Hydrogen migrations in mass spectrometry. VI—the chemical ionization mass spectra of substituted benzoic acids and benzyl alcohols

The H₂ and CH₄ chemical ionization mass spectra of a series of series of substituted benzoic acids and substituted benzyl alcohols have been determined. For the benzoic acids the major fragmentation reactions of the protonated molecule involve elimination of H₂O or elimination of CO₂, the latter reaction involving migration of the carboxylic hydrogen to the aromatic ring. For the benzyl alcohols the major fragmentation reactions of [MH]⁺ involve loss of H₂O or CH₂O, analogous to the CO₂ elimination reaction for the benzoic acids. It is shown that the CO₂ and CH₂O elimination reactions occur only when a conjugated aromatic ring system is present, and that for the carboxylic acid systems, methyl groups and, to a lesser extent, phenyl groups are capable of migrating. The only discernible effect of substituents on the fragmentation of [MH]⁺ is an enhancement of the H₂O loss reaction in the benzoic acid system when an amino, hydroxyl, or halogen substituent is ortho to the carboxyl function. This ‘ortho’ effect, which differs in scope from that observed in electron impact mass spectra, is attributed to an intramolecular catalysis by the ortho substituent of the 1,3 hydrogen migration in the carbonyl protonated acid followed by H₂O elimination. Apparently, this route is favoured over the direct elimination of H₂O from the carbonyl protonated acid, since the latter has a high activation energy barrier because of unfavourable orbital symmetry restrictions.     

519—Reduction of hydrophobic porphyrin at the octane/water interface controlled by the specific adsorption of halogen anions

The redox reaction between the ferric complex of hydrophobic porphyrin and sodium dithionite in two different phases occurring at the interface between two immiscible liquids has been investigated by Volta potential measurements and spectroscopy. The reduction of the ferric complex of hydrophobic porphyrin adsorbed at the interface was found to be accompanied by a potential shift in the negative direction and to depend significantly on the nature of the anion and the ionic strength of the supporting electrolyte. Specifically adsorbed halogen anions inhibited the redox reaction in the sequence: Cl^?, Br^?, I^?. Depending on pH, the ferric complex of hydrophobic porphyrin exists in the uncharged (FeP-O-PFe) form or in the cation FeP⁺ form. The interaction between the ferric complex hydrophobic porphyrin and water has also been investigated.     

Zur struktur von CaPdF4, CdPdF4, HgPdF4 und HpPdF2

Single crystals of CaPdF₄ (purple) and CdPdF₄ (dark blue) have been obtained by heating CaF₂ (CdF₂) with PdF₂ at 820°C (900°C) for ca. 20–30 d in sealed Pd (Pt) tubes. CaPdF₄ crystallizes tetragonal (KBrF₄-Type) with a = 5.52₁, c = 10.57₀ Å (space group I4/mcm ? D^18_4h, No. 140) Z = 4, 283 unique reflexions, R = 0.083; R_w = 0.079, CdPdF₄ cubic (CaF₂-variant) with a = 5.40₃ Å (space group Pa3 ? T^6_h, No. 205) Z = 4, 165 unique reflexions, R = 0.047, R_w = 0.032. The high pressure modification of PdF₂, obtained by heating PdF₂ in closed Pt-tubes under a pressure of ≈ 60 kbar and ‘HgPdF₄’, both black, a = 5.32₇ Å and a = 5.43 Å are isotypic. CaPdF₄ is diamagnetic, CdPdF₄ and HPPdF₂ are antiferromegnetic.     

N-dealkylation of 2-(tert-butyl)-3-hydroxy-3-(4-chlorophenyl)isoindolinone and n-(tert-alkyl)-2-aroylbenzamides in concentrated sulfuric acid

It has been established that 2-(tert-butyl)-3-hydroxy-3-(4-chlorophenyl)isoindolinone and N-(tert-Alkyl)-2-aroylbenzamides are dealkylated in concentrated sulfuric acid to give 3-hydroxy-3-arylisoindolinones. The reaction is realizable. only when there is a tert-alkyl group attached to the nitrogen atom. The reaction mechanism is discussed on the basis of data on the change with time in the electronic spectra of the investigated compounds in concentrated sulfuric acid and a comparison with the spectra of model structures.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 763–765, June, 1977.     

Determination of metal traces in tantalum by proton activation analysis

Procedures for determining traces of calcium, titanium, vanadium, chromium, iron, copper, niobium, molybdenum and tungsten in tantalum are described utilizing 11 MeV proton activation. The instrumental method of analysis with the use of a Ge(Li) detector and the radiochemical separation of the corresponding fractions are described. The formula for the calculation of the concentration of traces with the use of thick target yields is given. Experimental data on the thick target yields of radioisotopes⁴⁴Sc,⁵²Mn,⁵⁶Co,⁶⁵Zn,^93mMo,⁹⁶Tc are presented. Based on the experimental data, the detection limits are estimated at 1–10 ppb for the above mentioned metal traces in tantalum. The successful solution of the task of the simultaneous determination of nine elements in tantalum confirms the wide applicability of proton activation analysis.     

