Oxidative amidation of benzyl alcohols with amino acid esters mediated by N-hydroxysuccinimide/phenyliodine diacetate

A simple protocol involving metal-free oxidative amidation of benzyl alcohols with amino acid esters has been presented. The amidation proceeds in a radical pathway unlike in conventional metal-mediated extrusion of dihydrogen. The method is advantageous in terms of metal-free conditions, nonexpensive commercial starting substrates. Also various substituents in the starting materials are tolerated and sterically hindered amino acid side chains could provide good yields of amide products.     

Synthesis and structural characterization of Pd(II) thiosemicarbazonato complex: Catalytic evaluation in synthesis of diaryl ketones from aryl aldehydes and arylboronic acids

A simple route to synthesize triphenylphosphinopalladium(II) thiosemicarbazonato complex has been described. Elemental analysis, spectral (IR, NMR) and single crystal X-ray diffraction techniques were employed for the complete characterization of the complex. The latter was found to be effective catalyst for carbon–carbon cross-coupling reaction of aryl- and heteroarylboronic acids with aromatic and heteroaromatic aldehydes to form the corresponding diaryl ketones. The influence of reaction parameters such as solvent, base, reaction temperature and catalyst loading was also investigated.     

Comparison of geometry dependent resistance models with conventional models for estimation of effective thermal conductivity of two-phase materials

The geometry dependent resistance models are used to estimate the effective thermal conductivity of two-phase materials based on the unit cell approach. The algebraic equations are derived based on isotherm approach for various geometries. The effective thermal conductivity of the above models are found and compared with experimental data with a minimum and maximum deviation of ±3.976 and ±19.55%, respectively. The present models are good agreement with experimental results.     

A fluctuation theory for Markov chains

A fluctuation theory for Markov chains on an ordered countable state space is developed, using ladder processes. These are shown to be Markov renewal processes. Results are given for the joint distribution of the extremum (maximum or minimum) and the first time the extremum is achieved. Also a new classification of the states of a Markov chain is suggested. Two examples are given.     

An improved synthesis of N-aryl and N-heteroaryl substituted homopiperazines—from conventional thermal conditions to scaling-up using microwave heating

An efficient Pd(0)-catalyzed Buchwald-Hartwig protocol for the facile preparation of N-aryl and N-heteroaryl substituted homopiperazines is described. The syntheses proceeded with aryl- and heteroaryl halides in high yields using X-Phos as best ligand. The C-N coupling products were prepared both under conventional as well as microwave heating conditions and examples for microwave-assisted upscaling are included in this study.     

A new vector field method for eigen-decomposition of symmetric matrices

We study a new approach to eigen-decomposition of symmetric matrices, called the vector field method. In contrast to the methods currently in use, the vector field method computes an eigenvector by computing a discrete approximation to the integral curve of a special tangent vector field on the unit sphere. The optimization problems embedded in each iteration of the vector field algorithms admit closed-form solutions making the vector field approach promisingly efficient.     

The first examples of supramolecular discotic C3h tris(N-salicylideneamine)s featuring inter- and intra-molecular H-bonding: synthesis and characterization

Supramolecular liquid crystalline tris(N-salicylideneamine)s (TSANs) featuring both inter- and intra-molecular hydrogen bonding have been synthesized and characterized for the first time. These TSANs formed by condensing 3 equiv of 3,4,5-trialkoxybenzoylhydrazine with 1,3,5-triformylphloroglucinol exist as the single C_3h-symmetric keto-enamine product solely, unlike the previously reported TSANs. Their self-assembly into supramolecular fluid hexagonal columnar phase over a wide thermal range is evidenced with the aid of optical microscopic, calorimetric, and powder X-ray diffraction techniques.     

Azonium-Ammonium Tautomerism and Inclusion Complexation of 1-(2,4-diamino phenylazo) Naphthalene and 4-aminoazobenzene

Spectral characteristics of 1-(2,4-diamino phenylazo) naphthalene (FBRR, fat brown RR) and 4-aminoazobenzene (AAB) have been studied in various solvents, varying hydrogen ion concentrations and in β-cyclodextrin (β-CD). The inclusion complex of FBRR and AAB with β-CD were analysed by UV-visible, fluorometry and CAche-DFT methods. Solvent study reveals that only azo tautomer is present in both compounds and the large red shifted absorption and emission maxima of FBRR indicate naphthalene ring effectively increases the π-π* transition. Unusual red shift is observed in acid solutions suggests azonium-ammonium tautomer is present in both molecules. In β-CD solutions, the large hypsochromic shift is observed in S₀ and S₁ states indicates ortho amino group of FBRR molecule is entrapped in the β-CD cavity and the large bathochromic shift for AAB in the S₁ state indicates 1:1 inclusion complex is formed.