Über die Alkaloide der Granatapfelbaumrinde. IV

Zusammenfassung Die früheren Befunde über den Gehalt an Isopelletierin in der Granatapfelbaumrinde wurden an 5 weiteren Rindenproben bestätigt. Isopelletierin wurde zu 30 bis 40% in den Gesamtalkaloiden aufgefunden.Versuche zeigen, daß das opt.-akt. Methylisopelletierin in schwach alkalischer Lösung bei 20° wohl racemisiert, aber nicht zersetzt wird.I.:F. Galinovsky undO. Vogl, Mh. Chem.83, 1055 (1952). b) II.:F. Galinovsky, G. Bianchetti undO. Vogl, Mh. Chem.84, 1221 (1953). c) III.:F. Galinovsky undF. Höllinger, Mh. Chem.85, 1012 (1954).     

Graft polymers with macromonomers. II. Copolymerization kinetics of methacrylate-terminated polystyrene and predicted graft copolymer structures

Copolymerization studies of methacrylate-terminated polystyrene macromonomers (M₁) with several comonomers (M₂) verified the modified kinetic scheme and permitted prediction of graft polymer compositions and structures. Instantaneous and cumulative copolymer compositions, average graft distributions, and grafts per molecule are predicted from FORTRAN IV or BASIC programs. The r₂ relative reactivity ratios determined from styrene copolymerization (0.61) or from low conversion acrylic monomer in aqueous suspension (～0.4) had good agreement with literature values (about 0.6 and 0.4, respectively). Decreased macromonomer reactivity determined at high acrylic monomer conversions was attributed to phase separation phenomena. The Macromers also exhibited lower reactivity than predicted when copolymerized with acrylic monomers in DMSO/benzene solutions (r₂ ～ 0.8).     

Factors affecting the endo : exo ratio in diels-alder reactions of cyclopentadiene

The ratio of endo-CHO:exo-CHO in the Diels-Alder addition of a trans-αβ-unsaturated aldehyde to cyclopentadiene can be changed from 1:2 to 8:1, depending on temperature and BF₃-catalysis.     

Calculation of band structure and deformation potentials for phthalocyanines

Calculation was made of the electronic structure of copper and platinum phthalocyanine crystals, and their deformation potentials were determined. The calculation was carried out on an electronic computer using the following basic assumptions: Bloch wave functions; Hückel molecular orbitals; Slater atomic orbitals. The pattern of the band spectrum obtained was used qualitatively to explain some kinetic relationships recently observed in copper and platinum phthalocyanines.     

Contribution to the mechanism of liquid membrane oscillators involving cationic surfactant

It is shown that liquid membrane oscillators with cationic surfactants have more complex oscillation patterns than observed previously. The actual details of the oscillations depend strongly on the nature of the membrane material, disclosing even the presence of parallel molecular events. It appears that sampling topology also has a great influence on the observed oscillatory behavior. Variation of oscillation patterns with diffusion path length in the membrane demonstrated the decisive role played by the actual timing of molecular events. The new evidences produced complete usefully the actual views concerning the mechanism of oscillations.     

Can semi-empirical models describe HCl dissociation in water?

We discuss the failure of commonly used AM1 and PM3 semiempirical methods to correctly describe acid dissociation. We focus our analysis on HCl because of its physicochemical importance and its relevance in atmospheric chemistry. The structure of non-dissociated and dissociated HCl – (H₂O) _n clusters is accounted for. The very bad results obtained with PM3 (and also with AM1) are related to large errors in gas-phase proton affinity of water and gas-phase acidity of HCl. Indeed, estimation of pKa values shows that neither AM1 nor PM3 are able to predict HCl dissociation in liquid water since HCl is found to be a weaker acid than H₃O⁺. We have proposed in previous works a modified PM3 approach (PM3-MAIS) adapted to intermolecular calculations. It is derived from PM3 by reparameterization of the core–core functions using ab initio data. Since parameters for H–Cl and O–Cl core–core interactions were not yet available, we have carried out the corresponding optimization. Application of the PM3-MAIS method to HCl dissociation in HCl–(H₂O) _n clusters leads to a huge improvement over PM3 results. Though the method predicts a slightly overestimated HCl acidity in water environment, the overall agreement with ab initio calculations is very satisfying and justifies efforts to develop new semiempirical methods.     

Flow injection turbidimetric determination of thiamine in pharmaceutical formulations using silicotungstic acid as precipitant reagent

A simple flow injection system is proposed for the determination of thiamine in pharmaceutical formulations. The determination is based on the precipitation reaction of thiamine with silicotungstic acid in acidic medium to form a thiamine silicotungstate suspension that is measured at 420 nm. Adding 0.05% (w/v) poly(ethyleneglycol) in the carrier solution (0.5 mol l(-1) hydrochloric acid), an improvement in the sensitivity, repeatability and baseline stability of the flow injection system was obtained. The calibration graph was linear in the thiamine concentration range from 5.0x10(-5) to 3.0x10(-4) mol l(-1) with a detection limit of 1.0x10(-5) mol l(-1). The relative standard deviations for ten successive measurements of 1.0x10(-4) mol l(-1) and 2.5x10(-4) mol l(-1) thiamine were less than 1% and an analytical frequency of 90 h(-1) was obtained.     

C-I stretching vibrations in iodobenzenes

Comparison of the calculated and experimental IR and Raman spectra of a series of iodobenzenes showed that the C-I stretching vibrations for these compounds correspond to a very highly polarized Raman band at 150–270 cm^–1 (=0.1). The position of this band depends on the mass of the para substituent and relative position of the fluorine and iodine atoms in the molecule. The UV absorption spectral data indicate an interaction of the iodine atom and para substituents through the -system. Opposite substituent effects on the change in intensity of the B-band in the UV spectra of iodobenzenes and tetrafluoroiodobenzenes were noted.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2637–2639, November, 1991.     

Derivatives of condensed systems based on pyrimidine,pyrazine, and pyridine

Pyrimido[4,5-b]-1,4-thiazin-6-one and pyrimido[4,5-b]-1,5-thiazepin-6-one derivatives were obtained by reaction of 5-amino-6-chloropyrimidines with thioglycolic acid and 5-amino-6-mercaptopyrimidines with -bromopropionyl chloride. The IR spectra of the compounds are presented.See [1] for communication XXXV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1332–1335, October, 1977.