Iterated Logarithm Law for Anticipating Stochastic Differential Equations

We prove a functional law of iterated logarithm for the following kind of anticipating stochastic differential equations

Seebach’s oxazolidinone is a good catalyst for aldol reactions

Seebach’s proline-derived oxazolidinone 2d overcomes (S)-proline and is at least as efficient as (S)-5-(pyrrolidin-2-yl)tetrazole in several organocatalytic aldol reactions examined. A quick exchange takes place between 2d and carbonyl compounds that gives new bicyclic oxazolidinones, in equilibrium with the very minor active species (enamines). Maximum yields of the aldols (β-hydroxy ketones) were achieved after 1-4 h when, with proline, they are attained after 30-48 h.     

Synthesis,Characterization and Explosive Properties of 1,3‐Dimethyl‐5‐amino‐1H‐tetrazolium 5‐Nitrotetrazolate

1,3‐Dimethyl‐5‐amino‐1H‐tetrazolium 5‐nitrotetrazolate ( 5b ) was synthesized in high yield from 1,4‐dimethyl‐5‐amino‐1H‐tetrazolium iodide ( 5a ) and silver 5‐nitrotetrazolate. Both new compounds ( 5a and 5b ) were characterized using vibrational (IR and Raman) and multinuclear NMR spectroscopy (¹H, ¹³C and ¹⁵N), elemental analysis and single‐crystal X‐ray diffraction. 5a crystallizes in an orthorhombic cell: Pbca, a = 11.5016(4), b = 13.7744(5), c = 13.7744(5) Å, V = 1638.2(1) ų, Z = 8, ρ = 1.955 g cm^?3, R₁ = 0.0210 (F > 4σ(F)), wR₂ (all data) = 0.0542; whereas 5b crystallizes in a monoclinic cell: C1c, a = 14.5228(8), b = 5.0347(2), c = 13.7217(7) Å, β = 112.11(1)°, V = 929.6(2) ų, Z = 4, ρ = 1.630 g cm^?3, R₁ = 0.0279 (F > 4σ(F)), wR₂ (all data) = 0.0585. The sensitivity of 5b to classical stimuli was determined by using standard BAM tests and its thermal stability was assessed by DSC measurements. In addition, its heat of combustion was determined by bomb calorimetry measurements. The EXPLO5 was used to calculate the detonation pressure (P) and velocity (D) of 5b (P = 13.3 GPa and D = 6379 m s^?1), as well as those of its mixtures with ammonium nitrate (P = 23.2 GPa and D = 7862 m s^?1) and ammonium dinitramide (P = 29.6 GPa and D = 8594 m s^?1). Compound 5b is a hydrolytically stable solid with a high melting point (160 °C) and thermally stable to 190 °C with a very low sensitivity to friction (>360 N) and impact (>30 J) and good performance in combination with an oxidizer making it of interest in new environmentally friendly, insensitive explosive formulations.     

Structural optimization of enantiopure 2-cyclialkylamino-2-aryl-1,1-diphenylethanols as catalytic ligands for enantioselective additions to aldehydes

The structural optimization of a family of modular, enantiopure beta-amino alcohol ligands with a common 2-amino-2-aryl-1,1-diphenylethanol skeleton, whose stereogenicity was introduced through the Jacobsen epoxidation of 1,1-diphenyl-2-arylethylenes, has led to the identification of a small set of optimal catalysts with enhanced activity and enantioselectivity in the addition of alkylzinc and arylzinc reagents to aldehydes. Criteria for the discrimination between apparently analogous, highly enantioselective ligands are proposed.     

Eine Verf?lschung von Tomaten-Conserven

Ohne Zusammenfassung     

Synthesis,Characterization and HPLC Analysis of the (1S,2S,5R)-Diastereomer and the Enantiomer of the Clinical Candidate AR-15512

AR-15512 (formerly known as AVX-012 and WS-12) is a TRPM8 receptor agonist currently in phase 2b clinical trials for the treatment of dry eye. This bioactive compound with menthol-like cooling activity has three stereogenic centers, and its final structure and absolute configuration, (1R,2S,5R), have been previously solved by cryo-electron microscopy. The route of synthesis of AR-15512 has also been reported, revealing that epimerization processes at the C-1 can occur at specific stages of the synthesis. In order to confirm that the desired configuration of AR-15512 does not change throughout the process and to discard the presence of the enantiomer in the final product due to possible contamination of the initial starting material, both the enantiomer of AR-15512 and the diastereomer at the C-1 were synthesized and fully characterized. In addition, the absolute configuration of the (1S,2S,5R)-diastereomer was determined by X-ray crystallographic analysis, and new HPLC methods were designed and developed for the identification of the two stereoisomers and their comparison with the clinical candidate AR-15512.     

Solvation in octanol: parametrization of the continuum MST model

This study reports the parametrization of the HF/6‐31G(d) version of the MST continuum model for n‐octanol. Following our previous studies related to the MST parametrization for water, chloroform, and carbon tetrachloride, a detailed exploration of the definition of the solute/solvent interface has been performed. To this end, we have exploited the results obtained from free energy calculations coupled to Monte Carlo simulations, and those derived from the QM/MM analysis of solvent‐induced dipoles for selected solutes. The atomic hardness parameters have been determined by fitting to the experimental free energies of solvation in octanol. The final MST model is able to reproduce the experimental free energy of solvation for 62 compounds and the octanol/water partition coefficient (log P_ow) for 75 compounds with a root‐mean‐square deviation of 0.6 kcal/mol and 0.4 (in units of log P), respectively. The model has been further verified by calculating the octanol/water partition coefficient for a set of 27 drugs, which were not considered in the parametrization set. A good agreement is found between predicted and experimental values of log P_o/w, as noted in a root‐mean‐square deviation of 0.75 units of log P. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1180–1193, 2001     

On triangular norm based axiomatic extensions of the weak nilpotent minimum logic

In this paper we carry out an algebraic investigation of the weak nilpotent minimum logic (WNM) and its t‐norm based axiomatic extensions. We consider the algebraic counterpart of WNM, the variety of WNM‐algebras (?????) and prove that it is locally finite, so all its subvarieties are generated by finite chains. We give criteria to compare varieties generated by finite families of WNM‐chains, in particular varieties generated by standard WNM‐chains, or equivalently t‐norm based axiomatic extensions of WNM, and we study their standard completeness properties. We also characterize the generic WNM‐chains, i. e. those that generate the variety ?????, and we give finite axiomatizations for some t‐norm based extensions of WNM. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)