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751.
Sterically stabilized alpha-lactams react by two distinct acid-catalyzed pathways. Protonation on oxygen results in nucleophilic attack at the acyl carbon and gives C-2 products. Protonation on nitrogen leads to nucleophilic attack at the C-3 carbon and yields C-3 products. The mechanism thus developed is very useful for understanding the changes in rates and product distributions in the reactions of sterically stabilized alpha-lactams with nucleophiles. It can also be extrapolated to other alpha-lactams so that a more coherent picture of alpha-lactam reactivity can be developed. 相似文献
752.
Synthesis, properties, and reactivity of cocaine benzoylthio ester possessing the cocaine absolute configuration 总被引:1,自引:0,他引:1
Isomura S Hoffman TZ Wirsching P Janda KD 《Journal of the American Chemical Society》2002,124(14):3661-3668
One aspect of immunopharmacotherapy for cocaine abuse involves the use of a catalytic monoclonal antibody (mAb) to degrade cocaine via hydrolysis of the benzoate ester. A cocaine benzoylthio ester analogue provides a means to implement high-throughput selection strategies to potentially isolate mAbs with high activity. The required analogue was synthesized starting from (-)-cocaine hydrochloride and possessed the cocaine absolute configuration. Key points in the preparation were the introduction of the sulfur atom at C-3 via a bromomagnesium thiolate addition to the exo face of anhydroecgonine, separation of C-2 diastereomers, recycling of a C-2 thio ester byproduct, and formation of the necessary C-2 methyl and C-3 benzoylthio esters. Effects resulting from the lower electronegativity and greater hydrophobicity of sulfur compared to oxygen were observed. These characteristics could result in interesting drug properties. Furthermore, the analogue was found to be a substrate for catalytic mAbs that hydrolyze cocaine as monitored by HPLC and also spectrophotometry by coupling cleavage of the benzoylthio ester to the disulfide exchange with Ellman's reagent. Screening antibody libraries with the new cocaine analogue using the spectroscopic assay provides an avenue for the high-throughput identification of catalysts that efficiently breakdown cocaine. 相似文献
753.
New methods for the synthesis of 2-oxazolone-4-carboxylates from 3-nosyloxy- and 3-bromo-2-ketoesters are described. Condensation of 3-nosyloxy-2-ketoesters with methyl carbamate in refluxing toluene in the presence of p-TSA provided 2-oxazolone-4-carboxylates in good yields (41-80%). Alternatively, bromination of alpha-ketoesters with CuBr2 provided 3-bromo-2-ketoesters which condensed with methyl carbamate in the presence of p-TSA and AgOTf under similar conditions to provide 2-oxazolone-4-carboxylates in comparable yields (30-79%). The 2-oxazolone-4-carboxylates bear functionality that can be elaborated to a variety of potentially useful compounds. For example, some of these heterocycles were readily N-acylated, reduced to alcohols, or saponified and coupled with amino acids. 相似文献
754.
The research described in this paper was supported by research grant DE-FG02-86ER250125 of the Applied Mathematical Science subprogram of the Office of Energy Research, U.S. Department of Energy, and National Science Foundation grants DMS-8503350 and DMS-8611574 相似文献
755.
J. D. Hoffman M. P. Scofield H. D. Thompson 《Journal of Optimization Theory and Applications》1972,10(3):133-159
An optimization analysis employing the calculus of variations and a numerical relaxation scheme for applying the results are presented for the design of axisymmetric, maximumthrust nozzle contours including boundary-layer effects. The method is illustrated by comparison with a known solution without boundary-layer effects. A parametric study of boundary-layer effects for a range of parameters typical of scramjet thrust nozzles is presented.This work was sponsored by the Air Force Aero-Propulsion Laboratory, Wright-Patterson Air Force Base, Ohio, under Contract No. F33615-67-C-1068. 相似文献
756.
757.
758.
We show that a complete multipartite graph is class one if and only if it is not eoverfull, thus determining its chromatic index. 相似文献
759.
760.
A simple physical approach for deriving the characteristic equations of fluid dynamics is presented. The approach is based on the physical concept that information propagates through a flowfield along pathlines due to particle motion and along wavelines due to acoustic wave motion. The characteristic equations and compatibility equations are derived in vector forms which are valid in any co-ordinate system. 相似文献