A. V. Khoroshutin

The Reactions of Brexadiene. A New Norbornene-Like Caged Diene.

Abstract The reactions of brexadiene I with bromine, iodine, deuterotrifluoroacetic and Tetradeuteroacetic acid are described. These reactions proceed mainly as electrophilic exo-attack followed by Wagner-Meerwein rearrangement.

Regioselective bromination of (Tetraphenyltetrabenzoporphyrinato)palladium(II). Synthesis of a new octabromo derivative of the tetraphenyltetrabenzoporphyrin series

Bromination of (meso-tetraphenyltetrabenzoporphyrinato)palladium(II) with bromine in the presence of tetramethylammonium bromide occurs exclusively at the benzene rings fused to the porphyrin system while the phenyl rings in the meso positions are not involved. The corresponding octabromo-substituted complex was obtained using a large excess of bromine on prolonged reaction time. The complex was isolated and characterized by 1H NMR spectra, electronic absorption spectra in the UV and visible regions, and MALDI-TOF mass spectra. It was assigned the structure of symmetric (22,23,72,73,122,123,172,173-octabromo-5,10,15,20-tetraphenyltetrabenzoporphyrinato)palladium(II).

Synthesis, complex-formation, and extracting ability of new derivatives of dithia-13(16)-crown-4(5) ethers

Various methods of synthesizing functional derivatives of dithia-13(16)-crown-4(5) ethers are proposed. Complex-formation of the obtained compounds with Ag+ and Pb2+ ions has been studied using 1H NMR. A radiometric method was used to investigate the extracting ability of substituted dithia-13(16)-crown-4(5) ethers in relation to Ag+ and Cd2+ ions from aqueous solution in the presence of anions of various degree of hardness, with determination of the metal content.

Synthesis and extraction properties of oxathiacrown compounds containing benzyl groups

Abstract8-Benzyl-1.4-dioxa-7,10-dithiacyclododecane and 11-benzyl-1,4,7-trioxa-10,13-dithiacyclopentadecane were obtained by the interaction of (2,3-dibromo-1-propyl)benzene with 1,8-dimercapto-3,6-dioxaoctane and 1,11-dimercapto-3,6,9-trioxaundecane. The extracting ability of the obtained compounds has been studied in relation to Sr2+ and Pb2+ ions from aqueous solutions in the presence of anions of various degrees of hardness with determination of the metal content by a radiometric method.

H2S Sensing by Hybrids Based on Nanocrystalline SnO2 Functionalized with Cu(II) Organometallic Complexes: The Role of the Ligand Platform

This paper deals with the functionalization of nanocrystalline SnO2 with Cu(II) complexes with organic ligands, aimed at the improvement of sensor selectivity towards gas molecules. For the synthesis of metalorganic/SnO2 hybrid material complexes of Cu(II) with phthalocyanine, porphyrinines, bipyridine and azadithiacrown etherwere used. The analysis of gas sensor properties showed the possibility of increasing the sensitivity and selectivity of hybrid materials in H2S detection due to the electron transfer from SnO2 to an adsorbed organic molecule, which changes during the interaction between H2S and Cu(II) ions.

Regioselective bromination of palladium tetraphenyltetrabenzoporphyrin to benzo-rings: Synthesis of mono- and octabromotetrabenzoporphyrins and their properties

Bromination of palladium meso-tetraphenyl tetrabenzoporphyrin (Pd Ph4TBP, 1) by Me4NBr3 or Me4NBr/Br2 was shown to proceed regioselectively to the benzo-rings annelated to main porphyrin macrocycle. Conditions for preferential mono- and octa-bromination have been established. The respective mono- and octa-bromide (Pd Ph4TBP(Br), 2 and Pd Ph4TBP(Br)8, 3) have been isolated and characterized by UV-vis, NMR and LDI-TOF spectroscopy. Changes of electrochemical properties of tetrabenzoporphyrins induced by Br atoms were found to follow the same trends as the changes in analogous non-extended porphyrins. Room temperature phosphorescence is not substantially influenced by the substitution.

