Ladder polymers for use as high temperature stable resins or coatings

An object of the invention is to synthesize a new class of ladder and partial ladder polymers. In accordance with the invention, the new class of ladder and partial ladder polymers are synthesized by polymerizing a bis-dienophile with a bis-diene. Another object of the invention is to provide a fabricated, electrically conducting, void free composite comprising the new class of the ladder and partial ladder polymers described above. The novelty of the invention relates to a new class of ladder and partial ladder polymers and a process for synthesizing these polymers. These polymers are soluble in common organic solvents and are characterized with a unique dehydration property at temperatures of 300 to 400 C to provide thermo-oxidatively stable pentiptycene units along the polymeric backbone. These polymers are further characterized with high softening points and good thermo-oxidative stability properties. Thus these polymers have potential as processable, matrix resins for high temperature composite applications

A solvent-free Diels-Alder reaction of graphite into functionalized graphene nanosheets

A solvent-free Diels-Alder reaction was carried out by heating a mixture of graphite and a typical dienophile, maleic anhydride (MA) or maleimide (MI), in a sealed glass ampoule of argon. The functionalization of graphite with dienophiles was confirmed by various characterization techniques, suggesting the efficient functionalization and delamination of graphite into a few layers of graphitic nanosheets.close0

A surprising steric effect on a tandem cycloaddition/ring-opening reaction : rapid syntheses of difluorinated analogues of (hydroxymethyl)conduritols

Difluorinated analogues of (hydroxymethyl)conduritols can be synthesised from selected furans and a difluorinated dienophile in two reaction steps

Network-analysis-guided synthesis of weisaconitine D and liljestrandinine.

General strategies for the chemical synthesis of organic compounds, especially of architecturally complex natural products, are not easily identified. Here we present a method to establish a strategy for such syntheses, which uses network analysis. This approach has led to the identification of a versatile synthetic intermediate that facilitated syntheses of the diterpenoid alkaloids weisaconitine D and liljestrandinine, and the core of gomandonine. We also developed a web-based graphing program that allows network analysis to be easily performed on molecules with complex frameworks. The diterpenoid alkaloids comprise some of the most architecturally complex and functional-group-dense secondary metabolites isolated. Consequently, they present a substantial challenge for chemical synthesis. The synthesis approach described here is a notable departure from other single-target-focused strategies adopted for the syntheses of related structures. Specifically, it affords not only the targeted natural products, but also intermediates and derivatives in the three families of diterpenoid alkaloids (C-18, C-19 and C-20), and so provides a unified synthetic strategy for these natural products. This work validates the utility of network analysis as a starting point for identifying strategies for the syntheses of architecturally complex secondary metabolites

Intramolecular Imino Diels-Alder Reaction: Progress toward the Synthesis of Uncialamycin

We herein described an intramolecular imino Diels-Alder reaction promoted with BF3.OEt2/DDQ affording substituted quinolines. Using this procedure, we prepared the chiral quitioline moiety of the uncialamycin, a new enediyne natural product

Quantitative representation of reactivity, selectivity and site activation concepts in organic chemistry

Indexación: ScieloReactivity, selectivity and site activation are classical concepts in chemistry which are amenable to quantitative representation, in terms of static global, local and non local density response functions. The use of these electronic indexes describing chemical interconversion is developed in this work along the perspective of the pioneering work conducted in Chile by the late Professor Fernando Zuloaga, to whom this article is dedicated in memoriam. While global responses, represented as derivatives of the electronic energy with respect to the total number of electrons quantitatively describe the propensity of a system to interconvert into another chemical species (chemical reactivity), the local counterparts assesses well those regions in the molecule where the reactivity pattern dictated by the global quantities is developed (selectivity). Site activation /deactivation may in turn be described by the variations in the local or regional patterns of reactivity, that may be induced by solvent effects or chemical substitution. These concepts are illustrated for a series of chemical reactions in Organic Chemistry, including electrocyclic processes, cycloadditions and electrophilic addition reactions. Some relationships between quantitative scales of reactivity and reaction mechanisms are discussed.http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072004000100010&lang=p

Unusual structure-energy correlations in intramolecular Diels–Alder reaction transition states

Detailed analysis of calculated data from an experimental/computational study of intramolecular furan Diels–Alder reactions has led to the unusual discovery that the mean contraction of the newly forming C-C σ-bonds from the transition state to the product shows a linear correlation with both reaction Gibbs free energies and reverse energy barriers. There is evidence for a similar correlation in other intramolecular Diels–Alder reactions involving non-aromatic dienes. No such correlation is found for intermolecular Diels–Alder reactions