Rh(III)-Catalyzed One-Step Synthesis of ortho-Alkynylated Perylene Imide Dyes: Optical and Electrochemical Properties of New Derivatives

A one-step Rh-catalyzed site-selective ortho-C−H alkynylation of perylene as well as naphthalene mono- and diimides is reported. A single step regioselective access to ortho-C−H alkynylated derivatives of these ryleneimides not only increases the step economy of the ortho-functionalization on these dyes but also provides a quick access route towards highly functionalized dyes that have potential optoelectronic applications. Increased solubility of tetra(triisopropylsilyl)acetylenyl PDIs in organic solvents greatly enhances their utility for further derivatization.     

Multifunctional ToF-SIMS: combinatorial mapping of gradient energy substrates

We present a simple method for chemical modification of chlorosilane self-assembled monolayers (SAMs) on Si surfaces by exposure to a gradient of UV-ozone radiation to create stable substrates with a range of contact angles (θ_H2O≈5–95°) and surface energies on a single substrate. These gradient energy substrates are developed to potentially generate libraries for combinatorial studies of thin film phenomenology, where a systematic variation of interfacial surface energy represents one of the significant parameters along one axis. The graded oxidation process presents a systematic variation of surface chemical composition. We have utilized contact angle measurements and time-of-flight secondary ion mass spectrometry (ToF-SIMS) to investigate this variation for a series of ions, among which are SiCH₃⁺, SiOH⁺ and COOH⁻. We show that the macroscopic measurements of surface free energy/contact angle correlate with the detailed analysis of surface chemistry (as assessed by ToF-SIMS) on these test substrates.     

Mössbauer studies of iron stabilised polymethacrylates

Polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA) and polybutyl methacrylate (PBuMA) containing ferric chloride and ferrous sulphate as stabilisers, were prepared by free radical polymerization. Mössbauer spactra of ferrous sulphate stabilised polymers don't show any change in the value of isomer shift (1.30 mm/s) while quadrupole splitting values are quite different from those for pure ferrous sulphate. This indicates that environment of Fe²⁺ moiety changes in polymers and thus stabilises the polymers. In case of ferric chloride stabilised polymers the isomer shift values don't differ significantly for different polymethacrylates but quadrupole splitting values increase from polymethyl methacrylate to polybutyl methacrylate. The TGA analysis shows that the inclusion of iron salts stabilises the polymers by 40°C (approx.) and at higher temperatures α-Fe₂O₃ is formed.     

Oxidation of cyclohexane with molecular oxygen using a Schiff base cobalt complex bonded to carbamate-modified silica gel

The Schiff base [1,2-bis(salicylidene amino)phenylene]cobalt(II) complex, chemically bonded to a carbamate-modified silica gel catalyst, has been prepared by a four step procedure. The oxidation of cyclohexane was studied in the presence of this catalyst under relatively mild conditions (150–200 °C, 15–20 atm) using molecular oxygen. The catalyst was found to be very selective for the production of cyclohexanol, with cyclohexanone formed in only a small amount (45:1). This is in contrast to the commercially available processes in which cyclohexanol and cyclohexanone are both formed in appreciable amounts. The t.g.a. analysis shows the catalyst to be stable up to 211 °C and atomic absorption spectroscopy indicated negligible metal loss during 50 h use of the catalyst up to 180 °C.     

Free-radical polymerization of methyl methacrylate in presence of the Cr(C5H7O2)3–Al(i-C4H9)3 catalyst system

Polymerization of methyl methacrylate has been studied with the chromium acetylacetonate–triisobutyl aluminum catalyst system in benzene medium at 40°C. These studies have been carried out at an Al/Cr ratio of 12 to compare the behavior with the previously studied chromium acetyl acetonate–triethyl aluminum catalyst system. The enhanced yield and gelling of polymer suggests a free-radical mechanism of polymerization. Further, the kinetics of polymerization and the heterotactic structure of polymer as determined by NMR examination have led to confirmation of the freeradical mechanism of polymerization of methyl methacrylate by an excess of triisobutylaluminum in the presence of catalyst complex.     

An efficient route to regioselective opening of N-tosylaziridines with zinc(II) halides

An efficient route for the regio- and stereoselective ring opening of N-tosylaziridines with zinc dihalides (ZnX₂, X = Cl, Br, I) is described. Depending on the solvent and Zn(II) halide, β-halo amines or imidazolines are obtained selectively in good to excellent yields.     

Cu-nanoparticles: a chemoselective catalyst for the aza-Michael reactions of N-alkyl- and N-arylpiperazines with acrylonitrile

A novel method for effecting the aza-Michael reactions of N-alkyl- and N-arylpiperazines with acrylonitrile using Cu-nanoparticles is described. The method features the use of 10 mol % Cu (14-17 nm) nanoparticles under mild reaction conditions to afford the addition products in good to excellent yields. The Cu-nanoparticles selectively catalysed the aza-Michael reaction of N-alkyl- and N-arylpiperazines in the presence of aromatic amino or aliphatic hydroxy groups.