Synthesis of 3‐Aryl/methoxycarbonyl‐3,4‐dihydroisocoumarin‐6‐carboxylic Acid Derivatives

3‐Substituted methyl 3,4‐dihydroisocoumarin‐6‐carboxylates were obtained by the intramolecular cyclization of 2,5‐dimethoxycarbonyl benzenediazonium bromides with methyl/ethyl acrylate and styrenes under Meerwein's arylation conditions.     

Approach for the Preparation of Various Classes of Peroxides Based on the Reaction of Triketones with H2O2: First Examples of Ozonide Rearrangements

The reaction of β,δ‐triketones with an ethereal solution of H₂O₂ catalyzed by heteropoly acids in the presence of a polar aprotic co‐solvent proceeds via three pathways to form three classes of peroxides: tricyclic monoperoxides, bridged tetraoxanes, and a pair of stereoisomeric ozonides. The reaction is unusual in that produces bridged tetraoxanes and ozonides with one of the three carbonyl groups remaining intact. In the synthesis of bridged tetraoxanes, the peroxide ring is formed by the reaction of hydrogen peroxide with two carbonyl groups at the β positions. The synthesis of ozonides from ketones and hydrogen peroxide is a unique process in which the ozonide ring is formed with the participation of two carbonyl groups at the δ positions. Rearrangements of ozonides were found for the first time after more than one century of their active investigation. Ozonides are interconverted with each other and rearranged into tricyclic monoperoxides, whereas ozonides and tricyclic monoperoxides are transformed into bridged tetraoxanes. The individual reaction products were isolated by column chromatography and characterized by NMR spectroscopy, mass spectrometry, and elemental analysis. One representative of each class of peroxides was characterized by X‐ray diffraction.     

Novel Peroxide Containing Maleinate Surface-Active Monomers for Obtaining Reactive Polymers

Novel surface-active monomers were synthesized by successive treatment of tert-butylperoxy-6-hydroxyhexanoate with maleic anhydride, 1,3-propane sultone and triethylamine or with maleic anhydride and poly(ethylene glycol) methyl ether. The surface-active properties of monomers were studied. The critical micelle concentrations (cmc) as well as the surface tension at the cmc were determined for obtained monomers. The synthesized compounds were shown to be suitable reactive surfactants for obtaining styrene latexes.     

An inverse problem for a parabolic equation in a free-boundary domain degenerating at the initial time moment

We consider an inverse problem for a one-dimensional parabolic equation with unknown time-dependent major coefficient in a domain whose unknown boundary weakly degenerates at the initial time moment. The conditions for existence and uniqueness of the classical solution of the problem are established.     

Induction of A549 Nonsmall-Cell Lung Cancer Cells Proliferation by Photoreleased Nicotine

Caged compounds comprise the group of artificially synthesized, light-sensitive molecules that enable in situ derivation of biologically active constituents capable of affecting cells, tissues and/or biological processes upon exposure to light. Ruthenium-bispyridine (RuBi) complexes are photolyzed by biologically harmless visible light. In the present study, we show that RuBi-caged nicotine can be used as a source of free nicotine to induce proliferation of A549 nonsmall-cell lung cancer (NSCLC) cells by acting on nicotinic acetylcholine receptors expressed in these cells. RuBi-nicotine was photolyzed using LED light source with the spectrum matching RuBi-absorption. Photorelease of free nicotine ([Nic]_p/r) was quantified by high-performance liquid chromatography (HPLC). 5-s-long light exposure of 10 μm of RuBi-nicotine generated 2 μm [Nic]_p/r which enhanced A549 cell proliferation similarly to the 2 μm of plain nicotine during 72 h of cell culturing. Both RuBi-nicotine per se and its photolysis byproduct exerted no effect on A549 cells. We conclude that RuBi-nicotine can be a good source of free nicotine for inducing short- and long-term biological effects. Photolysis of RuBi-nicotine is quite effective, and can produce biologically relevant concentrations of nicotine at acceptable concentrations of the source material with the use of simple, inexpensive, and easily accessible light sources.     

Halogenoarylation of allyl isothiocyanate: Synthesis of 2,5‐disubstituted 2‐thiazolines

A new approach to the synthesis of 2‐R‐5‐benzyl‐2‐thiazolines with the use of chloro‐ and bromoarylation products of allyl isothiocyanate with arenediazonium halides was elaborated. The isothiocyanates obtained were reacted with ammonia, aliphatic or aromatic amines, and sodium methoxide. The use of ammonia or weakly basic amines in this reaction allowed. Intermediate thioureas to be isolated. On the basis of ¹H NMR spectra, amino–imino tautomerism of the synthesized 2,5‐disubstituted 2‐thiazolines were analyzed. 2‐Arylamino‐5‐benzyl‐2‐thiazolines exist mainly in the Z‐configuration of the imino form. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 517–525, 1999