Untersuchungen in der Thiazolreihe. III—massenspektrometrische Untersuchung von 2-Amino-3-hydroxythiazoliumchloriden

The mass spectrometric decomposition of 2-aminothiazole-3-oxides is characterised by the abstraction of O and OH out of the molecule ion. Distinct differences between 4-alkyl and 4-aryl derivatives as well as defined dependence of the [M – O]⁺·: [M – OH]⁺ ratio on the substituents are interpreted by a stabilisation of the [M – O]⁺·: radical cation through aromatic substitution. The effects of temperature suggest an equilibrum between tautomers in the inlet system.     

Synthesis and properties of polycondensation polymers from compounds with asymmetric functional groups

The effect of conditions of polycondensation on the structure of polymers formed from monomers with symmetric and asymmetric functional groups by nonequilibrium polycondensation has been studied for the system with acceptor-catalytic polyesterification of β-hydroxyethyl ethers of bisphenols and terephthalic acid chloride in the presence of triethylamine. Polymers with statistical or regular arrangement of diol residues in the chain can be produced in such systems, depending on the way in which starting compounds are introduced in the reactor. A difference in the reactivity of functional groups in an asymmetric monomer is not sufficient to produce polycondensation polymers with a regular structure. Gradual introduction of the symmetric monomer is essential to yield polymers with predominant “head-to-head” (“tail-to-tail”) configurations. Some properties of the resulting polymers have been studied. Polymers with ordered residues of the asymmetric monomers in the macromolecules have higher softening temperatures and an increased tendency for crystallization than the statistic polymers.     

MECHANISM OF PHOTOREDUCTION OF THIAZINE DYES BY EDTA STUDIED BY FLASH PHOTOLYSIS-II. pH DEPENDENCE OF ELECTRON ABSTRACTION RATE CONSTANT OF THE DYES IN THEIR TRIPLET STATE

Abstract— The pH dependence of the apparent reactivity of thiazine dyes in their triplet states has been studied in aqueous solutions, using as electron donor HY^-3, the trianionic species of ethylene diamine tetraacetic acid (EDTA), in the pH range 4–8. The pH dependence is found to be related to a change in the degree of protonation of the triplet excited dye. The apparent reactivity and lifetime of two differently protonated forms of thionine, azur B and methylene blue were determined by classical and dye-laser flash techniques, making it possible to evaluate the rate constant for electron abstraction of these molecules in their triplet states. It is found that: (a) protonation on the ring nitrogen increases the electron-abstraction rate constant of the triplet-state species about twenty-fold, and (b) methylation on the side amino groups decreases it.     

Phenolic resins for solid-phase peptide synthesis: Copolymerization of styrene and p-acetoxystyrene

Details are given of the synthesis and purification of p-acetoxystyrene and its solution and suspension copolymerization with styrene. Reactivity ratios, evaluated by the Tidwell-Mortimer method, were r₁ (p-acetoxystyrene) = 1.18, and r₂ (styrene) = 0.88 for (bulk) solution copolymerization. Corresponding values of the reactivity ratios for suspension copolymerization were, within experimental error, indistinguishable from unity. Thus the copolymer composition is governed simply by the monomer feed composition. Use of a specially designed reactor vessel permits convenient suspension copolymerization of styrene, p-acetoxystyrene, and divinylbenzene to give crosslinked resins having comparatively narrow particle size distributions. Acetoxy groups in the crosslinked resin are cleaved by hydrazine hydrate under very mild conditions to give crosslinked polystyrenes having phenolic groups which, in turn, provide a useful alternative to the more usual chloromethylated polystyrene resins for solid-phase peptide synthesis.     

3-Furylchromones

-[2-(5-Methoxycarbonyl)furyl]-2,4-dihydroxy- and 2,4,6-trihydroxyacetophenones were obtained by the condensation of polyphenols with (2-methoxycarbonyl-5-furyl)acetonitrile. 7-Acetoxy- and 5,7-diacetoxy-2-methyl-3-[2-(5-methoxycarbonyl)furyl]chromones were obtained from them by reaction with acetic anhydride in the presence of triethylamine and were subsequently deacylated to 7-hydroxy and 5,7-dihydroxy compounds. 7-Hydroxy- and 5,7-dihydroxy-2-ethoxycarbonyl-3-[2-(5-methoxycarbonyl)furyl]chromones were obtained from the indicated acetophenones by reaction with ethoxalyl chloride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1317–1320, October, 1972.