Intramolecular cyclization with nitrenium ions generated by treatment of N-acylaminophthalimides with hypervalent iodine compounds: formation of lactams and spiro-fused lactams

N-Phthalimido-N-acylnitrenium ions are generated from N-acylaminophthalimides, a new class of precursors, by treatment with hypervalent iodine compounds (PIFA and HTIB). In HFIP, the nitrenium ions undergo intramolecular electrophilic substitution reactions to afford N-aminonitrogen heterocycles in high yields. In TFEA, spirodienones bearing the 1-azaspiro[4.5]decane skeleton are obtained by treatment of N-phthalimido-3-(4-halogenophenyl)propanamides with HTIB as a result of ipso attack of the intermediate nitrenium ion. Similarly, using PIFA in TFEA, ipso cyclization of unactivated benzenoid compounds occurs to afford spirodiene derivatives. This involves loss of aromaticity despite the absence of other activating substituents on the phenyl group.     

N-tert-Butylbenzenesulfenamide-catalyzed oxidation of alcohols to the corresponding carbonyl compounds with N-chlorosuccinimide

N-tert-Butylbenzenesulfenamide (1)-catalyzed oxidation of various primary and secondary alcohols to the corresponding aldehydes and ketones was efficiently carried out by using N-chlorosuccinimide (NCS) in the coexistence of potassium carbonate and molecular sieves 4 Å at easy-to-control temperatures ranging from 0°C to room temperature. The present catalytic oxidation was performed without giving any damage to the functional groups in alcohols, and was particularly effective in the oxidation of alcohols that formed labile aldehydes because of its mild reaction conditions. Further, selective oxidation of primary hydroxy groups took place in 1-catalyzed oxidation of several diols. Mechanistic investigation suggested that the chlorination of the sulfenamide 1 by NCS led to the formation of a key species, N-tert-butylbenzenesulfinimidoyl chloride (2), which in turn oxidized alcohols in the presence of potassium carbonate to afford carbonyl products by accompanying regeneration of the catalyst 1.     

Distributivity and stationary reflections

In this paper, we present some relations between generalized distributivity of quotient algebras and Mahlo operations, and show that the distributivity implies some variants of stationary relections.

     

Fabrication of high performance Gd–Ba–Cu–O single grains in air using a practical melt processing technique

A practical processing route for the fabrication of LRE-Ba–Cu–O single grain superconductors has been developed at the University of Cambridge based on a generic, Mg-doped Nd-123 melt textured seed and suppression of the formation of the solid solution phase in air by enriching the precursors with higher Ba concentration. The processing of high performance Gd–Ba–Cu–O single grains using this processing route is described. The Mg-doped generic seed crystal has been used effectively to promote heterogeneous nucleation via a cold-seeding process. The Gd/Ba solid solution has been suppressed by enriching Gd–Ba–Cu–O precursor powders with two different Ba-rich compositions. This involved adding BaO₂ and GdBa₆Cu₃O_y (Gd-163) (a novel Ba-rich second phase) to the precursor powders, respectively. The Gd-163 phase has been observed not only to suppress formation of the solid solution phase, but also to promote increased heterogeneous grain size. A detailed further study has been carried out with an initial aim of optimizing the BaO₂ and Gd-163 phase content of the precursor composition to produce a single grain almost free of solid solution. Based on the optimized parameters, large single grain Gd–Ba–Cu–O superconductors have been fabricated in an air atmosphere and demonstrated to exhibit record trapped magnetic fields for this material melt processed in air in relatively small single grain samples. The trapped fields of samples produced in air atmosphere are at least comparable to those processed under reduced oxygen partial pressure.     

Inlet throttling effect on the boiling two-phase flow stability in a natural circulation loop with a chimney

 Experiments have been conducted to investigate an effect of inlet restriction on the thermal-hydraulic stability. A Test facility used in this study was designed and constructed to have non-dimensional values that are nearly equal to those of natural circulation BWR. Experimental results showed that driving force of the natural circulation at the stability boundary was described as a function of heat flux and inlet subcooling independent of inlet restriction. In order to extend experimental database regarding thermal-hydraulic stability to different inlet restriction, numerical analysis was carried out based on the homogeneous flow model. Stability maps in reference to the core inlet subcooling and heat flux were presented for various inlet restrictions using the above-mentioned function. Instability region during the inlet subcooling shifted to the higher inlet subcooling with increasing inlet restriction and became larger with increasing heat flux. Received on 17 January 2000