SNAr iodination of 6-chloropurine nucleosides: aromatic Finkelstein reactions at temperatures below -40 degrees C

Mesitoyl or toluoyl esters of inosine and 2'-deoxyinosine were deoxychlorinated at C6 to give the crystalline 6-chloropurine nucleoside derivatives, which underwent quantitative conversion to the 6-iodo analogues with NaI/TFA/butanone at -50 to -40 degrees C. The 6-iodo compounds were efficient substrates for SNAr, Sonogashira, and Suzuki-Miyaura reactions, in contrast with the 6-chloro analogues, and gave good to high yields of C-N and C-C coupled products.     

Quantum-mechanical analysis of a longitudinal Stern-Gerlach effect

We present the results of a rigorous quantum-mechanical calculation of the propagation of electrons through an inhomogeneous magnetic field with axial symmetry. A complete spin polarization of the beam is demonstrated assuming that a Landau eigenstate can be inserted into the field. This is in contrast with the semiclassical situation, where the spin splitting is blurred.     

Cavitation in adhesives

The bubbles that usually appear in the bulk of an adhesive film during separation allow for a significant deformation of the adhesive material and are therefore an essential ingredient for a high dissipation. Recent observations have shown that they appear in the early stages of separation. The present model describes the early deformations induced in the film by the bubbles, and predicts how many will appear, depending on the separation velocity and on the number of weak points in the film. The trends we obtain are in agreement with observations.     

Ueber Untersuchung von Jodoform und Jod enthaltenden Verbandstoffen und Arzneimitteln

Ohne Zusammenfassung     

Quantitative determination of N-[trans-2-(dimethylamino)-cyclopentyl]-N-(3',4'-dichlorophenyl)propan amide, its 2H5-labeled analogue and their N-dealkylated metabolites in dog serum by capillary gas chromatography-mass spectrometry

This paper describes the development of a capillary gas chromatographic--mass spectrometric method for the determination of N-[trans-2-(dimethylamino)cyclopentyl]-N-(3',4'-dichlorophenyl)propan amide and its metabolites in serum. The method utilizes an automated sample preparation whereby drug, metabolites and internal standard are extracted from polar serum components by adsorption chromatography onto an XAD-type resin. The N-demethylated metabolites are derivatized by acetylation prior to chromatography. Detection is by mass spectrometry with chemical ionization. This method was utilized to determine levels of unlabeled and pentadeuterated drug and their respective metabolites in canine serum after oral co-administration. No significant kinetic isotope effects were observed for either absorption or metabolism.     

Direct synthesis of pyrrole nucleosides by the stereospecific sodium salt glycosylation procedure

A stereospecific high-yield glycosylation of preformed fully aromatic pyrroles has been accomplished for the first time. Reaction of the sodium salt of pyrrole-2-carbonitrile ( 1a ) and pyrrole-2,4-dicarbonitrile ( 1b ) with 1-chloro-2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranose ( 2 ) gave exclusively the corresponding blocked nucleosides with β-anomeric configuration 3a and 3b , which on deprotection gave 1-(2-deoxy-β-D-erythro-pentofuranosyl) derivatives of 1a ( 3c ) and 1b ( 3d ). Functional group transformation of 3c and 3d provided a number of 2-monosubstituted 4a-c and 2,4-disubstituted 4d-f derivatives of 1-(2-deoxy-β-D-erythro-pentofuranosyl)pyrrole. Similar glycosylation of the sodium salt of 1a and 1b with 1-chloro-2,3,5-tri-O-benzyl-α-D-arabinofuranose ( 5 ) and further functional group transformation of the intermediate blocked nucleosides 6a and 6b provided 1-β-D-arabinofuranosyl derivatives of pyrrole-2-carboxamide ( 7b ) and pyrrole-2,4-dicarboxamide ( 7d ). The synthetic utility of this glycosylation procedure for the preparation of 1-β-D-ribofuranosylpyrrole-2-carbonitrile ( 12 ) has also been demonstrated by reacting the sodium salt of 1a with 1-chloro-2,3-O-isopropylidene-5-O-(t-butyl)dimethylsilyl-α-D-ribofuranose ( 10 ) and subsequent deprotection of the blocked intermediate 11 . This study provided a convenient route to the preparation of aromatic pyrrole nucleosides.