Direct N- and C-alkenylation of nitrogen-containing heterocycles with magnesium alkylidene carbenoids

Treatment of magnesium alkylidene carbenoids, which were generated from 1-chlorovinyl p-tolyl sulfoxides with isopropylmagnesium chloride at −78 °C in toluene, with N-lithio nitrogen-containing heterocycles gave N-alkenylated products in moderate to good yields. Also, the reaction of C-lithio indoles, which were generated from N-protected indoles, with magnesium alkylidene carbenoids gave C-2 or C-3 alkenylated products, corresponding to the protective group. The intermediate of these reactions were found to be the alkenyl anion, which could be trapped with electrophiles to give the heterocycles having fully substituted alkenes.     

Generalized coulomb barrier transmission coefficient for solar neutrino and astrophysical problems

For astrophysical calculations, it is customary to extrapolate higher-energy (20keV) data using the Gamow transmission coefficient in estimating the nonresonance nuclear fusion reaction cross sections (E) for charged particles at low energies (<20 keV). We present a general extrapolation method based on a more realistic Coulomb barrier transmission coefficient, which can accommodate simultaneously both nonresonance and resonance contributions.     

Maximizing the xylitol production from sugar cane bagasse hydrolysate by controlling the aeration rate

Batch fermentations of sugar cane bagasse hemicellulosic hydrolysate treated for removing the inhibitors of the fermentation were performed byCandida guilliermondii FTI20037 for xylitol production. The fermentative parameters agitation and aeration rate were studied aiming the maximization of xylitol production from this agroindustrial residue. The maximal xylitol volumetric productivity (0.87 g/L h) and yield (0.67 g/g) were attained at 400/min and 0.45 v.v.m. (K_La 27/h). According to the results, a suitable control of the oxygen input permitting the xylitol formation from sugar cane bagasse hydrolysate is required for the development of an efficient fermentation process for large-scale applications.     

Copolymerization of ethylene and 1-butene with highly active Ticl4/THF/Mgcl2, Ticl4/THF/Mgcl2/SiO2, and TiCl3.1/3AlCl3 catalysts

Highly active catalysts for copolymerization have been prepared by the precipitation of MgCl₂/ToCl₄ complex with or without high surface area silica. Copolymerization of ethylene and 1-butene has been tested by using the prepared catalysts at various concentrations of 1-butene. The catalytic activities are 20–80 kg/g Ti h. The rate of copolymerization is strongly affected by the addition of 1-butene. The decay rate of copolymerization is first order with respect to time. Analyses of copolymers with solvent extraction, DSC, IR, XRD, and NMR were performed. Ethylene reactivity ratio (k₁₁) for TiCl₄/MgCl₂/THF catalyst is calculated to be about 26 by NMR spectrum. © 1994 John Wiley & Sons, Inc.     

Formation of nanostructured polymer filaments in nanochannels

We describe the use of hard etching methods to create nanodimensional channels and their use as templates for the formation of polymer filament arrays with precise dimensional and orientational control in a single integrated step. The procedure is general as illustrated by the radical, coordination, and photochemical polymerizations that were performed in these nanochannels. The nanochannel templates (20 nm high, 20-200 nm wide, and 100 mum long) were fabricated by the combined use of electron-beam lithography and a sacrificial metal line etching technique. Radical polymerization of acrylates, metal-catalyzed polymerization of norbornene, and photochemical polymerization of 1,4-diiodothiophene were carried out in these nanochannels. The polymers grown follow the dimensions and orientation of the channels, and the polymer filaments can be released without breaking. The approach opens up the possibility of just-in-place manufacturing and processing of patterns and devices from nanostructured polymers using well-established polymer chemistry.     

