Combining chiral elements: a novel approach to asymmetric phase-transfer catalyst design

A new dicationic asymmetric phase-transfer catalyst, designed by combining chiral elements, is described. Catalytic testing using standard glycine imino ester alkylations shows good yields and moderate enantioselectivities.     

CHANGES IN TOTAL DIFFUSE SPECTRAL REFLECTANCE OF AMINO ACIDS AND PROTEINS AFTER ULTRAVIOLET IRRADIATION

Abstract— Total diffuse reflectance spectra of air-dried surfaces of free and neutralized amino acid preparations before and after irradiation in vitro are reported. It was found that some free or neutralized amino acid surfaces underwent modification which resulted in changes in the diffuse reflectance spectra after U.V. exposure. It is suggested that these reflectance changes result from transformations in the side chains of the amino acids and that the transformations may differ from those occurring when amino acids in solution are irradiated. Histidine, cystine, hydroxyproline and some protein surfaces showed changes in reflectance of 330–400 nm light similar to those reported in skin after U.V. irradiation in viuo.     

Dynamic NMR investigation of two new interconvertible diasteriomeric epimers of natural 2-benzyl-2-hydroxybenzofuranone derivative from Pterocarpus marsupium

The first example of a pair of interconvertible diastereomeric epimers 2α/2β-hydroxy-2-p-hydroxybenzyl-3(2H)-benzofuranone-7-C-β-d-glucopyranoside isolated from the heartwood of Pterocarpus marsupium is reported. The predominance of 1a over 1b was supported by dynamic exchange rates and activation parameters obtained from NMR studies. The mechanism of this unique phenomenon is thought to be operative by the formation of diketone as suggested by deuterium exchange.     

Combining chiral elements in asymmetric phase-transfer catalysts: styrene oxide and chiral α,α-disubstituted pyrroline and piperidine derived structures

A new asymmetric phase-transfer catalyst, designed by combining the chiral building blocks styrene oxide and 2,5-dimethylpyrroline, is described. Catalytic testing using standard glycine imino ester alkylations shows good yields and moderate to good enantioselectivities with a surprising change in enantioselectivity over the course of the reaction. Alkylation of the β-hydroxyl group lead to catalysts with improved selectivity and a larger change in enantioselectivity during the reaction.     

Facile Reduction of Chalcones to Dihydrochalcones with NaBH4/Ni2+ System

Chalcones have been found to undergo facile reduction on treatment with sodium borohydride-nickel chloride system in dioxan-methanol medium to afford dihydrochalcones.     

Phase relation studies in the CeO2-Gd2O3-ZrO2 system

The phase relations in the CeO₂-Gd₂O₃-ZrO₂ system have been established after slowly cooling the samples from 1400 °C. Ceria has been used as a surrogate material in place of plutonia. About 80 compositions in Zr_1−xGd_xO_2−x/2, Ce_1−xGd_xO_2−x/2, Ce_1−xZr_xO_2.00, (Zr_0.5Ce_0.5)_1−xGd_xO_2−x/2, (Ce_0.5Gd_0.5)_1−xZr_xO_1.75+x/4, (Zr_0.5Gd_0.5)_1−xCe_xO_1.75+x/4, and (Ce_0.8Zr_0.2)_xGd_1−xO_1.5+x/2 were prepared by a three steps heating protocol. Based on the refinement of the XRD data, several phase regions namely; cubic fluorite type solid solution, C-type solid solution, and various biphasic regions could be delineated. This system showed the existence of a very wide cubic phase field. About 17.5 mol% GdO_1.5 was found to fully stabilize the cubic zirconia. On the other hand ceria did not stabilize the cubic zirconia. The anion-excess gadolinia, i.e., Gd_1−xCe_xO_1.5+x was found to retain the C-type lattite unlike pure gadolinia. The ternary phase relations were mainly characterized by the presence of wide homogeneity ranges of fluorite type or C-type phases.     

Some Characterizations of VNL Rings

A ring R is said to be von Newmann local (VNL) if for any a ∈ R, either a or 1 ?a is (von Neumann) regular. The class of VNL rings lies properly between exchange rings and (von Neumann) regular rings. We characterize abelian VNL rings. We also characterize and classify arbitrary VNL rings without an infinite set of orthogonal idempotents; and also the VNL rings having a primitive idempotent e such that eRe is not a division ring. We prove that a semiperfect ring R is VNL if and only if for any right uni-modular row (a ₁, a ₂) ∈ R ², one of the a _i 's is regular in R. Formal triangular matrix rings that are VNL are also characterized. As a corollary, it is shown that an upper triangular matrix ring T _n (R) is VNL if and only if n = 2 or 3 and R is a division ring.     

Description of K-spaces by means of J-spaces and the reverse problem in the limiting real interpolation

We establish conditions under which K-spaces in the limiting real interpolation involving slowly varying functions can be described by means of J-spaces and we also solve the reverse problem. To this end, we prove several versions of the fundamental lemma of the real interpolation theory. We apply our results to obtain density theorems for the corresponding limiting interpolation spaces.     

Simulation of three-phase displacement experiments

Three-phase displacement experiments for a water-benzyl alcohol-decane system are simulated. Literature experimental three-phase relative permeabilities for the system are used to describe the relative permeabilities in the three-phase region for different three-phase relative permeability models. Saturation trajectories and elliptical regions are mapped in the three-phase region. Simulations are performed to model displacement experiments including breakthrough and the formation of multiple shocks. The model can be used to predict the results for other displacements. In an experiment where significant gravity segregation is present, the displacement is more accurately modeled by assuming a uniform initial condition than by using the actual vertical saturation and assuming no cross flow. It is shown how different residual saturation values can be measured in the laboratory depending on the initial saturation conditions in the core. The experimental residual saturations can be significantly different than the ‘theoretical’ or model values.