Copolymers of the C9 hydrocarbon fraction of liquid pyrolysis products with maleic anhydride and their esterification products as additives to paper pulp

The influence exerted by copolymers of the C₉ fraction of liquid pyrolysis products of petroleum raw materials with maleic anhydride and by their esterification products, added to paper pulp, on the main paper properties was examined.     

MONOFUNCTIONAL3,4-and4',5'-PHOTOCYCLOADDUCTS BETWEEN 4,5'-DIMETHYLANGELICIN and THYMINE

By irradiating (365 nm) an aqueous liquid solution of 4,5'-dimethylangelicin. a monofunctional photosensitizing furocoumarin, in the presence of an excess of thymine, two new compounds, I and II, have been obtained; they do not show fluorescence when observed with Wood's light. The nuclear magnetic resonance data, the marked similarity of UV absorption and fluorescence spectra of these compounds with those of synthetic 3.4-dihydro-4,5'-dimethylangelicin and their capacity to undergo photodissociation (254 nm) yielding the starting thymine and 4,5'-dimethylangelicin in equimolecular amounts, are consistent with C₄-cycloadducts between the 3,4-double bond of the furocoumarin and 5,6-double bond of thymine. Nuclear magnetic resonance data indicate for I and II a head-to-head and a head-to-tail structure, respectively. When irradiation is carried out in the frozen state, two adducts. III and IV, fluorescent at Wood's light, have been obtained other than the two above-mentioned compounds I and II. Compounds III and IV have been identified as 4'.5'-fluorescent adducts between the 4',5'-double bond of the furocoumarin and the 5.6-double bond of thymine; one of them (III) is identical to that formed in the photoreaction between DNA and 4,5'-dimethylangelicin; for this last compound a cis head-to-head structure has been suggested.     

Temperature-programmed reduction and oxidation of bimetallic Pd?Ni/Al2O3 catalysts

Temperature-programmed reduction and oxidation of bimetallic catalysts Pd–Ni/Al₂O₃ seem to indicate phase segregation of palladium and nickel oxides and alloying of palladium and nickel in the process of reduction of oxidized catalysts.

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- Pd–Ni/Al₂O₃ , .

     

Gas chroamtographic separation of optically active compounds in glass capillaries

Summary Chiral compounds may be separated by gas chromatography by direct enantiomer separation on optically active stationary phases. More generally the separation can be achieved on conventional stationary phases after formation of diastereoisomeric derivatives. In this work we report on new results in enantiomer separation, indicating that hydrogen bond association is not the only kind of molecular interaction responsible for enantiomer separation. For the separation of a wide variety of chiral compounds with amino or hydroxy groups diastereo-isomeric derivatives may be formed by reaction with L--chlorisovaleryl chloride. The derivatives of amino acids, aliphatic and aromatic amines, amino alcohols and of some alcohols are separated in glass capillaries. Gas chromatography as a separation technique of high selectivity is specifically useful for the separation of mixtures of chemically related components with comparable molecular interactions with the molecules of the stationary phase of a gas chromatographic column. The separation of optically active compounds, particularly, requires highly efficient columns. Glass capillary chromatography is a tool that meets this standard and was applied exclusively in this work.     

A study of the reaction kinetics of electrogenerated superoxide ion with benzylbromide

The reaction kinetics between O₂^? and C₆H₅CH₂Br has been investigated in N,N′-dimethylformamide by electroanalytical techniques. A mechanism is proposed in which two molecules of the primary electrode product regenerate, via a following chemical reaction, one molecule of the original electroactive species. Furthermore, evidence for a S_N2 reaction mechanism between O₂^? and C₆H₅CH₂Br has been obtained. Second order rate constants resulted to be 11000 M^?1s^?1 and 3000 M^?1s^?1at room temperature and 0°C, respectively. The main products of the reaction were found to be benzylalcohol, benzaldehyde, benzene and biphenyl.     

