Chemistry of thienopyridines. XXXVI. Further studies on nitration in the thieno[2,3-b]- and thieno[3,2-b]pyridine systems

Three compounds, thieno[3,2-b]pyridine 4-oxide, 7-nitrothieno[3,2-b]pyridine 4-oxide ( 1 c), and 6-cyano-thieno[2,3-b]pyridine, undergo nitration by means of a mixture of nitric and sulfuric acids to yield 3,7-dinitro-thieno[3,2-b]pyridine (3%), 3,7-dinitrothieno[3,2-b]pyridine 4-oxide ( 1d ) (26%), and 6-carbamoyl-5-nitrothieno[2,3-b]pyridine ( 6b ) (11%), respectively. Structures of the products were ascertained by spectral means, notably infrared, ¹H nmr, and ¹³C nmr. It is proposed that 1d exists (at least in part) as a tricyclic structure and that 6b may result from an intramolecular mechanism of nitration. An attempt to de-N-oxygenate 1c with excess triphenylphosphine removes more than one oxygen atom per molecule (as triphenylphosphine oxide) without producing an identified thienopyridine product.     

Tracelessness Unmasked: A General Linker Nomenclature

Nowadays it is rare to find an issue of a major chemistry journal without at least one article on solid-phase synthesis. This is hardly surprising: the technique promises an end to arduous work-up procedures and the ability to facilitate the creation of vast libraries of compounds using combinatorial techniques. No longer is the technique only of interest to those involved in peptide synthesis: an enormous variety of product classes have now been prepared on and isolated from the solid phase. It is the "linker" which is the focus of this article. The linker's ultimate function is to release a product from the support into solution: it does this, without exception, with a chemical change to the product at the former linkage site. Some linkers, apparently, are "traceless". But what, in fact, is "tracelessness"? Twenty years ago, in a climate where cleavage of a linker resulted in formation of a polar carboxylic acid as the vestige of the support, the concept was attractive. Today the chemist is faced with a myriad of novel linkers which have the ability to release products bearing most major functionalities at the former linkage site and we will argue here that the term "traceless", although currently in widespread use, is meaningless. Instead, we propose a new categorization of linkers based on the functionality they release upon cleavage, and suggest a nomenclature to underpin this categorization. We anticipate that the article will also serve to highlight areas of linker technology in need of further research.     

A note on the numerical evaluation of finite integrals of oscillatory functions

A method is described for the numerical evaluation of integrals of the form ∫ _?1 ¹ f(x)K(m,x)dx, wheref(x) is smooth in [?1,1], whileK(m,x) is highly oscillatory for large values ofm.     

Nitrilotriacetamide: Synthesis in Concentrated Sulfuric Acid and Stability in Water

Acid hydrolysis of N(CH₂CN)₃ leads either nitrilotriacetamide, 1, and/or 3,5-dioxopiperazineacetamide, 4, in quantitative yield. 1 slowly and cleanly converts to 3,5-dioxopiperazineacetic acid, 5, in water, although ammonium salts prevent this reaction.     

Detonation performance of nitroaromatic decorated carbon nanotubes

Structural Chemistry - In this study, density functional theory (DFT) was employed to predict thermochemical and energetic properties for single-walled carbon nanotubes (SWCNTs) decorated with one...     

Binding Study of the [Ru(NH3)5pz]2+ Complex to Bile Anion Aggregates through Kinetic Measurements

The electron transfer reaction between [Ru(NH₃)₅pz]²⁺ and [Co(C₂O₄)₃]^3? was studied in the presence of monomers and aggregates of bile salts (sodium deoxycholate, sodium taurodeoxycholate, and sodium glycocholate) at 298.2 ± 0.1 K. The results show a decreasing rate constant with the successive addition of bile salts. To rationalize the trends of the reaction rate on the [bile salts], two models were used. One of them takes into account the aggregation feature by considering a stepwise self‐association between monomers, whereas the other assumes the formation of a critical micellar concentration. Binding constants between [Ru(NH₃)₅pz]²⁺ species and deoxycholate or taurodeoxycholate aggregates were higher than that for glycocholate aggregates. These results are consistent with the way in which the monomers are added to form the bile anion aggregates.     

Hölder Continuity of Solutions to the Kinematic Dynamo Equations

We study the propagation of regularity of solutions to a three dimensional system of linear parabolic PDE known as the kinematic dynamo equations. The divergence free drift velocity is assumed to be at the critical regularity level with respect to the natural scaling of the equations.     

Copper activation of boronic acids: factors affecting reactivity

The generation of nucleophiles from the combination of aryl boronic acids and catalytic amounts of copper salt allows a reactivity distinct from other organometallic species, such as organolithiums or Grignard reagents. Here we examine how the electronic and steric properties of the boronic acid affect the formation of active nucleophiles and their subsequent reactivity with iminium‐type compounds, showing that electron‐rich substrates display reduced reactivity. Copyright © 2014 John Wiley & Sons, Ltd.