Synthesis of 2-amino-5-substituted-1,3,4-oxadiazoles using 1,3-dibromo-5,5-dimethylhydantoin as oxidant

A scalable synthesis of 5-substituted-2-amino-1,3,4-oxadiazoles via oxidation of a thiosemicarbazide precursor is described. The thiosemicarbazide intermediates are easily accessed from the corresponding acid chlorides. Oxidative cyclization using 1,3-dibromo-5,5-dimethylhydantoin as the primary oxidant, in the presence of potassium iodide, gives a variety of oxadiazoles in good yields. This methodology utilizes a commercially inexpensive and easily handled oxidant.     

Linear relaxation times of stochastic processes driven by non-Gaussian noises

The linear relaxation time (LRT) associated with steady-state correlation functions is studied for Langevin equations with non-Gaussian noises: dichotomous Markov noise and Poissonian white shot noise. Exact results for arbitrary models are obtained and compared with results for Gaussian noises. Some general features of LRTs are discussed. The concept of dynamic effective diffusion is introduced and the existence of an optimal effective Fokker-Planck approximation is discussed. Explicit examples for prototype models are presented and briefly compared with the analogs for Gaussian noises.     

Semi-Classical Calculation of the Particle Production in QED via the Schwinger Dynamical Principle

The Schwinger quantum dynamical principle is used to calculate the free vacuum persistence amplitude in the presence of a prescribed electromagnetic background, and the probability that free pairs are created from the vacuum state. An explicit expression of these amplitudes is obtained in the semi-classical approach, showing that, in this approach, the particle production is a stochastic Poisson process. PACS subject classifications. 02.30.Xx, 11.15.Bt, 12.20.Ds, 12.20.-m.     

Orientation-preserving self-homeomorphisms of the surface of genus two have points of period at most two

We show that for any orientation-preserving self-homeomorphism of the double torus there exists a point of such that . This answers a question raised by Jakob Nielsen in 1942.

     

The first NH aldimine organometallic compound. Isolation and crystal structure

The first NH aldimine organometallic derivative is unexpectedly formed by the cleavage of the nitrogen-carbon bond of the amino acid fragment of the Schiff base 2,4,6-Me3C6H2CH=NCH(CH2Ph)COOEt when the imine is treated with palladium acetate.     

Magneto-structural characterization of metallocene-bridged nitronyl nitroxide diradicals by X-Ray, magnetic measurements, solid-state NMR spectroscopy, and ab initio calculations

Crystallization of ferrocene and ruthenocene substituted in the 1- and 1'-positions by two nitronyl nitroxide radicals gave the new crystal phases beta-1 (besides the known phase alpha-1), alpha-2, and beta-2 whose structures were determined by X-ray analysis. In beta-1 the radical moieties adopt transoid positions, whereas two different cisoid conformations are adopted by alpha-2 and beta-2. These conformations result from inter- and intramolecular hydrogen bonds, respectively. All compounds experience antiferromagnetic interactions, and J/k(B) values up to -7 K have been found by fitting the experimental magnetic susceptibilities to a modified Bleaney-Bowers equation. The solid diradicals alpha-1, beta-1, alpha-2, and beta-2 as well as the ferrocene 3, which was substituted by a unique nitronyl nitroxide, were investigated by (13)C and (1)H NMR spectroscopy with magic angle spinning. The carbon signals cover a range of 2000 ppm, and are well resolved such that the structure could be confirmed. Conversion of the signal shifts into spin densities disclosed the mechanisms by which spin delocalization from the nitronyl nitroxide substituents to the metallocene core occurs. The spin density distribution in alpha-1, beta-1, and 3 was also predicted by DFT calculations. There is good agreement between the experimental and theoretical trends of the spin delocalization. The magnetic interactions were discussed in the light of intramolecular spin transfer and its dependence on geometric constraints, demonstrating that the 1,1'-metallocenylene bridge is not a robust magnetic coupler.     

19F-19F Coupling constants in the azole series. Synthesis of 3,4-, 4,5-, and 3,5-difluoropyrazoles

Stepwise syntheses of difluoroazoles $\text{1}$, $\text{2}$, and $\text{3}$ have been performed. The J_FF coupling constants are reported for the first time. Surprisingly, no coupling between F₄ and F₅ is observed.     

Three-dimensional six-connecting organic building blocks based on polychlorotriphenylmethyl units--synthesis, self-assembly, and magnetic properties

The synthesis of a three-dimensional, six-connecting, organic building block based on a robust, rigid, and open-shell polychlorotriphenylmethyl (PTM) unit (radical 1) is reported, and its self-assembly properties are described in detail. The tendencies of this highly polar molecule and its hydrogenated precursor, compound 4, to form hydrogen bonds with oxygenated solvents ([1THF(6)] and [4THF(6)]) were reduced by replacing THF with diethyl ether in the crystallization process to yield two-dimensional (2D) hydrogen-bonded structures ([1(Et(2)O)(3)] and [4(Et(2)O)(3)]). The presence of direct hydrogen bonds between the radicals in the latter phase of 1 gives rise to very weak ferromagnetic intermolecular interactions at low temperatures, whereas when the radicals are isolated by THF molecules these interactions are antiferromagnetic and very weak. The role played by the carboxylic groups not only in the self-assembly properties but also in the transmission of the magnetic interactions has been illustrated by determination of the crystal structure and measurement of the magnetic properties of the corresponding hexaester radical 6, in which the close packing of molecular units gives rise to weak antiferromagnetic intermolecular interactions. Attempts to avoid solvation of the molecules in the solid state and to increase the structural and magnetic dimensionality were pursued by recrystallization of both compounds 1 and 4 from concentrated nitric acid, affording two three-dimensional (3D) robust hydrogen-bonded structures. While the structure obtained with compound 4 is characterized by the presence of polar channels and boxes containing water guest molecules along the c axis, radical 1 was oxidized to the corresponding fuchsone 10, which presented a completely different close-packed, guest-free structure.