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.     

An optically active vinyl sulfoxide copolymer and the configuration of sulfoxide adjacent to radical or anionic sites

Optically active vinyl p-tolyl sulfoxide was synthesized and copolymerized with styrene to produce an optically active copolymer. The question of the configuration of sulfur in a sulfoxide when adjacent to a radical site is discussed. The configuration of sulfur in a sulfoxide is proven to be nonplanar when adjacent to an anionic site.     

Al(Cap)3 as initiator in the anionic polymerization of ε-caprolactam at high temperature

Mechanism for polymerization of ε-caprolactam in the presence of both sodium and aluminum caprolactamate was investigated at 171°C. The role of Al(Cap)₃ as an initiator was revealed. The apparent rate constant of propagation reaction decreased with the increase in the concentration of Al(Cap)₃, as the two different metal salts interact even at 171°C. The activation energy of the overall polymerization reaction with this catalyst system was estimated to be 41.18 kcal/mole.     

Synthesis and reactions of β-(5-halo-3-uracyl) propionic acids

The reaction of elementary bromine and iodine with -(3-uracyl)-propionic acid has given the corresponding -(5-bromo-3-uracyl) and -(5-iodo-3-uracyl)propionic acids. The methyl esters and amides of the acids have also been synthesized for the first time.     

TOPICAL UROCANIC ACID ENHANCES UV-INDUCED TUMOUR YIELD AND MALIGNANCY IN THE HAIRLESS MOUSE

Epidermal urocanic acid has been postulated to be the mediator of the specific state of immunosuppression induced by UV irradiation, by which UV-initiated tumour cells are able to evade normal recognition and can survive to grow progressively into malignant tumours. These experiments demonstrate that topical application of UV-irradiated urocanic acid systemically suppresses the contact type hypersensitivity response to oxazolone in hairless mice. In addition, topically applied urocanic acid markedly increases the overt tumour yield and the degree of malignancy in hairless mice exposed chronically to daily minimally erythemal doses of simulated solar UV light. Topical urocanic acid also increases the number of latent UV-initiated tumours, detectable by croton oil promotion. Therefore UV photoproducts of urocanic acid can both systemically suppress contact hypersensitivity in the epidermis, and also enhance early survival of UV-initiated tumour cells resulting in augmentation of UV photocarcinogenesis.     

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.     

Matrixreaktion von GaF mit o-atomen: ir-spektrum von OGaF

It is possible to synthesize OGaF in an argon matrix by co-condensation of GaF with O atoms. The stretching vibrations of this compound are found at 943 and 690 cm⁻¹ (¹⁶O⁶⁹GaF). An exact calculation of the force field is possible with the aid of the observed ¹⁶O/¹⁸O and ⁶⁹Ga/⁷¹Ga shifts. The following force constants are found: f(GaO) = 6.32; f(GaF) = 4.69; f(GaO/GaF) = −0.1 [10²Nm⁻¹]     

Ligand exchange reactions of ferrocene with phenanthrene or 9,10-dimethylphenanthrene in the presence of aluminum chloride and aluminum

Ligand exchange reactions between phenanthrene or 9,10-dimethylphenanthrene with ferrocene effected in the presence of AlCl₃-Al were carried out under a variety of conditions. With phenanthrene (I), hydrogenation at the C-9 and C-10 positions could take place during the reaction and the cationic products obtained were the η⁶-phenanthrene-η⁵-cyclopentadienyliron and η⁶-9,10-dihydro-phenanthrene-η⁵-cyclopentadienyliron moncations (II and III), and the η⁶-phenanthrene-$\text{trans}$-$\text{bis}$-η⁵-cyclopentadienyliron and η⁶-9,10-dihydrophenanthrene-$\text{trans}$-$\text{bis}$-η⁵-cyclopentadienyliron dications (IV and V). With 9,10-dimethylphenanthrene (VI), reactions carried out in refluxing cyclohexane gave the non-hydrogenated η⁶-9,10-dimethylphenanthrene-η⁵-cyclopentadienyliron monocation (VII) and η⁶-9,10-dimethylphenanthrene-$\text{trans}$-$\text{bis}$-η⁵-cyclopentadienyliron dication (VIII). When higher temperatures were used in an attempt to promote hydrogenation, decomposition predominated and no cationic product could be obtained. These finding are discussed and contrasted with previous results obtained from similar reactions using anthracene or 9,10-dimethylanthracene.     

Polyélectrolytes amphipathiques en milieu organique I. Propriétés thermodynamiques et structurales des échangeurs d'ions liquides

Resume Un polyélectrolyte dérivé de la poly (4 vinylpyridine) a été utilisé comme échangeur d'ions liquide pour des anions mono-et-divalents entre une phase aqueuse et l'octanol normal. Le polysavon sous forme sel de pyridinium est soluble dans l'octanol et la solution organique en contact avec une phase aqueuse contenant un mélange d'électrolytes possède des propriétés échangeuses d'ions. La sélectivité de l'échangeur vis à vis d'anions de nature différente est interprétée en fonction de la polarisabilité des anions. On a déterminé l'indice viscosimétrique des solutions organiques en fonction de la composition ionique du polymère et on a établi un parallèle entre les dimensions du polymère et l'affinité des ions pour les sites pyridinium compte-tenu de la faible constante diélectrique du milieu. Les variations de la viscosité en fonction de la composition sont interprétées à partir de la théorie de Flory transposée aux copolymères statistiques.

---

Summary A polymer obtained by quaternizing poly (4-vinylpyridine) with N-octadecyl bromide was used in developing liquid ion-exchange of mono- and divalent anions between water and 1-octanol phases. The polymer has a high solubility in 1-octanol and the organic polymeric solution in contact with aqueous phase containing a mixture of simple electrolytes behave similary to an anion exchange resin with selective properties. The mechanism by which selective association of anions on the polymeric pyridinium sites occurs is discussed from the data concerning the polarisability of anions. The conformational properties of the polymeric chain was determined from viscosity measurements. It is shown that the trend in chain dimensions parallels the affinity of the anions to bind on polymeric pyridinium sites in the low dielectric medium. The chain dimensions as a function of the ionic composition are discussed on the basis of a simple theoretical model in analogy with the behaviour of statistical copolymers.

---

Zusammenfassung Eine Lösung von Poly(-4-vinylpyridinium)salz in Octanol wurde als flüssiger Anionenaustauscher zwischen einer wässerigen Lösung und Octanol gebraucht. Diese organische Lösung in Berührung mit einer wässerigen Electrolytmischung behält die Eigenschaften der Ionenaustauscher. Die Selektivität des Austauschers für verschiedene Anionen wird durch die Polarisabilität der Ionen erklärt. Die Konformation der Polymeren wurde durch Viskositätsmessungen bestimmt und mit der verschiedenen Ionenaffinität in Vergleich gestellt. Die Dimensionsveränderungen der Polymeren während des Ionenaustausches wurden durch ein einfaches Modell erklärt, analog dem der statistischen Copolymeren.

     

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.