The furan approach to oxacycles. Part 5: Synthesis of a chiral butenolide, building block towards biologically interesting natural products

We describe an efficient new approach for the synthesis of a chiral butenolide that is based on the oxidation of a chiral furan ring with singlet oxygen in the presence of Hünig’s base, followed by Luche reduction and in situ lactonization.     

Cure kinetics of epoxy resin and thermoplastic polymer

The cure kinetics and morphology of diglycidyl ether of bisphenol A (DGEBA) modified with polyvinyl acetate (PVAc) using diaminodiphenylmethane (DDM) as hardener were investigated through differential scanning calorimetry (DSC) and environmental scanning electron microscopy (ESEM). Isothermal curing measurements were carried out at 150, 120 and 80°C. The kinetic parameters were obtained using the general autocatalytic chemically controlled model. The comparison of the kinetic data indicates that the presence of PVAc does not change the autocatalytic nature of the cure reaction. Two T _g’s were observed in the fully cured samples of the modified systems. ESEM micrographies confirm the biphasic morphology.     

Application of capillary electrophoresis with different sample stacking strategies for the determination of a group of nonsteroidal anti-inflammatory drugs in the low microg x L(-1) concentration range

Several on-column sample preconcentration modes--large-volume sample stacking using the EOF pump (LVSEP), LVSEP with anion-selective exhaustive injection (LVSEP-ASEI) and field-amplified sample injection with sample matrix removal using the electroosmotic flow (EOF) pump (FAEP)--were used to analyze some nonsteroidal anti-inflammatory drugs (NSAIDs) by capillary electrophoresis, and then compared. Methanol was the background electrolyte solvent to suppress the EOF. The effect of the type and length of the solvent plug, and the sample injection time were investigated in FAEP to determine the conditions that provided the best response. LVSEP, LVSEP-ASEI, and FAEP improved the sensitivity of the peak area by 100-, 1200-, and 1800-fold, respectively. The methodology developed, in combination with solid-phase extraction (SPE), was applied to the analysis of water samples.     

Solutions of logarithmic type for elliptic and hypoelliptic equations

LetK be an algebraically closed field withp:=char (K)>0 andX a bielliptic curve over Spec(K) with genus≥6 and such that the canonical model ofX is ordinary. In this paper we determine all the possible gap sequences of Weierstrass points on such curves.     

The law of the solution to a nonlinear hyperbolicSPDE

Let { _s,t ,(s,t ₊ ² } be a white noise on ₊ ² . We consider the hyperbolic stochastic partial differential equation {ie863-3} The purpose of this paper is to study the law of the solution to this equation. We analyze the existence and smoothness of the density using the tools of Malliavin Calculus. Finally we prove a large deviation principle on the space of continuous functions, for the family of probabilities obtained by perturbation of the noise in the equation.This work has been partially supported by the grant of the DGICYT No. PB 930052 and the EU Science project CT 910459.     

An Efficient and Simple Entry to N-Substituted beta-Enamino Acid Derivatives from 2-Alkyl-2-oxazolines and 2-Alkyl-2-thiazolines

Reaction of azaenolates of 2-alkyl-oxa(thia)zolines 6 with imidoyl chlorides 7 as electrophiles to furnish masked N-substituted beta-enamino acid derivatives 1-2 in 70-90% yield is described. Alternative routes are discussed. Compounds 1-2 generally appear in one tautomeric form, imino or enamino, depending on the nature of the imidoyl chloride. The configuration of the enamino moiety (Z) and the conformation (s-cis) of compounds 1-2 obtained were established by an NMR study and unequivocally set by nuclear Overhauser effect difference experiments. An X-ray structure of compound 1e is also reported, showing a strong intramolecular NH.N hydrogen bond. Ab initio calculations (HF/3-21G and HF/3-21+G) have been carried out on several representative examples (1e, 1p, and 1l) in an attempt to support and provide the correct geometry of these derivatives. Structural considerations among the possible isomers of compounds 1 are discussed. From these studies it was concluded that the theoretical calculations agree with the experimental results. In addition, a very simple one-pot procedure for the preparation of masked N-substituted alpha-alkylated beta-enamino acid derivatives 2 from 6, 7, and different alkyl halides (R(3)Y) is described.     

SOOT combustion. co and k catalysts supported on different supports

The catalytic combustion of particulate material was studied on cobalt catalysts promoted with potassium using different supports for its preparation. Silica, aluminium oxides and hydroxides, zirconium oxide and hydroxide were used as supports. The catalytic activity for combustion depends on the type of support used, the higher activity corresponding to the supported catalyst on zirconium oxide. TPR studies indicate that the interaction metal/support allows to explain the higher activity of the CoK/SiO₂ catalyst with respect to the CoK/Al₂O₃ but the high activity found in CoK/ZrO₂is not explained by this interaction. In all cases the Co and K improved the performance of the catalysts.     

An effective enantioselective approach to the securinega alkaloids: total synthesis of (-)-norsecurinine

[reaction: see text] A highly versatile approach to the enantioselective synthesis of securinega alkaloids is presented. Crucial steps are a palladium-catalyzed enantioselective imide alkylation, a vinylogous Mannich reaction, and a ring-closing metathesis process. Through this strategy, the synthesis of (-)-norsecurinine has been accomplished in nine steps and 11% overall yield.     

Enantioselective synthesis of 1-deoxy-d-gulonojirimycin from a phenylglycinol-derived lactam

Cyclocondensation of (R)-phenylglycinol with appropriately γ-substituted δ-oxo acid derivatives provides bicyclic lactams from which the enantioselective synthesis of 1-deoxy-d-gulonojirimycin has been reported.     

Synthesis and structure of [(Sn(mu-PCy))3(Na x PMDETA)2], containing an electron-deficient [(Sn(mu-PCy))3]2- dianion

The reaction of CyPHNa with Sn(NMe2)2 in the presence of PMDETA (= (Me2NCH2CH2)2NMe) gives the title compound [(Sn(mu-PCy))3(Na x PMDETA)2] (1), containing an electron-deficient [(Sn(mu-PCy))]3(2-) dianion with a novel two-electron, three centre (2e-3c) bonding arrangement.