Researches on synthetic dyes

Reaction of phenyl-ß-naphthylamines with formaldehyde and acetone in the presence of HCl and nitrobenzene in butanol solution leads to cyclization involving the naphthalene and phenyl rings, and formation of N-aryllepidine salts. 15 lepidine and 5, 6-benzoepidine salts are synthesized and characterized by their UV absorption spectra, as well as by their picrates.For Part LIII see [3].     

Variation of free volume parameters of polyalkylmethacrylate derivatives in the range from 15 to 300 K probed by positron annihilation lifetime measurement

Positron annihilation lifetime measurements of PMMA, PEMA, PiPMA, PnPMA and PnBMA were performed in the temperature range between 15 and 300 K, where , and relaxational transitions occur for these polyalkylmethacrylates. The variations of free volume size and content calculated from the longest lifetime component against temperature are correlated to the results obtained by dielectric, viscoelastic and dynamic mechanical relaxation data of the polymers. The variations of free volume sizes and contents, apparent free volume fraction and size distribution of the polyalkylmethacrylates are well correlated with the rotational transitions of side chains. The location of free volumes, in which positronium annihilates can be estimated near the vicinity of alkyl groups bound to oxygen atom of side ester chains.     

Topochemical investigations of peptide systems

The basic principles of the topochemical approach to the investigation of the structure-function relation in peptide systems are formulated. This approach makes use of the new possibility of transforming natural peptides, consisting in the modification of the molecule as a whole and utilization of the resultant analogs to elucidate the boundaries of the stereoelectronic complementarity of the biologically active peptide to the corresponding receptor. In particular, on the example of depsipeptide antibiotics and their topochemical analogs the fruitfulness of using such compounds as tools in elucidating the physicochemical basis of functioning of biological membranes is shown. The topochemical principle has also been applied in preparing specific competitive inhibitors of proteolytic enzymes, whose study may shed light on the nature of the forces binding the substrate to the contact site of the corresponding enzyme.     

Vanadium Oxide: From Gels to Nanotubes

Vanadium oxide nanotubes (VO _x -NT) have been prepared by mixing hexadecylamine with V₂O₅·nH₂O gels. This procedure was followed by an hydrothermal treatment (150–180°C, 2–7 days) which leads to a large quantity of VO _x -NT. SEM and XRD analysis have been used to optimize the temperature and reaction time required for production of VO _x -Nt and morphology of the nanotubes investigated by TEM.     

The thermal decomposition of NaHCO3 powders and single crystals

The thermal decomposition of four commercial powders and of differently stored single crystals of sodium hydrogen carbonate is studied by power compensation DSC and by optical and FT-IR microscopy. Independently of manufacturer, specified purity and price, the thermal curves of all the commercial powders show a more or less pronounced low temperature peak preceding the one due to the main decomposition. Such small peak is not observed when samples of laboratory recrystallized material are used. However the thermal behaviour of the latter preparation differs remarkably depending on storage conditions: the material kept in closed glass containers decomposes at temperatures higher than those of the material stored in a dessiccator in the presence of concentrated H₂SO₄. The observation by optical microscopy of the behaviour of the surfaces of single crystals coming from different storage conditions when the temperature is raised in a Kofler heater helps the interpretation of the data collected. The mechanism of the decomposition is discussed and the relevant kinetic parameters reported.     

Studies on organophosphorus compounds—V: Pyridines from secondary car☐amides and HMPA

A new pyridine synthesis has been found by refluxing certain simple secondary car☐amides in HMPA. Thus 2,6-dimethylpyridine, 2-ethyl-6-methylpyridine, 2,3,6-trimethylpyridine, 2-ethyl-3,6-dimethylpyridine, 2-benzyl-6-methyl-3-phenylpyridine, 2-ethyl-3-methyl-5,6,7,8-tetrahydroquinoline and 2-t-butyl-6-methylpyridine were prepared in 15–40% yield.     

Poly(phosphoramidites)-Polycondensation Products of Phosphorous Triamides with Aliphatic Diols and Dibasic Phenols

Phosphorous triamides react with aliphatic diols and dibasic phenols: 1,6-hexanediol, 2,2'-(4-hydroxyphenyl)propane, 1,4-hydroquinone, and 4,4'-dihydroxybiphenyl in the temperature range 80-110°C in diethylene glycol dimethyl ether or without a solvent to afford phosphorus-containing regular high-molecular products having an O₂P(NR₂) moiety in the monomeric unit. The resulting poly(phosphoramidites) are capable of swelling in organic solvents, and they can be used as macroligands in the catalytic hydrogenation of styrene over rhodium(I) complexes.     

Structure,tautomerism, and transformations of β-(3-nitro-2-pyridyl)- and β-(3-nitro-4-pyridyl)pyruvic acid esters

It was shown by means of IR, UV, and PMR spectra that -(3-nitro-2-pyridyl)pyruvic acid esters are practically completely enolized in the crystal state and in solution; ethyl -(3-nitro-4-pyridyl)pyruvate has an enol structure in the crystalline state and in pyridine solution but exists as a mixture of keto and enol forms in low-polarity solvents.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 389–393, March, 1974.