Pattern generation of biological ligands on a biodegradable poly(glycolic acid) film

The micropatterns of biological ligands (biotin and RGD peptides) were generated on a flat surface of biodegradable polymer, poly(glycolic acid) (PGA). The immobilization of biological ligands onto the surface of biodegradable polymers (especially aliphatic polyesters) is usually hampered by the absence of functionalizable groups on the polymer backbone. We demonstrate herein that PGA polymer films were modified by surface hydrolysis to introduce carboxylic acid groups on the film surfaces, which were subsequently used for patterning amine-terminated ligands by microcontact printing. Fluorescence microscopy was used to verify the pattern of biotin on the surface of the PGA films after complexation with fluorescein-conjugated streptavidin. In addition, the cellular micropatterns were obtained from micropatterns of RGD peptides on the surface-hydrolyzed PGA films.     

Methyl abstraction kinetics of CpFe(CO)2Me using the benzyl radical clock

The rate constant for the methyl abstraction reaction of CpFe(CO)₂Me has been measured with the benzyl radical clock as (1.1 ± 0.2) × 10⁵ M⁻¹ s⁻¹ at room temperature. Time-resolved Fourier-transform Infrared (FTIR) absorption spectroscopy pointed towards the formation of the CpFe(CO)₂ radical upon benzyl abstraction. The main stable product has been established by a linear scan of the reaction mixture as Cp₂Fe₂(CO)₄ produced by the dimerization of the CpFe(CO)₂ radicals. The transition state structure for the abstraction process was also found at UB3LYP/6-311+G* level of theory to contain a planar CH₃ group.     

Reversal of facial selectivity in complex Diels-Alder reactions

A complex Diels-Alder reaction between a semi-cyclic diene with allylic silyloxy substituents and a bromo enone presented an unusual diastereoselectivity: attack of the diene occured on its more hindered face, and this reversal of selectivity was shown to be induced by the presence of a bromo substituent in the dienophile.     

Infrared-visible and visible-visible double resonance spectroscopy of 1-hydroxy-9,10-anthraquinone-(H2O)n (n=1,2) complexes

The structures of hydrated 1-hydroxyanthraquinone complexes (1-HAQ), 1-HAQ(H2O)n=1,2, with intramolecular and intermolecular hydrogen bonding interactions were studied using laser spectroscopic methods such as laser induced fluorescence, fluorescence-detected infrared, infrared-visible hole burning, and visible-visible hole burning spectroscopy. In the 1:1 complex 1-HAQ(H2O)1, the water binds to the free carbonyl group of 1-HAQ not associated with intramolecular hydrogen bond. The second water in the 1:2 complex, 1-HAQ(H2O)2, binds to the first water of the 1:1 complex rather than other hydrogen bonding sites of 1-HAQ. A pair of two geometric isomers was produced in a supersonic jet for each of the 1:1 and 1:2 complexes. Both isomers of each complex have the same vibrational spectra in the region of the OH stretching vibration of water, but have different energies for the 0-0 band of vibronic transition due to the asymmetry of the two phenyl rings in 1-HAQ. The 0-0 bands for all four species of 1-HAQ(H2O)n=1,2 were unambiguously assigned by comparing with the results of ab initio calculations, which yielded the structures, vibrational frequencies, and relative energies of the frontier molecular orbitals.     

Mononuclear and dinuclear copper(I) complexes with a particularly bulky phosphine ligand. Unusual synthesis and crystal structure characterizations

Summary The addition of NPm (diphenylaminodiphenylphosphinomethane) to CuI or the addition of KI to (NPm)₂CuNO₃ leads to the same P-bonded Cu^I complex, (NPm)₂CuI, presenting a trigonal geometry around the Cu atom. The reaction of this new complex (or of its chloro analogue) with a Cu^II salt yields dinuclear species of general formula [(NPm)Cu(-X)₂Cu(NPm)] (X = Cl or I). X-ray analysis of these complexes show that they are isostructural and retain the trigonal geometry around the metal atom. The Cu···Cu distances are 2.775(1)Å for X = Cl and 2.642(1) Å for X = I. The Cu-(-X)-Cu angle is more acute for the iodide [61.48(3)°] than for the chloride [74.17(8)°] complex. These values are discussed in terms of Cu···Cu interactions induced by the electron donor ability of X and the bulk of the phosphine L.