Arylsulfimide Polymers. IV. Prototype Transamidations–A Comparison of the Reactions of Benzamides,Benzimides, Sulfonamides,Sulfonimides, and Saccharins

Transamidation reactions of nonpolymerizing systems involving benzamides, phthalimides, arylsulfonamides, benzenedisulfonamides and -disulfonim-ides, and saccharins are described. The study includes reactions of both N-substituted and unsubstituted amides and imides with anilines and aniline hydrochlorides. An evaluation of the results of these reactions, aimed at establishing the optimum conditions for transamidations in polymerizing systems, is also presented.     

A review of: “Instrumental HPTLC,by W. Bertsch,S. Hara,R. E. Kaiser,and A. Zlatkis,editors, H. Verlag,Heidelberg, West Germany, 1980, 390 pp., cloth bound.”

Abstract

To understand the retention mechanisms involved in reversed-phase micelle chromatography, two models were examined to study the temperature and micelle concentration contribution to the retention process. the first model described the temperature contribution, using the van's Hoff equation, for each of the three equilibria: micelle-to-extra-micelle-mobile-phase, extra-micellar-mobile-phase-to-stationary phase and micelle-to-stationary phase. the second model described the temperature contribution on k' irrespective of the various equilibria involved. It was found that the enthalpy of retention obtained with the second model decreased with increasing micelle concentration. This contradicted a primary assumption in the first model that the equilibrium constants were independent of micelle concentration. No relationship was found between the enthalpy of retention evaluated with either model and the polarity of the partitioned solute molecules. A correlation was found between the entropy of retention and the polarity of these molecules. Fluorescence studies indicated that the micelle solvated molecules were probably located in the core of the micelles which contained other mobile phase components such as 1-propanol and water.     

A review of: “The Effects of Hostile Environments on Coattings and Plastics,Acs. D. P. Garner and G. A. Stahl (Editors): Symposium Series 229, American Chemical Society,Washington, D.C., 1983, 339 pp., U.S. and Canada $47.95, export $57.95.”

Rh‐catalyzed polymerization of a new N‐propargylamide monomer having a galactose residue was investigated. The polymerization proceeded in a mixed solvent of THF and water to produce the galactose‐carrying poly(N‐propargylamide) consisting of cis‐isomer. The copolymerization of the monomer with the N‐propargylamide having the alkyl chain was also carried out.     

A review of: “Principles of Colloid and Surface Chemistry”. Paul C. Hiemanz. Marcel Dekker,Inc., New York and Basel, 1977. xi+516 pp.m $22.50

A general reaction model for styrene hydrogenation in the CTAB/l-hexanol(l-pentanol or l-butanol)/water reversed micellar solutions was proposed to interpret the catalytic behavior of monodisperse nickel boride particles prepared in situ. Based on this model, the effect of reversed micellar components on hydrogenation activity of the catalyst has been discussed in detail. It is worth noticing that, in the three reversed micellar systems, adding ethanol into the reversed micellar solutions will result in the change of catalyst's activity in the different ways, i.e. decrease for the reversed micellar solution with the low CTAB concentration (6 wt%) and increase for those with the high CTAB content (23 wt % or 38 wt%). The result is attributed to the combined     

A Study of Synthesis, Immobilization and Catalytic Capability of Metalloporphyrin

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A review of: “ELECTRICAL PHENOMENA AT INTERFACES (Fundamentals,Measurements and Applications) A. Kitahara and A. Watanabe,Eds., Marcel Dekker,New York, 1984; hardbound, 463 pages, $79.50”

Electrokinetic analysis is a family of techniques for estimating the charge on solid surfaces, macroscopic particles, colloidal species, and macromolecular aggregates. Charges on surfaces are critical to the behavior of colloids, coatings, films, fibers, and many other materials in a variety of application areas. In addition to estimating the charge, electrokinetic analysis provides the means for measuring how the surrounding medium and imposed electric fields interact with extended flat surfaces, channels, pores, particles, and molecular aggregates to produce motion. Such motion has found wide use as a means for separating complex mixtures into their components. This section will present how measurements are made, some theoretical underpinnings, and examples of the instrumentation used for making measurements.     

Total Syntheses of Kopsaporine,Kopsinol and Kopsiloscine A

Kopsia alkaloids represent a complex class of natural products bearing a polycyclic ring system with two or three consecutive quaternary carbon centers. In this article, we report the first total synthesis of Kopsaporine related alkaloids. Features of our structure-unit-based strategy are an intramolecular Pummerer rearrangement induced nucleophilic cyclization/aza-Prins cyclization to construct the highly functional hexahydrocarbazole skeleton, an olefin migration vinylogous alkylation to establish the C20 all-carbon quaternary center, an iridium complex mediated radical addition to fuse the aspidofractine framework, an unprecedented IBX oxidation to introduce the α-hydroxyketone moiety, and a bioinspired retro-Aldol/Aldol reaction to convert kopsaporine to kopsiloscine A.     

Effect of urea on the structure and functional activity of proteins. Chymotrypsinogen A and α-chymotrypsin

The effect of urea on the structural stability and functional activity of globular proteins,viz., chymotrypsinogen A (ChtG) and -chymotrypsin (Cht), was studied over a wide range of concentrations (0.5–6 rnol L-1), and the existence of two different mechanisms of the action of urea on these proteins was demonstrated. No changes in the spatial structure of ChtG were observed in the concentration range from 0,5 to 3 mol L^–1 (region 1). Differential UV spectroscopy shows tile redistribution of aromatic groups between the inner volume and the outer surface of a protein molecule (protein denaturation) at concentrations >3 mol L^–1 (regionII), In regionI, urea changes the kinetic parameters of enzymatic reactions involving Cht, which is explained on the basis of millimeter spectroscopy data by its action on the structure and nucleophilic reactivity of water.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 998–1002, April, 1996.     

Partial Protection of Carbohydrate Derivatives. Part 13.1 Chemical Conversion of Kanamycin A Into 2′-Deoxykanamycin A, 2′-Epi-Kanamycin A,and 2′-Epi-Kanamycin B

Abstract

Hydrazinolyses of hexa-0-benzoyl-tetra-N-benzyloxycarbonyl-and N-ethoxycarbonylkanamycin A were performed and found to be sufficiently regioselective to give the corresponding 2′-hydroxyl derivatives in good yields under controlled conditions. The products were converted into the corresponding 2′-triflates, which were then subjected to nucleophilic substitution reactions with sodium benzenethioxide, sodium benzoate, and sodium azide to give the corresponding d-mannopyranosyl derivatives in good yields. Deprotection of the phenylthio (10) and azido (12) derivatives, and hydrogenolysis, gave 2′-deoxykankmycin A and 2′-epi-kanamycin B, respectively. Moreover, deprotection of the benzoyl compound 11 gave 2′-epi-kanamycin A.     

A note to the article “polarographic reduction of germanium” by A.K. Dasgupta and C.K.N. Nair

The nature of the two reduction waves of tetravalent germanium in ammonia-ammonium chloride buffer is described. Contrary to the statement of dasgup'ta and NAIR1 only the height of the first diffusion current should be used for analytical purposes. The second wave corresponds to a catalytic hydrogen evolution. The use of cthylenediaminetetra-acetic acid of pH 6–8 for the analysis of germanium is preferable².