Electron impact and chemical ionization mass spectra of 2,2-diphenyl-3-arylcyclobutanone oximes. Formation of ion m/z 167

The electron impact (EI) and chemical ionization (CI) spectra of 2,2-diphenyl-3-aryl cyclobutanone oximes (1–5) are reported. Formation of diphenylmethyl cation at m/z 167 is a major fragmentation process in both EI and CI spectra. Labelling studies established that the hydrogen involved in this rearrangement transfers from the NOH group and not from cyclobutane ring positions. The [M + 3]⁺ ions are formed under CI conditions as a result of C?N double bond reduction. An interesting secondary kinetic isotope effect is observed in the formation of ion e at m/z 183 in both EI and CI spectra. Other characteristic fragmentation pathways occurring in the EI and CI spectra of these compounds are outlined.     

Block copolymerization initiated by Mn(III)-poly(ethylene glycol) redox system — general features and kinetics

The kinetics and mechanism of thermal polymerization of acrylonitrile initiated by Mn(III) pyrophosphate — poly(ethylene glycol) (PEG, molecular weight 6000) redox system in aqueous sulfuric acid medium was studied in the temperature range 30–60°C. The overall rates of polymerization and the disappearance of Mn³⁺ were determined. The polymerization was initiated by the organic free radical produced from the Mn³⁺-PEG reaction and the termination was by the metal ions. The rate of polymerization of acrylonitrile was found to be directly proportional to the square of the monomer concentration and first power of PEG concentration, and inversely proportional to the concentration of Mn³⁺. The rate of manganic ion disappearance was found to be directly proportional to manganic ion concentration and PEG concentration, and independent of the monomer concentration. Based on these observations, a plausible reaction scheme was suggested and suitable kinetic expressions were evaluated.     

Efficient light harvesting and energy transfer in organic-inorganic hybrid multichromophoric materials

Thin films of silica hybrid materials consisting of two to three covalently bound organic chromophores at different ratios were conveniently synthesized and fabricated. The photophysical properties of these materials have been studied. The fluorescence spectra reveal complete fluorescence resonance energy transfer (FRET) from donor to acceptor, and the light-harvesting ability of these hybrid materials increases with increasing the molar fraction of donor chromophore. In a three-chromophore system, the energy is transferred from 300 to 530 nm successfully. Time-resolved fluorescence experiments are employed to elucidate the average rates and efficiencies (84-97%) of energy transfer in these organic/inorganic hybrid systems. The hybrid materials have been shown to provide antenna effect to facilitate energy transfer and light harvesting.     

Synthesis of Conjugated Optically Active Polymetallocenes

The development of methodology for synthesizing new materials in which metal atoms are linked by hydrocarbons whose electronic conjugation is unbroken is described. The fundamental idea is to twist the hydrocarbons into helices. By attaching bulky groups to their precursors, the helices can be made to twist mainly in one direction. The molecules synthesized are helicenes capped by five-membered rings to which metals are attached. If the size of the helix is chosen appropriately, a polymeric structure forms in which hydrocarbon rings and metal atoms alternate. An oligomer with Structure 22 is the first such material prepared. It and related structures might be precursors of molecular solenoids, examples of which are not yet known.     

Improved Procedure for the Synthesis of DAMGO

A short and straightforward synthesis of DAMGO is described.     

CeCl3·7H2O-Catalyzed Synthesis of 1-Oxo-hexahydroxanthene Derivatives in Aqueous Media

Cerium(III) chloride heptahydrate (CeCl₃·7H₂O) catalyzes the reaction of substituted salicylaldehydes with 1,3-cyclohexane dione or dimedone in aqueous medium at reflux temperature to afford the corresponding 1-oxo-1,2,3,4,9,10-hexahydroxanthene derivatives4 0 in high yields.     

Efficient Bromination of Alkenes and Alkynes Using Potassium Bromide and Diacetoxy Iodobenzene

Bromination of alkenes and alkynes has efficiently been carried out at room temperature in short reaction times using KBr and diacetoxy iodobenzene in CH₂Cl₂-H₂O (1:1) to prepare the corresponding trans-dibromo compounds in excellent yields.     

Studies on thermotropic main chain liquid crystalline segmented polyurethanes I. Synthesis and properties of polyurethanes from high aspect ratio mesogenic diol as chain extender

Thermotropic main chain liquid crystalline polyurethanes were prepared from 4-{[4-(6-hydroxyhexyloxy)phenylimino]methyl}benzoic acid 4-{[4-(6-hydroxyhexyloxy)phenylimino]methyl}phenyl ester (mesogenic diol) and 1,6-hexamethylene di-isocyanate. The effects of partial replacement of the mesogenic diol by 20-50 mol% of poly(tetramethylene oxide)glycol (PTMG) of varying molecular mass (M _n =650, 1000, 2000) on the liquid crystalline properties were studied. Structural characterization was carried out by FTIR spectroscopy and the molecular mass distribution was determined by GPC. Differential scanning calorimetry and hot stage polarizing optical microscopy were used to study the mesomorphic properties. It was observed that the partial replacement of the mesogenic diol by PTMG of varying molecular masses influenced the phase transitions and the occurrence of mesophase textures. When the molecular mass of PTMG was enhanced, a higher content of mesogenic agent was needed to obtain liquid crystalline properties.     

Zinc triflate catalyzed acylation of alcohols,phenols, and thiophenols

An expedient procedure for the acylation of alcohols, phenols, and thiophenols using catalytic amount of Zn(OTf)₂ is described. This procedure is highly suitable for industrial application due to use of less toxic metal as a part of catalyst, short reaction time at ambient temperature, without any racemization of chiral alcohols.