Catalyst-free 1 : 2 annulation of quinolines with trifluoroacetylacetylenes: an access to functionalized oxazinoquinolines.

Metal- and solvent-free reaction of quinolines with two molecules of aryltrifluoroacetylacetylenes afforded 3-arylethynyl-3-trifluoromethyl-1,3-oxazinoquinolines in up to 92% yields. The formation of a zwitterionic intermediate in the first step triggered a multistep domino reaction. This one-pot synthesis opens an easy access to novel quinoline derivatives bearing trifluoromethyl, acetylene and ketone functions, thus providing a powerful tool for drug design.

Synthesis, structure, spectral and luminescence studies of novel guanidinium aryl(oxy)(sulfanyl)(sulfonyl)acetates.

A series of promising luminescent materials, nonlinear optical crystals, and physiologically active compounds - aryl(oxy)(sulfanyl)(sulfonyl)acetates of guanidine (A) of unknown type was synthesized. Various functional groups present in (A) were identified using FTIR spectroscopy. 1H and 13C NMR spectral studies further confirm the molecular structure (A). Crystals of guanidinium 4-chlorophenyl(sulfanyl)acetate (1) and guanidinium 4-chlorophenyl(sulfonyl)acetate (2) were successfully grown. They belong to the same lowest symmetry category, but to different crystal systems: monoclinic (1) and orthorhombic (2). It has been established that intrinsic optical absorption begins at a wavelength of âˆ¼ 290 nm for crystalline compound (1) and âˆ¼ 335 nm for crystal (2). The intrinsic luminescence spectrum of crystal (1) includes two bands with maxima at 300 and 515 nm. In the intrinsic luminescence spectrum of crystal (2), only one band is observed with a maximum at 350 nm. Such luminescence in both crystals is excited in the intrinsic absorption bands, as well as by X-ray radiation. In addition, in the near ultraviolet and throughout the visible region, where optical absorption is not detected (it is very weak), low-inertia (less than 10 ns) rather intense luminescence of uncontrolled impurity-defect centers is excited. The spectral bands of optical absorption, photo- and X-ray luminescence discovered in experiments were systematized using a diagram of energy levels and quantum transitions in crystals and defect centers of the compounds under study.

[Kawasaki disease in an adult European].

A case of Kawasaki disease is reported with manifestations of autoimmune vasculitis and predominant affection of coronary arteries. The relevant literature review describes major symptoms of this pathology and risk factors of its atypical forms. It is emphasized that rare occurrence of Kawasaki disease among non-mongoloid subjects should not make the general practitioner les suspicious of this condition.

Metal-free stereoselective annulation of quinolines with trifluoroacetylacetylenes and water: an access to fluorinated oxazinoquinolines.

Metal-free reaction between quinolines, aryltrifluoroacetylacetylenes and water at -18 °C-rt in MeCN resulted in stereoselective assembly of trifluoromethylated oxazinoquinolines with up to 99% yield that was essentially in contrast to a similar reaction with pyridines. The annulation proceeded via the 1,3-dipolar adducts of quinolines with trifluoroacetylacetylenes followed by intramolecular cyclization involving the trifluoroacetyl group and a molecule of water.

Transition metal-free one-pot double C-H functionalization of quinolines with disubstituted electron-deficient acetylenes.

Transition metal-free one-pot reaction of quinolines with acylarylacetylenes and water proceeds in the presence of KOH (55-60 °C, MeCN, 48 h) to afford 2-aryl-3-acylquinolines in up to 66% yield. Here, a formal replacement of the acetylene moiety by the aryl and acyl substituents in the quinoline scaffold takes place. In fact, it has been proved experimentally that the reaction involves the ring cleavage, accompanied by the rearrangement and insertion of the electron-deficient acetylene moiety to form a dihydroquinoline intermediate with an aldehyde functional group in position 4. This intermediate gives the corresponding doubly functionalized quinolines.