Evidence for the intermediacy of arylbenzylnitrenium ions in the thermal rearrangement of isoxazolidines derived from C,N-diarylnitrones and 2-morpholin-4-yl-acrylonitrile

In contrast to the diaryl, dialkyl, alkylaryl, and parent series, nothing is known about the generation and chemical behavior of arylbenzylnitrenium ions. Herein, we report that these species can be generated by a process involving an unprecedented thermal rearrangement of isoxazolidines derived from C,N-diarylnitrones and 2-morpholin-4-yl-acrylonitrile. The products from these reactions are dramatically dependent upon the nature of the nitrone. Most of the observed chemistry originates from the singlet state.     

Numerical study of the axially symmetric motion of an incompressible viscous fluid in an annulus between two concentric rotating spheres

The research reported herein involved the study of the transient motion of a system consisting of an incompressible Newtonian fluid in an annulus between two concentric, rotating, rigid spheres. The primary purpose of the research was to study the use of a numerical method for analysing the transient motion that results from the interaction between the fluid in the annulus and the spheres which are started suddenly by the action of prescribed torques. The problems considered in this research included cases where: (a) one or both spheres rotate with prescribed constant angular velocities and (b) one sphere rotates due to the action of an applied constant or impulsive t?orque. In this research the coupled solid and fluid equations were solved numerically by employing the finite difference technique. With the approach adopted in this research, only the derivatives with respect to spatial variables were approximated with the use of the finite difference formulae. The steady state problem was also solved as a separate problem (for verification purposes), and the results were compared with those obtained from the solution of the transient problem. Newton's algorithm was employed to solve the algebraic equations which resulted from the steady state problem, and the Adams fourth-order predictor–corrector method was employed to solve the ordinary differential equations for the transient problem. Results were obtained for the streamfunction, circumferential function, angular velocity of the spheres and viscous torques acting on the spheres as a function of time for various values of the system dimensionless parameters.     

Potentiometric PVC membrane sensor for the determination of scopolamine in some pharmaceutical formulations.

A novel PVC membrane electrode for the determination of scopolamine ion based on the formation of an ion-association complex of scopolamine with the phosphotungstate counter anion as an electroactive material dispersed in a PVC matrix is described. The sensor shows a fast, stable, near-Nenstian response for 1 x 10(-2) mol dm(-3) to 1 x 10(-6) mol dm(-3) scopolamine at 25 degrees C over the pH range of 3 - 7 with a cationic slope of 54.5 +/- 0.5 mV/decade. The lower detection limit is 8 x 10(-7) mol dm(-3) and the response time is 15 -45 s. The selectivity coefficients for scopolamine relative to the number of interfering substances were investigated. There was negligible interference from the studied cations, anions, and pharmaceutical excipients. The determination of scopolamine in aqueous solution shows an average recovery of 100.0% and a mean relative standard deviation (RSD) of 1.5% at 500 microg/cm3. The direct determination of scopolamine in some formulations (scopolamine injection and eye drops) gave results that compare favorably with those obtained by the United State of Pharmacopoeia method. Potentiometric titration of scopolamine with sodium tetraphenylborate and phosphotungstic acid as a titrant was monitored with the developed scopolamine electrode as an end point indicator electrode.     

Palladium(II) acetate catalyzed efficient synthesis of N‐aryl‐α,β‐unsaturated amides via carbonylative addition of aniline derivatives to aromatic alkynes

A series of new N‐aryl‐α,β‐disubstituted amides (gem or E1; trans or E2) were synthesized in good yields by carbonylative addition of aniline derivatives 1a–f to aromatic alkynes 2a,b catalyzed by Pd(OAc)₂ and 1,3‐bis(diphenylphosphino)propane. The catalytic synthesis of tertiary α,β‐unsaturated amides was also successfully achieved. Traces of products were observed in the absence of p‐toluenesulfonic acid used as an additive. The reaction is sensitive to the type of phosphine ligand and solvent. Copyright © 2002 John Wiley & Sons, Ltd.     

Synthesis of New Fused and Spiro 1,5‐Benzodiazepines

[1,3‐Dihydro‐4‐phenyl(1,5)benzodiazepin‐2‐ylidene]malononitrile 1_a was treated with formaline and some different primary amines to give the corresponding pyrimido(1,5)benzodiazepines 2_a–d . Treatment of compound 1_a with halo reagents yielded the corresponding pyrrolobenzodiazepines 3_a,b . The reaction of compound 1_a with active methylenes, bidentates, S,S‐ and N,S‐acetals afforded the corresponding spiro(1,5)‐benzodiazepines 4_a‐c–8_a,b , respectively.     

Banchromene and other secondary metabolites from the endophytic fungus Fusarium sp. obtained from Piper guineense inhibit the motility of phytopathogenic Plasmopara viticola zoospores

A new chromene, (S)-banchromene (1), together with seven known compounds, ergosterol, beauvericin (2), fusaproliferin (3), radicinin (4), poly(3-hydroxybutyric acid) (PHB, 5), N-methylpyrrolidone and an inseparable mixture of isochromene derivatives 6a, 6b, were isolated from a culture of Fusarium sp. strain CAMKT24b1, an endophytic fungus from the leaves and twigs of Piper guineense (Piperaceae). The structures of these metabolites were elucidated on the basis of their spectroscopic data; the absolute configuration of 1 was determined by ab initio-calculation of the optical rotation. In tests with the zoospores of the grapevine downy mildew pathogen Plasmopara viticola, compounds 1–4 showed moderate to high levels of motility-impairing activity at concentrations as low as 2.5 μg/mL. Compound 2 was the most active, exhibiting both motility-halting and lytic activities. Furthermore, compounds 2 and 3 displayed significant cytotoxic activity against brine shrimp larvae (Artemia salina) at 10 μg/mL. This is the first report on motility inhibitory and lytic activities of metabolites from an endophytic Fusarium species against the zoospores of the downy mildew pathogen P. viticola.     

Potential of Mg–Zn–Al layered double hydroxide (LDH)/montmorillonite nanocomposite in remediation of wastewater containing manganese ions

Research on Chemical Intermediates - A Mg–Zn–Al (LDH)/MMT nanocomposite was prepared by physical interaction between Mg–Zn–Al layered double hydroxide (LDH) and...     

Low temperature phases of the Andelman-de Gennes model of chiral discrimination: rigorous results

We determine the ordered low temperature phases of the Andelman-de Gennes model of chiral discrimination, using rigorous statistical mechanical methods. The system is considered in the close-packed regime, equivalent to placing the molecules at every site of a honeycomb lattice. If the system contains an equimolar mixture of each of a pair of enantiomers, we prove in general that a heterochiral phase (disfavoring enantiomeric segregation) as well as a homochiral phase (favoring the segregation) is possible, depending on the types of intermolecular interactions. We apply our general results to the specific examples of the interactions considered by Andelman and de Gennes and provide a comparison with their conjectures that were based on two-molecule partition functions.