Indolopyridines with a hetero atom at a position of fusion. 5. Catalytic synthesis of indolo[2,1-a]isoquinoline by pyrolysis of benzylisoquinolines

High-temperature heterocyclization of -benzylisoquinolines on oxide-type catalysts gave angular indolo[2,1a] isoquinoline.For Communication 4 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 79–82, January, 1994.     

Hexacyanocobaltate(III) anions as precursors of Co(II)-Ni(II) cyano-bridged multidimensional assemblies: hydrothermal syntheses, crystal and powder X-ray structures, and magnetic properties

Three novel cyanide-bridged heterobimetallic coordination polymers have been synthesized by hydrothermal routes, in superheated water solutions, by using K3[Co(CN)6], NiCl2.6H2O, and alpha-diimine ligands: [Ni(CN)4Co(phen)] (1; phen = 1,10-phenanthroline), [Ni(CN)4Co(2,2'-bipy)] (2; 2,2'-bipy = 2,2'-bipyiridine), and [Ni(CN)4Co(2,2'-bipy)2] (3). The isostructural compounds 1 and 2 contain a two-dimensional network with Co(II) centers octahedrally coordinated by one chelating 2,2'-bipy ligand and four cyanide groups of four distinct [Ni(CN)4]2-, through crystallographically equivalent, bridging units. Compound 3 contains one-dimensional zigzag chains in which the Co(II) ion is coordinated by two chelating 2,2'-bipy ligands and two cyanides from two different [Ni(CN)4]2- units cis to each other. These compounds have been fully characterized by single-crystal or unconventional powder X-ray diffraction analyses and variable-temperature magnetic measurements.     

Isolation,Structure Determination and Synthesis of New Acetylenic Steroids from the Sponge Calyx nicaaensis

Two acetylenic steroids, cholest-5-en-23-yn-3β-ol ( 5 ) and 26,27-dinorcholest-5-en-23-yn-3β-ol ( 3 ), and another unsaturated steroidalcohol, stigmasta-5,23-dien-3β-ol ( 7 ), were isolated from the sponge Calyx nicaaensis. The structures of these two acetylenic steroids were established by synthesis. Several attempts to synthesize the marine steroids alcohol calysterol ( 1 ), with a cyclopropene-containing side chain, starting from cholest-5-en-23-yn-3β-ol are also recorded. Addition of ethyl-diazo-acetate to the triple bond was performed, but the reduction to the methyl derivative yielded decomposition products.     

Effect of Showerhead Configuration on Coherent Raman Spectroscopically Monitored Pulsed Radio Frequency Plasma Enhanced Chemical Vapor Deposited Silicon Nitride Thin Films

The effect of showerhead design, number of holes and geometry, in a parallel plate reactor was studied by measuring the concentration of silane reactant by coherent anti-Stokes Raman scattering (CARS) spectroscopy as a function of radio frequency (rf) pulse width and peak power during pulsed power plasma enhanced chemical vapor deposition (PECVD) of silicon nitride thin films. Film deposition rate, stress, SiH/NH ratio, and thickness and index of refraction homogeneity were correlated with the change in silane concentration for each of the three head geometries: radial, square, and asymmetrical. The asymmetrical head caused plasma quality problems which affected the films' qualities. The square pattern showed good mixing qualities, but produced a film with high compressive stress. The radial head provided the most homogenous film, with respect to index of refraction and film thickness. With a 10 ms pulse width, however, the radial head plasma acted as a continuous plasma for depletion and stress data. The showerhead geometry affects plasma qualities, like stability and intensity, and reactant gas velocities, which in turn affect the nitride film thickness, nitride composition, and stress.     

Cyclopentathiadiazines, new heterocyclic materials from cyclic enaminonitriles

Indene and cyclopentene enaminonitriles were reacted with SCl2, iBu3N and NCS to give the first cyclopenta[1,2,6]thiadiazines that showed unusual characteristics, one as a NIR dye and another as a liquid crystal.     

Generation and fate of free radicals of Δ2-oxazolin-5-ones

The reaction of Δ² -oxazolin-5-ones 1a and 1b with nickel peroxide in benzene produces the corresponding 4,4-dehydrodimers 5a and 5b as the main products in yields over 75%. Under the same conditions, the 2-aryl -4-methyl - Δ²-oxazolin-5-ones 1c, 1d and 1e yield five products. In the case of 1c, the constituents of the product mixture were separated and identified as two 4,4-dehydrodimers ( meso and d] pair isomers) 5c and 5c', (40.7%), 2,4-dehydrodimer 6c (34.9%), acetylanisoylimide 8c (8.5%) and anisamide (15.9%). Adequate mechanistic schemes are discussed to account for the products formed.     

