SnCl4 and SbCl5 promoted aromatization of enamines

Aromatic amines have been synthesized efficiently from enamines using SnCl₄ and SbCl₅ in CH₂Cl₂ at room temperature.     

Monolayers as models for supported catalysts: zirconium phosphonate films containing manganese(III) porphyrins

Organized monolayer films of a manganese tetraphenylporphyrin have been prepared and used as supported oxidation catalysts. Manganese 5,10,15,20-tetrakis(tetrafluorophenyl-4'-octadecyloxyphosphonic acid) porphyrin (1) has been immobilized as a monolayer film by a combination of Langmuir-Blodgett (LB) and self-assembled monolayer techniques that use zirconium phosphonate linkages to bind the molecule to the surface. Analysis by FTIR, XPS, UV-vis and polarized optical spectroscopy show that the films consist of noninteracting molecules effectively anchored and oriented nearly parallel to the surface. The monolayer films are stable to the solvent and temperature conditions needed to explore organic oxidations. The activity of films of 1 toward the epoxidation of cyclooctene using iodosylbenzene as the oxidant was compared to that of Manganese 5,10,15,20-tetrakis(pentafluorophenyl) porphyrin (2) and 1 under equivalent homogeneous conditions. The immobilized porphyrin 1 shows an enhanced activity relative to either homogeneous reaction. The main difference between 1 and 2 is the four alkyl phosphonate arms in 1 designed to incorporate the porphyrin within the films. The increased activity of immobilized 1 is a combination of the porphyrin structure, which prohibits the formation of mu-oxo dimers even in solution, and a change in conformation when anchored to the surface. The study demonstrates that careful monolayer studies can provide useful models for the design and study of supported molecular catalyst systems.     

Insecticidal Activity and Free Radical Scavenging Properties of Isolated Phytoconstituents from the Saudi Plant Nuxia oppositifolia (Hochst.)

Chromatographic purification of the alcoholic extract from the aerial parts of the Saudi plant Nuxia oppositifolia (Hochst.), Benth., resulted in five isolated phenolic compounds. Two flavones, hispidulin (1) and jaceosidin (2), and the phenylethanoid glycosides, verbascoside (3), isoverbascoside (4), and conandroside (5), were identified and their chemical structures were determined by spectroscopic analyses. The insecticidal activity of compounds 1 and 2, in addition to 11 compounds isolated in a previous research (6–16), was evaluated against the Yellow Fever mosquito, Aedes aegypti. Four compounds displayed adulticidal activity with LD₅₀ values of 2–2.3 μg/mosquito. Free radical scavenging properties of the plant extracts and compounds (1–5) were evaluated by measuring the 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) and 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonate radical cation (ABTS^•+) scavenging activity. All compounds exhibited notable activity, compared with the positive control, l-Ascorbic acid. This study suggests that N. oppositifolia could be a promising source of secondary metabolites, some with lethal adulticidal effect against Ae. aegypti.     

Light-regulated electrostatic interactions in colloidal suspensions

The net charge of a colloidal particle was controlled using light and a new photocleavable self-assembled monolayer (SAM). The SAM contained a terminal ammonium group and a centrally located carboxylic acid group that was masked with an ortho-nitrobenzyl functionality. Once exposed to UV light, the 2-nitrobenzyl group was cleaved, therefore transforming the colloidal particle from a net positive (silica-SAM-NH3+) to a net negative (silica-SAM-COO-) charge. By varying the UV exposure time, their zeta potential could be tailored between +26 and -60 mV at neutral pH. To demonstrate a photoinduced gel-to-fluid phase transition, a binary colloidal suspension composed of silica-SAM-NH3+ and negatively charged, rhodamine-labeled silica particles was mixed to form a gel. Exposure to UV light rendered all of the particles negative and therefore converted the system into a colloidal fluid that settles to form a dense sediment.     

“Living” radical graft polymerization of styrene to styrene butadiene rubber (SBR) with 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO)

Well‐defined graft copolymers with styrene butadiene rubber (SBR) backbones and polystyrene branches were synthesized by living free radical polymerization (LFRP) techniques. Thus 1‐ benzoyl‐2‐phenyl‐2‐(2′,2′,6′,6′‐tetramethyl‐piperidinyl‐1′‐oxy)ethane (BZ‐TEMPO) was synthesized and hydrolyzed to the corresponding 1‐hydroxyl derivative. This functional nitroxyl compound was coupled with brominated SBR (SBR‐Br). The resulting macroinitiator (SBR‐TEMPO) for “living” free radical polymerization was then heated in the presence of styrene for the formation of the controlled graft copolymer. ¹H‐NMR and IR spectroscopy were used to investigate the structure of the polymers. Copyright © 2004 John Wiley & Sons, Ltd.     

