on measures that have been taken to modify the electroosmotic flow velocity. Pseudostationary phases (or separation carriers) that are taken into consideration are anionic and cationic micelles, mixed micelles, microdroplets (microemulsions), polymeric pseudostationary phases and dendrimers.     

Collision-energy-resolved Penning ionization electron spectroscopy of p-benzoquinone: study of electronic structure and anisotropic interaction with He(*)(2 (3)S) metastable atoms

Collision energy dependence of partial ionization cross sections (CEDPICS) of p-benzoquinone with He(*)(2 (3)S) metastable atoms indicates that interaction potentials between p-benzoquinone and He(*)(2 (3)S) are highly anisotropic in the studied collision energy range (100-250 meV). Attractive interactions were found around the C==O groups for in-plane and out-of-plane directions, while repulsive interactions were found around CH bonds and the benzenoid ring. Assignment of the first four ionic states of p-benzoquinone and an analogous methyl-substituted compound was examined with CEDPICS and anisotropic distributions of the corresponding two nonbonding oxygen orbitals (n(O) (+),n(O) (-)) and two pi(CC) orbitals (pi(CC) (+),pi(CC) (-)). An extra band that shows negative CEDPICS was observed at ca. 7.2 eV in Penning ionization electron spectrum.     

1,4‐Addition polymerization of 1,4‐bis(4‐benzylpyridinium)butadiyne triflate in a dipolar aprotic solvent

1,4‐Bis(4‐benzylpyridinium)butadiyne triflate was aggregated in dimethylformamide and spontaneously converted into the 1,4‐addition type of polydiacetylene. The polymerization took place in a dipolar aprotic solvent with a large dielectric constant that could enhance the aggregation of the ionic diacetylene salt through the electrostatic interaction. The molecular weight of the diacetylene was leveled off after 30 h at 80 °C to reach 1.5 × 10⁴ (number‐average molecular weight) that consisted of the 1,4‐addition type of polydiacetylene similar to polydiacetylenes obtained in the conventional solid‐state polymerization. Electron spin resonance spectra revealed that diradicals were generated at the earlier state aggregation to give rise to a solution polymerization. The UV spectra also suggested the presence of the activated aggregation associated with the polymerization as well as the eximer emission spectra. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3534–3541, 2002     

Photoelectron and penning ionization electron spectroscopic investigation of trimethylsilyl- and t-butyl-thiophenes

Penning ionization electron spectroscopy and CNDO/S calculations have been successfully applied to the analyses of the UV photoelectron spectra of 2- and 2,5-bistrimethylsilylthiophene and 2-t-butylthiophene. The relative intensities of the π type bands are greatly enhanced in the Penning spectra compared with those of the UV photoelectron spectra.