Characterization and quantitation of mixtures of alkyl ether sulfates and carboxylic acids by capillary electrophoresis with indirect photometric detection

The separation, characterization, and determination of mixtures of alkyl ether sulfates (AES) and fatty acids (C10-C16) in background electrolytes (BGEs) containing acetonitrile (ACN)-water mixtures is addressed. Due to inhibition of the ionization of the carboxylate groups, the migration time and the resolution between the fatty acids decreased when the water content of the BGE was reduced, but efficiency and resolution between the AES oligomers improved. The migration times increased and resolution improved by substituting 5% ACN by an equivalent amount of dioxane. A complete separation of the two surfactant classes, up to the AES oligomers with 8 ethylene oxide units (EOs) with respect to C10, with excellent resolution between the AES oligomers, while preserving a satisfactory resolution between the fatty acids, was achieved with a BGE containing 5 mM trimethoxybenzoic acid, 7 mM dipentylamine, 85% ACN, 5% dioxane, and 10% water. The two surfactant classes were increasingly resolved by further reducing the water content of the BGE. Thus, C2 (acetate) was resolved from the AES oligomers up to 7 EOs using 90% ACN and 5% dioxane, but the resolution between the heavier fatty acids was poor with this BGE. Identification of the AES oligomers was eased by the excellent regularity of the successive migration times; thus, within each AES subclass or series of oligomers with the same number of carbon atoms in the alkyl chain, the migration times decreased following a mild curve as the number of EOs increased. The way how the data obtained by indirect photometry (corrected peak areas that are proportional to the molar concentrations) should be managed to avoid systematic error when the calibration curve is constructed using an AES standard with an oligomer distribution different from that of the samples is discussed and equations are given. Decyl sulfate was successfully used as internal standard. The detection limits (S/N = 3) were of ca. 2 microM for individual AES oligomers.     

Reactions of NO3-naphthalene adducts with O2 and NO2

The kinetics of the gas-phase reaction of the NO₃ radical with naphthalene have been investigated at 150 torr O₂ + 590 torr N₂ and 600 torr O₂ + 140 torr N₂ at 298 ± 2 K. Relative rate measurements were carried out in reacting NO₃? N₂O₅-naphthalene-propene-O₂? N₂ mixtures by longpath Fourier transform infrared absorption spectroscopy. A rate constant ratio for the reactions of O₂ and NO₂ with the NO₃-naphthalene adduct of k/k < 4 × 10^?7 was obtained from the competition between O₂ and NO₂ for reaction with the NO₃-naphthalene adduct and thermal decomposition of the adduct back to reactants. Atmospheric pressure ionization MS/MS measurements of the nitronaphthalene products of the NO₃ radical-initiated reaction of naphthalene are consistent with the proposed reaction mechanism, and the atmospheric implications of the data are discussed. © 1994 John Wiley & Sons, Inc.     

PCDD, PCDF, and PCB contamination of air and inhalable particulate in Rome

Summary The isomer specific determination of PCDD, PCDF and PCB was carried out on samples of air and inhalable particulate from Rome. Samples were taken daily for six months and pooled to yield two samples per month. Normal PCDD+PCDF concentrations expressed in TEQ ranged from 48 to 87 fg/m³, while total PCB ranged from 0.1 to 1.4 ng/m³. The 2, 3, 7, 8-substituted PCDD and PCDF congener pattern is shown together with the PCB congener pattern.     

Synthesis, crystal structure, spectroscopic and electrochemical characterization of the dinuclear complex {tetra-μ-[(±)-2-(p-methoxyphenoxy)-propionato-O,O′]bis(aqua)dicopper(II)}

Structural, electrochemical and spectroscopic data of a new dinuclear copper(II) complex with (±)-2-(p-methoxyphenoxy)propionic acid are reported. The complex {tetra-μ-[(±)-2-(p-methoxyphenoxy)propionato-O,O′]-bis(aqua)dicopper(II)} crystallizes in the monoclinic system, space group P2₁/n with a = 14.149(1) ?, b = 7.495(1) ?, c = 19.827(1) ?, β = 90.62(1) and Z = 4. X-ray diffraction data show that the two copper(II) ions are held together through four carboxylate bridges, coordinated as equatorial ligands in square pyramidal geometry. The coordination sphere around each copper ion is completed by two water molecules as axial ligands. Thermogravimetric data are consistent with such results. The ligand has an “L” type shape due to the angle formed by the β-carbon of the propionic chain and the linked p-methoxyphenoxy group. This conformation contributes to the occurrence of a peculiar structure of the complex. The complex retains its dinuclear nature when dissolved in acetonitrile, but it decomposes into the corresponding mononuclear species if dissolved in ethanol, according to the EPR measurements. Further, cyclic voltammograms of the complex in acetonitrile show that the dinuclear species maintains the same structure, in agreement with the EPR data in this solvent. The voltammogram shows two irreversible reduction waves at E _pc = −0.73 and −1.04 V vs. Ag/AgCl assigned to the Cu(II)/Cu(I) and Cu(I)/Cu° redox couples, respectively, and two successive oxidation waves at E _pa =− 0.01 and +1.41 V vs. Ag/AgCl, assigned to the Cu°/Cu(I) and Cu(I)/Cu(II) redox couples, respectively, in addition to the oxidation waves of the carboxylate ligand.