Synthesis and Properties of First Bis(fluoreno)crownophanes

Alkylation of 2,7-dihydroxy-9H-fluoren-9-one with 2-(2-chloroethoxy)ethanol, 2-[2-(2-chloroethoxy)-ethoxy]ethanol, and 2-{2-[2-(2-chloroethoxy)ethoxy]ethoxy}ethanol in dimethylformamide in the presence of potassium carbonate gave 78–80% of the corresponding diols which were treated with p-toluenesulfonyl chloride in a dioxanechloroform mixture in the presence of triethylamine at 0– 5°C (30 h). The resulting bis(p-toluene-sulfonates) were brought into condensation with 2,7-dihydroxy-9H-fluoren-9-one in a very dilute solution in dimethylformamide containing anhydrous potassium carbonate at 80–85°C. Appropriate treatment of the reaction mixture, followed by chromatographic purification afforded 53–27% of the first representatives of a new class of cyclophanes, bis(oxofluoreno)crownophanes. Raising the temperature to 95–105°C resulted in an appreciable decrease of the product yield. The yield of the target products did not increase on replacement of potassium carbonate by cesium carbonate.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 144–149.Original Russian Text Copyright © 2005 by Lyapunov, Kirichenko, Kulygina, Luk’yanenko.     

Bis(oxofluorenediyl)oxacyclophanes: synthesis, crystal structure and complexation with paraquat in the gas phase

The first three representatives of the new family of oxacyclophanes incorporating two 2,7-dioxyfluorenone fragments, connected by [-CH(2)CH(2)O-](m) spacers (m=2-4), have been synthesized. The yield of the smallest oxacyclophane (m=2) is considerably higher with respect to the larger ones (m=3 and m=4), which are formed in comparable yields. Molecular modeling and NMR spectra analysis of the model compounds suggest that an essential difference in oxacyclophanes yields is caused by formation of quasi-cyclic intermediates, which are preorganized for macrocyclization owing to intramolecular pi-pi stacking interactions between the fluorenone units. The solid-state structures of these oxacyclophanes exhibit intra- and intermolecular pi-pi stacking interactions that dictate their rectangular shape in the fluorenone backbone and crystal packing of the molecules with the parallel or T-shape arrangement. The crystal packing in all cases is also sustained by weak C--HO hydrogen bonds. FAB mass spectral analysis of mixtures of the larger oxacyclophanes (m=3 and m=4) and a paraquat moiety revealed peaks corresponding to the loss of one and two PF(6) (-) counterions from the 1:1 complexes formed. However, no signals were observed for complexes of the paraquat moiety with the smaller oxacyclophane (m=2). Computer molecular modeling of complexes revealed a pseudorotaxane-like incorporation of the paraquat unit, sandwiched within a macrocyclic cavity between the almost parallel-aligned fluorenone rings of the larger oxacyclophanes (m=3 and m=4). In contrast to this, only external complexes of the smallest oxacyclophane (m=2) with a paraquat unit have been found in the energy window of 10 kcal mol(-1).     

The influence of a fluoroorganic modifier—stillage residues of alcohol-telomeres—on properties of filled poldienurethanes

The results of an investigation of the influence of stillage residues of polyfluorinated alcoholtelomeres on the properties of polydienurethane compositions and elastomers based on them are presented. It is shown that such modification allows one to raise the sedimentation stability of the compositions and increase the characteristics of physicochemical and dynamic properties of elastomers.     

Facile Synthesis of Bis(crown ether)benzils: Prospective Building Blocks for Metal Ion Sensors

A new facile synthetic route to benzils containing fragments of 12-crown-4, 15-crown-5, and 18-crown-6 by oxidation of corresponding stilbenes was developed. The first representative of a new family of fluorescent sensors was obtained by reaction of bis(15-crown-5)benzil with o-phenylenediamine. The latter exhibits great fluorescence enhancement upon association with K⁺ and Rb⁺ compared to Na⁺ and Cs⁺.     

Sorption of strontium by sorbents on the base of di-(tert-butylcyclohexano)-18-crown-6 with use of various diluents

Journal of Radioanalytical and Nuclear Chemistry - Set of sorbents were obtained on the base of di-(tert-butylcyclohexano)-18-crown-6, various diluents and styrene–divinylbenzene support for...     

Synthesis,properties, and interaction with paraquat of new fluorenonocrownophanes containing a hydroquinone fragment

New crownophane family was synthesized containing fragments of 2,7-dioxyfluorenone and hydroquinone connected with residues of tri- and tetraethylene glycols. The formation of inclusion complexes of these ligands with paraquat was established by means of mass spectrometry (fast-atom bombardment), ¹H NMR and electronic spectroscopy. The crownophane with a larger ring formed the more stable complex.

     

Synthesis and properties of new fluorenonocrownophanes having a stilbene fragment and their reaction with paraquat

New crownophanes containing 2,7-dioxyfluorenone and 4,4??-dioxystilbene fragments linked through di-, three, tetra-, and pentaethylene glycol linkers were synthesized. The formation of pseudorotaxanetype host-guest complexes in reactions of these crownophanes with 1,1??-dimethyl-4,4??-bipyridinium dication was detected by fast atom bombardment mass spectrometry, ¹H NMR, and electron spectroscopy.     

Photoelectric Properties of Photodetectors Based on Silicon–Platinum Silicide Schottky Barriers with a Highly-Doped Surface Layer

We have calculated the spectral, threshold, and noise characteristics of p-Si–PtSi photodetectors with highly-doped surface layers produced by molecular-beam epitaxy and short-pulse ion implantation by a recoil method.     

Numerical prediction of transonic viscous separated flow past an airfoil

A method for the numerical treatment of transonic viscous flows past an airfoil has been developed allowing for calculation of both attached flows and flows with large separation regions including shock-induced separation. The method accounts for the entropy correction and the presence of vorticity behind the shock. The method is based on a zonal approach. The computation of the separated-flow regimes is provided by a quasi-simultaneous method of viscous—inviscid interaction. A computer code, called VISTRAN, is developed on the basis of this method and extensive comparisons of computed results with experimental data are made.