Spectrophotometric Determination of Thorium with Disodium Salt of Arsenazo-III in Perchloric Acid

A rapid and sensitive spectrophotometric method has been developed for the determination of thorium using 0.04% Arsenazo-III in a 2M perchloric acid solution. Absorbance was measured in 1 cm cell and the complex has a sensitive absorption peak at 654 nm. The complex is formed instantly in perchloric acid and remains stable for 45 minutes with constant absorbance. Beer's law is obeyed in the range 1–60 g·g^–1 of thorium concentration with a molar absorptivity at 654 nm = 3.07·10⁵ M^–1·cm^–1 at 24±2°C. The foreign ions interference in thorium determination have been checked. The cations were tested at >60-fold excess of thorium, Mn(II), Fe(III), Co(II) and Ni(II) interfere negatively, whereas only Ce(III) has increased the absorbance. Among the anions, cyanide, phosphate, thiocyanate and acetate at 150-fold excess of thorium cause significant interference. However, thorium can bedetermined in the presence of nitrate, chloride, oxalate, tartrate, ascorbate, thiosulphate and citrate. The method has been applied on certified reference material for thorium determination after extractive separation and the result was found in good agreement with the certified value. The method has been also applied successfully to determine thorium at g·g^–1 level in local ore samples with a precision of ±0.04%.     

Ammonia chemical ionization tandem mass spectrometry in structural determination of alkaloids. II. Tetraponerines from pseudomyrmecine ants

Chemical ionization tandem mass spectrometry (CI-MS/MS) of alkaloids with ammonia reagent gas and collision-activated dissociation as well as EI-MS/MS were applied to the tetraponerine alkaloids in extracts from six pseudomyrmecine ants of the genus Tetraponera. The MS/MS techniques along with gas chromatography Fourier transform infrared (GC/FTIR) spectra allowed identification in two extracts of seven of the eight known tetraponerines. The EI-MS/MS fragmentations proved diagnostic for the ring system and the CI-MS/MS patterns for the C-8 or C-9 substitution, while the Bohlmann bands in FTIR spectra were diagnostic for the C-8 or C-9 configurations. An Indian ant (T. allaborans) had T-2, T-4 and T-8, while a Chinese ant (T. binghami) had T-5, T-6, T-7 and T-8. Four other ants, T. rufonigra (India), T. penzigi (Africa), T. clypeata (Africa) and T. sp. cf. emeryi (Africa), had no tetraponerines.     

Enhancement of distillate selectivity in Fischer-Tropsch synthesis by using iron and cobalt catalysts in a novel dual-bed reactor ?

Summary An integrated process for producing liquid fuels from synthesis gas via a two-stage Fischer-Tropsch (FT) reaction is disclosed. An iron catalyst was used in the first bed of a fixed-bed reactor followed by a ruthenium promoted cobalt catalyst in the second bed. The activity and selectivity of the dual-bed system were assessed and compared with those using catalysts in a single bed system, separately. The methane selectivity in the dual-bed reactor was about 11% less compared to that of the single-bed system. The C₅⁺ selectivity for the dual-bed reactor was 19.7% higher than that of the single-bed system.     

Fine characterization of the ethylene and ethane sorption in poly(amide 12-block-tetramethylenoxide) copolymer/AgBF4 membranes

Ethylene/ethane sorption characteristics were determined for dry Pebax™ (poly(amide 12-block-tetramethylenoxide) copolymer)/AgBF₄ membranes by using an electronic microbalance. The membranes containing 0.7 and 22 wt.% AgBF₄ showed a dual-mode sorption isotherm. The ethane isotherms for all the membranes were of the Henry-type, which is the normal sorption for gases in rubbery polymers. The abnormal presence of Langmuir sorption sites only for ethylene in the rubbery copolymer, never reported sofar, is attributed to the silver-based specific complexation sites. The silver salt which dissolved in limited amounts in the rubbery copolymer had a much smaller Langmuir sorption capacity than the salt that crystallized in the copolymer. The sorption kinetics indicate that the crystallized salt did adsorb slowly ethylene according to a zeroth-order kinetics, but not ethane. The gas uptake kinetics resulting from a step of the pressure surrounding the copolymer exhibited one stage for ethane but two stages for ethylene. For the latter, there was first a fast Fickian sorption stage, then a drift of the zeroth-order sorption of ethylene on salt crystals, which contributes for a large part to the total uptake. The zeroth-order sorption suggests that the sorbed ethylene amount in the second-stage is independent of the crystal-surface coverage. The value of the Fickian diffusion coefficient calculated by fitting the kinetics with a solution of the second Fick’s law was 5 × 10⁻¹² m²/s for both ethylene (the first stage) and ethane, and is typical for small organic compounds in a rubbery material.     

Pyrrole studies part 41. Reactivity of 3,4-diformyl-2,5-dimethylpyrrole with diaminoalkanes. An unusual formation of 2-azafulvenes

3,4-Diformyl-2,5-dimethylpyrrole (1) reacts with ,ω-diamino-alkanes, NH₂(CH₂)_nNH₂t' to form either the potentially tautomeric 2:2 macrocyclic adduct (7a) (8), when N = 2, or the potentially tautomeric 1:1 bicyclic adduct (18) (19), when N = 4, 5, 6, and 12. ¹H and ¹³C N.m.r. spectral data indicate that the 2-azafulvene structures predominate for both types of cycloadducts. Only polymeric material was obtained when N = 3.