Reaction of N‐Heterocyclic Silylenes with Thioketone: Formation of Silicon–Sulfur Three (Si‐C‐S)‐ and Five (Si‐C‐C‐C‐S)‐Membered Ring Systems

Three‐ and five‐membered rings that bear the (Si‐C‐S ) and (Si‐C‐C‐C‐S ) unit have been synthesized by the reactions of L SiCl ( 1 ; L =PhC(NtBu)₂) and L′ Si ( 2 ; L′ =CH{(C?CH₂)(CMe)(2,6‐iPr₂C₆H₃N)₂}) with the thioketone 4,4′‐bis(dimethylamino)thiobenzophenone. Treatment of 4,4′‐bis(dimethylamino)thiobenzophenone with L SiCl at room temperature furnished the [1+2]‐cycloaddition product silathiacyclopropane 3 . However, reaction of 4,4′‐bis(dimethylamino)thiobenzophenone with L′ Si at low temperature afforded a [1+4]‐cycloaddition to yield the five‐membered ring product 4 . Compounds 3 and 4 were characterized by NMR spectroscopy, EIMS, and elemental analysis. The molecular structures of 3 and 4 were unambiguously established by single‐crystal X‐ray structural analysis. The room‐temperature reaction of 4,4′‐bis(dimethylamino)thiobenzophenone with L′ Si resulted in products 4 and 5 , in which 4 is the dearomatized product and 5 is formed under the 1,3‐migration of a hydrogen atom from the aromatic phenyl ring to the carbon atom of the C? S unit. Furthermore, the optimized structures of probable products were investigated by using DFT calculations.     

[2,6‐Bis(1H‐benzimidazol‐2‐yl‐κN3)­pyridine‐κN](di­methyl­form­amide‐κO)­(thio­sulfato‐κ2O,S)­nickel(II) mono­hydrate

The structure of the title compound, [Ni(ths)(bbip)(dmf)]·­H₂O [ths is thio­sulfate, S₂O₃; bbip is 2,6‐bis(1H‐benz­imidazol‐2‐yl)­pyridine, C₂₁H₁₃N₅; and dmf is di­methyl­form­amide, C₃H₇NO], is monomeric, with the nickel ion octahe­drally surrounded by an N,N′,N′′‐tridentate bbip mol­ecule, an S,O‐bidentate ths mol­ecule and an O‐monodentate dmf mol­ecule. The H atoms of the hydration water mol­ecule and the amino groups of bbip are involved in hydrogen bonding and determine a spatial organization of broad layers parallel to (001), which are connected by weak interactions.     

Enantiomeric separation of several antimycotic azole drugs using supercritical fluid chromatography

The chiral resolution of four antifungal compounds, three imidazoles (miconazole, econazole and sulconazole) and one triazole (itraconazole) using supercritical fluid chromatography on the amylose-based chiral stationary phase Chiralpak AD, is presented in this work. The influence of pressure, type and percentage of organic modifier and temperature on retention times and resolution was studied. The enantiomeric separation of the three imidazoles was achieved with resolutions higher than two and analysis times lower than 10 min, obtaining the best results using methanol as modifier. However, the analysis time of the triazole was higher than 80 min due to the existence of a high number of functional groups that were able to interact with the chiral stationary phase. In this case, the resolution of the four stereoisomers was achieved only partially with mixtures of ethanol and 2-propanol as modifier. The isoenantioselective temperatures were obtained from the study of the influence of the temperature, they were above the range of temperatures assayed, except for sulconazole using 2-propanol.     

A posteriori error analysis of an augmented fully mixed formulation for the nonisothermal Oldroyd–Stokes problem

In this article, we consider an augmented fully mixed variational formulation that has been recently proposed for the nonisothermal Oldroyd–Stokes problem, and develop an a posteriori error analysis for the 2‐D and 3‐D versions of the associated mixed finite element scheme. More precisely, we derive two reliable and efficient residual‐based a posteriori error estimators for this problem on arbitrary (convex or nonconvex) polygonal and polyhedral regions. The reliability of the proposed estimators draws mainly upon the uniform ellipticity of the bilinear forms of the continuous formulation, suitable assumptions on the domain and the data, stable Helmholtz decompositions, and the local approximation properties of the Clément and Raviart–Thomas operators. On the other hand, inverse inequalities, the localization technique based on bubble functions, and known results from previous works are the main tools yielding the efficiency estimate. Finally, several numerical results confirming the properties of the a posteriori error estimators and illustrating the performance of the associated adaptive algorithms are reported.     

