Aromatic S-Approach to Fluorinated Phenyl -Butyl Nitroxides.

The interaction of octafluorotoluene (), as well as pentafluorobenzonitrile () with -butylamine, followed by the oxidation of thus formed -butylanilines (,) with -chloroperoxybenzoic acid led to functionalized perfluorinated phenyl -butyl nitroxides [namely, 4-(--butyl(oxyl)amino)heptafluorotoluene () and 4-(--butyl(oxyl)amino)tetrafluorobenzonitrile ()] with nearly quantitative total yields. The molecular and crystal structures of nitroxide were proved by single crystal X-ray diffraction analysis. The radical nature of both nitroxides was confirmed by ESR data.

Radical Anions of Aromatic Carbonitriles as Reagents for Arylation of Fluorinated Benzonitriles.

The first example of phenylation of fluorobenzonitriles with the sodium salt of a benzonitrile radical anion in liquid ammonia is presented. The reaction regioselectivity corresponds to the ortho- and para-fluorine atom substitution in fluorobenzonitrile with the phenyl moiety of the benzonitrile radical anion and affords 2- and 4-cyanobiphenyls in 40-90% yields. 3-Methoxybenzonitrile as well as 1-cyanonaphthalene radical anions were also successfully subjected to this interaction forming 3'-methoxycyanobiphenyls and (1-naphthyl)benzonitriles, respectively.

Substitution of a Fluorine Atom in Perfluorobenzonitrile by a Lithiated Nitronyl Nitroxide.

A 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (1) lithium derivative was found to react with perfluorobenzonitrile (2) substituting its para-fluorine atom to form 2-(4-cyanotetrafluorophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl (3), a new nitronyl nitroxide containing a multifunctional framework of strong electron-withdrawing nature. This result shows the possibility of obtaining multifunctional nitronyl nitroxides via the interaction of paramagnetic lithium derivatives as C-nucleophiles with polyfluoroarenes activated for nucleophilic substitution. The reaction regioselectivity is supported by the data of quantum-chemical calculations, which also show that the reaction follows a concerted pathway without formation of an intermediate.

[Chronic Heart Failure Due to Formation of Giant Left Ventricular Pseudoaneurysm After Painless Myocardial Infarction in a Female Patient With Diabetes].

Rupture of the free wall of the left ventricle with the formation of a false aneurysm (pseudoaneurysm, PA) - is a rare complication of acute myocardial infarction. Given the high risk of rupture of the PA and other life-threatening consequences (progressive heart failure, thromboembolic events), as well as the absence of pathognomonic signs and the difficulty in determining treatment strategy (feasibility and timing of surgery), early diagnosis of this complication appears to be especially important. We present here an overview of literature data on prevalence, specific features of diagnostics, and problems related to selection of method of treatment of PA.

One-pot synthesis of 4'-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling.

A convenient one-pot approach to alkylcyanobiaryls is described. The method is based on biaryl cross-coupling between the sodium salt of the terephthalonitrile dianion and a neutral aromatic nitrile in liquid ammonia, and successive alkylation of the long-lived anionic intermediate with alkyl bromides. The reaction is compatible with benzonitriles that contain methyl, methoxy and phenyl groups, fluorine atoms, and a 1-cyanonaphthalene residue.