NMR.-Investigation of the Formaldehyde Addition and Oligomerisation Equilibria in the System Formaldehyde/Water/Acetic Acid/Hydrochloric Acid

An NMR. investigation of the state of formaldehyde in acidic solutions has been carried out. Solutions of DCl/D₂O/CD₃COOD containing two sources of formaldehyde, i.e. paraformaldehyde (I) and trioxane (II), were used for this purpose. In systems I and II the effect of various D₂O/CD₃COOD ratios, at a constant DCl concentration, was studied, while for II the effect of changing DCl concentration was also investigated. The results show that in aqueous solution, formaldehyde exists primarily as the monomeric and linear oligomeric forms of methylene glycol. Reducing the amount of D₂O (at constant DCl concentration), while increasing the CD₃COOD content, results in an increase in the polymeric species and in trioxane. In addition, substitution of water by acetic acid results in systems that are catalytically more active than aqueous solutions of the same hydrochloric acid concentration. Along with the usual polymer-monomer equilibria which exist in such solutions, side reactions of methylene glycol with the hydrochloric acid present also occur to a small extent, e.g. acetylation, substitution of OH by Cl and the Cannizzaro reaction. It is suggested that these findings will result in a better understanding of the formaldehyde crosslinking reactions in cotton cellulose.     

The pectin of ginseng. The structure of the poly-galacturonide

Conclusions The partial hydrolysis of the pectin ofPanax ginseng C. A. Mey gives a polygalacturonide which has a linear carbohydrate chain consisting of residues of D-galacturonic acid in the pyranose form linked by -(1 4)-bonds.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 4, pp. 201–203, 1969     

Ortho effects in organic molecules on electron impact: XI—the interesting ortho effect of the methoxy group in o-methoxy aromatic thioamides

It has been noticed that the major part of the loss of ?H from the molecular ion of most of the o-methoxythioamides results from an ortho effect of the methoxy group. Comparison of the MIKE spectra of the [M? SH]⁺ of 1-(2-methoxyphenylthioxomethyl)piperidine and 1-(2-methoxyphenylthioxomethyl)pyrrolidine with the MIKE spectra of [M? SH]⁺ of the corresponding unsubstituted compounds, reported earlier, indicated two parallel pathways for the formation of [M? SH]⁺ in the o-methoxy compounds. In the first pathway, as has been noticed in thioamides in general, the loss of ?H involves the migration of either the α-hydrogen in the amine moiety or the hydrogen attached to nitrogen. In the second pathway, the migration of a hydrogen from the o-methoxy group to the sulphur atom followed by ejection of SH from the molecular ion leads to a stable cyclized ion. Interesting secondary fragmentations as a consequence of this ortho effect have also been noticed.     

Investigations into functionally substituted azines.

Reaction of 2-N-potassiocyanamino-4,6-bisisopropyl(dimethylamino)-sym-triazines with acid 1,2,2,2-tetrachloroethylamides leads to the formation of 2-N-cyano-N-(1-acylamino-2,2,2-trichloroethyl)amino-4,6-bisisopropyl(dimethylamino)-sym-triazines. Reaction with 1-hydroxy(methoxy)-2,2,2-trichloroethylamides of chloroacetic acid leads to 2-(2-imino-4-oxooxazolidin-1-yl)-4,6-bis(dimethylamino)-sym-triazine and its 1-methoxy-2,2,2-trichloroethyl derivative substituted at the position 3 of the oxazolidine ring.     

Percutaneous absorption of ketoprofen from acrylic gel patches containing d-limonene and ethanol as absorption enhancers.

The percutaneous absorption of ketoprofen (KPF) from gel patches containing d-limonene and ethanol was investigated in rats. Plasma levels of KPF varied with the kind of polymers which constitute the gel patch, and the highest level was observed when the copolymer of ethylacrylate (EA) and diethyleneglycolmethacrylate (DEGMA) was used as a vehicle. The amount of KPF permeating through the rat skin from the gel patch was well correlated with that of ethanol. Permeations were enhanced with increase in the amount of d-limonene distributed from the vehicle to the skin tissue. The amount of d-limonene accumulated in the skin varied greatly with the kind of polymers; the highest accumulation was observed with the EA-DEGMA copolymer, and decreased with increasing affinity of d-limonene to the polymers. The reason EA-DEGMA copolymer showed the highest percutaneous absorption of KPF from gel patches containing d-limonene may be the hydrophilic nature of this polymer which showed the lowest affinity to d-limonene.