Semiempirical fine-tuning for Hartree–Fock ionization potentials of atomic ions with non-integral atomic number

Amovilli and March (2006) [8] used diffusion quantum Monte Carlo techniques to calculate the non-relativistic ionization potential I(Z)$I(Z)$ in He-like atomic ions for the range of (fractional) nuclear charges Z   lying between the known critical value _Zc=0.911$Z_{\mathrm{c}}=0.911$ at which I(Z)$I(Z)$ tends to zero and Z=2$Z=2$. They showed that it is possible to fit I(Z)$I(Z)$ to a simple quadratic expression. Following that idea, we present here a semiempirical fine-tuning of Hartree–Fock ionization potentials for the isoelectronic series of He, Be, Ne, Mg and Ar-like atomic ions that leads to excellent estimations of _Zc$Z_{\mathrm{c}}$ for these series. The empirical information involved is experimental ionization and electron affinity data. It is clearly demonstrated that Hartree–Fock theory provides an excellent starting point for determining I(Z)$I(Z)$ for these series.     

Complete assignment of NMR data of 22 phenyl‐1H‐pyrazoles' derivatives

Complete assignment of ¹H and ¹³C NMR chemical shifts and J(¹H/¹H and ¹H/¹⁹F) coupling constants for 22 1‐phenyl‐1H‐pyrazoles' derivates were performed using the concerted application of ¹H 1D and ¹H, ¹³C 2D gs‐HSQC and gs‐HMBC experiments. All 1‐phenyl‐1H‐pyrazoles' derivatives were synthesized as described by Finar and co‐workers. The formylated 1‐phenyl‐1H‐pyrazoles' derivatives were performed under Duff's conditions. Copyright © 2011 John Wiley & Sons, Ltd.     

Liquid chromatography coupled with ultraviolet absorbance detection,electrospray ionization,collision‐induced dissociation and tandem mass spectrometry on a triple quadrupole for the on‐line characterization of polyphenols and methylxanthines in green coffee beans

Liquid chromatography coupled with a photodiode array detector, electrospray ionization, collision‐induced dissociation and tandem mass spectrometry (LC‐DAD/ESI‐CID‐MS/MS) on a triple quadrupole (QqQ) has been used to detect and characterize polyphenols and methylxanthines in green coffee beans: three phenolic acids (caffeic acid, ferulic acid and dimethoxycinnamic acid), three isomeric caffeoylquinic acids (M_r 354), three feruloylquinic acids (M_r 368), one p‐coumaroylquinic acid (M_r 338), three dicaffeoylquinic acids (M_r 516), three feruloyl‐caffeoylquinic acids (M_r 530), four p‐coumaroyl‐caffeoylquinic acids (M_r 500), three diferuloylquinic acids (M_r 544), six dimethoxycinnamoyl‐caffeoylquinic acids (M_r 544), three dimethoxycinnamoyl‐feruloylquinic acids (M_r 558), six cinnamoyl‐amino acid conjugates, three cinnamoyl glycosides, and three methylxanthines (caffeine, theobromine and theophylline). Dimethoxycinnamic acid, three isomers of dimethoxycinnamoyl‐caffeoylquinic acids and another three of dimethoxycinnamoyl‐feruloylquinic acids, as well as the three cinnamoyl glycosides, had not previously been reported in coffee beans. Structures have been assigned on the basis of the complementary information obtained from UV‐visible spectra, relative hydrophobicity, scan mode MS spectra, and fragmentation patterns in MS² spectra (both in the positive and negative ion modes) obtained using a QqQ at different collision energies. A structure diagnosis scheme is provided for the identification of different isomers of polyphenols and methylxanthines. Copyright © 2009 John Wiley & Sons, Ltd.