9-Alkylideneazafluorenes

A number of tertiary aza-9-fluorenols were obtained from 4- and 2-azafluofenones and were subjected to dehydration in order to synthesize the previously unknown 9-methyleneazafluorenes. The corresponding 9-methyleneazafluorenes and their polymers were obtained simultaneously in relatively stable form from both pyridine-ring-substituted and -unsubstituted 4-aza-9-fluorenols and from 1,3-diphenyl-2-aza-9-fluorenol. On the basis of an analysis of the mass spectrum of the polymer obtained from 9-methylene-4-azafluorene it was concluded that it is evidently isolated in the form of two dimers — dispiro [bis (4-aza-9-fluorene)-1, 3-cyclobutane] and the analogous product of dispiro addition with a 1,2-substituted cyclobutane ring. Condensation of the corresponding azafluorenes with benzaldehyde gave their 9-benzylidene derivatives in the form of geometrical isomers, the structures of which were established on the basis of the PMR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1234–1240, September, 1978.     

Angular distributions of photoelectrons in resonantly enhanced multiphoto ionization via the 7s[1 1/2]0 1 and 8s[1 1/2]0 1 states of Xe

Photoelectron angular distributions have been measured for the three-photon resonant one-photon ionization, (3+1), of Xe via the 7s[1 1/2]⁰ ₁ and 8s[1 1/2]⁰ ₁ states. The results are in good agreement with the theoretical predictions of Tang and Lambropoulos [13] for the 8s[1 1/2]⁰ ₁, but not for the 7s[1 1/2]⁰ ₁ state. Furthermore, the results are compared to those which have been obtained by Blazewicz et al. [1] for the three-photon resonant two-photon ionization, (3+2), of Xe via the 6s[1 1/2]⁰ ₁ state.     

Substituted chromans and tetrahydrofuro[2,3-b]benzofurans (trapped tetrahedral intermediates) from 3-phenyl-2-benzofuranones

The previously discovered neighboring group reaction has been extended to the synthesis of chroman derivatives (i.e., 4, 5, 6) containing geminal methyls in the 2-position, a feature common to certain physiologically active natural chromans. In two instances, cyclic ortho ester by-products (8), not observed in previous work, were formed as a result of the intramolecular trapping of tetrahedral intermediates. Reasons for the incursion of this unexpected side reaction are discussed.     

Electron-impact studies—LXX. Substituent effects in the negative-ion spectra of nitroaryl esters

The negative-ion mass spectra of a variety of substituted nitroaryl benzoates and aryl nitrobenzoates have been studied. Pronounced proximity effects are observed in the spectra of ortho-substituted compounds. The meta and para pairs fragment in a similar manner. Linear plots are observed for many cleavages using either the McLafferty or Harrison methods. Evidence is provided which suggests that the fragmentations of meta and para isomers may proceed by the same mechanistic pathway. The magnitude of ρ does not appear to provide precise information concerning the nature of the transition state for a particular reaction of a negative ion.     

High frequency titrations involving chelation with ethylenediaminetetra-acetic acid. II. quantitative determination of some divalent metals

The high frequency oscillator provides an excellent means of detecting the end-points of titrations performed with ethylenediaminetetraacetic acid or its salts. The determination of various divalent metals is reported, based on both direct and indirect titrations. Because of the great sensitivity of the method it is possible to determine cobalt, nickel, copper (II), zinc, cadmium, lead and manganese (II) in concentration ranges of 1/1000 to 1/6000M.     

Preparation and properties of cross-linked fluorescent poly(methyl methacrylate) latex colloids

We report a single step preparation of monodisperse fluorescent poly(methyl)methacrylate (PMMA) lattices cross-linked with ethylene glycol dimethacrylate with radii in the range 150-1000 nm using dispersion polymerization. The particles are applied as fluorescent cores in core-shell PMMA particles for confocal microscopy (Dullens et al. Langmuir 2003, 19, 5963). Contrary to un-cross-linked particles, these cross-linked colloids are stable in good solvents for PMMA as well. Therefore we studied the properties of the cross-linked PMMA particles in the good solvents tetrahydrofuran (THF), chloroform, and toluene using light scattering and confocal scanning laser microscopy. We show that the particles swell instantaneously and that their volume can increase up to more than seven times their volume in poor solvents. Further, it is very likely that the particles are charged in THF.     

Electron paramagnetic resonance and spin trapping investigations of the photoreactivity of human lens proteins

Oxidation of cysteine, glutathione and ascorbate by photoexcited proteins from normal and cataractous lenses was investigated using electron paramagnetic resonance in combination with spin trapping. We report that illumination of these proteins in pH 7 buffer with light > 300 nm in the presence of thiols (RSH) and a spin trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO), afforded DMPO/S-cysteine and DMPO/SG adducts, suggesting the formation of the corresponding thiyl radicals. In a nonbuffered aqueous solution, illumination of the proteins and glutathione also produced superoxide detected as a DMPO/O2H adduct. Irradiation of these proteins in the presence of ascorbate generated ascorbate radical. We conclude that chromophores present in the natural normal and cataractous lenses are capable of initiating photooxidative processes involving endogenous thiols and ascorbic acid. This observation may be pertinent to UV-induced development of cataract.     

Acid-base equilibria in solutions of polyacid bases (Model and experiment): II. Thermodynamic dissociation constants of tribasic acids

A model is developed for estimating thermodynamic dissociation constants of tribasic acids in organic solvents, with an example of ethanol solution of citric acid in which the functional groups are neutralized jointly.     

Crystal structure of oxotitanium(IV) 2,2,6,6-tetramethyl-3,5-heptanedionate

The structure of titanyl dipivalylmethanate TiO(dpm)₂ has been studied by X-ray diffraction analysis. The compound has a molecular structure formed by isolated centrosymmetrical dimers [TiO(dpm)₂]₂; the unit cell contains two structurally related, crystallographically unique binuclear molecules. The Ti...Ti distance in the dimer is 2.73 Å. Crystal data for Ti₂C₃₆H₇₆O₁₀: a = 32.477(6) Å, b = 14.409(3) Å, c = 25.630(5) Å; β = 107.82(3)°, space group C2/c, Z = 8, d _calc = 1.002 g/cm³.     

New Synthetic Approaches to Functionally Substituted 4,5-Dihydro-1,2,3-oxadiazole 2-Oxides

A practical procedure has been proposed for the synthesis of functionally substituted 4,5-dihydro-1,2,3-oxadiazole 2-oxides on the basis ofsulfamic acid derivatives.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 121–123.Original Russian Text Copyright © 2005 by Tartakovskii, Ermakov, Strelenko, Vinogradov, Petrov.