Diethyl (Biscyclohexano)BODIPY * Dicarboxylates. Chelation of Alkaline-Earth Metal Ions and Sensor Properties

Abstractmeso-Aryl-substituted (biscyclohexano)bis(ethoxycarbonyl)BODIPY [aryl = phenyl, 3,4-dimethoxyphenyl, and 2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecin-15-yl-(m-{benzo-15-crown-5}-yl)] were synthesized. The effect of alkaline-earth metals on the absorption and fluorescence spectra of these compounds was investigated. In all compounds along with the mechanism of the photoinduced electron transfer (PET), well-known for the crown-containing BODIPY-based sensors, one more response pattern is observed. The large excess of Ca2+ and Ba2+ ions in the system leads to the changes both in the UV-Vis and emission spectra. The complex formation results in the decrease of emission intensity and in its red shift. Besides, a new longwave absorption band appears in the UV-Vis spectrum of the BODIPY-metal ion complex. The formation constants of the complexes corresponding to this response pattern is about 100 times less than the formation constant of Ca2+-crown ether complex. 1H, 13C, 11B, and 19F NMR spectra, the results of quantum-chemical calculations, and their comparison with the literature data of X-ray diffraction study suggest that the binding of Ca2+ and Ba2+ ions occurs in the cavity formed by the fluorine atoms and the carbonyl oxygen atoms of the ester groups.

Synthesis of Metallated (Cu, Pd) Crown Substituted Tetracyclohexenoporphyrins. Crown-Containing Pd Tetrabenzoporphyrin and Its Phosphorescence

Palladium and copper tetracyclohexenoporphyrins (cyclohexano rings annelated to pyrrole rings), tri-mesophenylsubstituted and mono-meso-substituted with benzo-15-crown-5 ether moiety (PdPh3[benzo-15-crown-5]TCP and CuPh3[benzo-15-crown-5]TCP) have been synthesized. Coupling of 1,1-(arylmethylene)bis-4,5,6,7-tetrahydro2H-isoindole with the corresponding aldehyde in Lindsey conditions has been used. Two variations of the reagents combinations have been tested. Phenyl substituted dipyrromethane reacted with the mixture of m-formylbenzo-15-crown-5 and benzaldehyde gave the best cyclization results. Separation of the mixture of the scrambled products was greatly enhanced by metallation prior to column chromatography, thus rendering the yields of PdPh3[benzo-15-crown-5]TCP and CuPh3[benzo-15-crown-5]TCP 16% and 18% respectively. An alternative combination of the reagents, i.e. benzo15-crown-5-substituted isoindole and benzaldehyde, afforded no porphyrin products besides H2Ph4TCP. Oxidation of PdPh3[benzo-15-crown-5]TCP by DDQ yielded the corresponding tetrabenzoporphyrin (PdPh3[benzo-15-crown-5] TBP) in 71%. Phosphorescence spectrum of the latter has been studied.

Facile transformation of the hydroxy-substituted oxathiacrown ethers

Abstract 9(12)‐Hydroxy‐dithia‐13(16)‐crown‐4(6)‐ethers have been prepared by the condensing an oligoethylene glycol dithiol with 2,3‐dibromo‐1‐propanol. Methods of oxidation, halogenation, amination, and esterification of the 9‐hydroxythiacrown ether, producing corresponding oxathiacrown ether derivatives in good yields, have been developed. Cyclic destruction has not been found in the studied reactions. The change of the oxathiamacrocyclic ring size in the course of the halogenation and amination reactions was revealed.

Addition of dichlorocarbene to tricyclo[4.3.0.03,7]nona-4,8-diene

Addition of dichlorocarbene to tricyclo[4.3.0.03,7]nona-4,8-diene (brexadiene) under conditions of phase transfer catalysis occurs from theexo side. Cyclopropyl-allyl rearrangement of intermediate chlorocyclopropanes yields tricyclo[5.4.0.03,8]undecadienes.