Ab initio molecular dynamics simulation of a room temperature ionic liquid

Ab initio molecular dynamics simulations have been performed for the first time on the room-temperature organic ionic liquid dimethyl imidazolium chloride [DMIM][Cl] using density functional theory. The aim is to compare the local liquid structure with both that obtained from two different classical force fields and from neutron scattering experiments. The local structure around the cation shows significant differences compared to both the classical calculations and the neutron results. In particular, and unlike in the gas-phase ion pair, chloride ions tend to be located near a ring C-H proton in a position suggesting hydrogen bonding. The results are used to suggest ways in which the classical potentials may be improved.     

Synthesis of homoallylic chiral tertiary alcohols via chelation-controlled diastereoselective nucleophilic addition on alpha-alkoxyketones: application for the synthesis of the C(1)-C(11) subunit of 8-epi-fostriecin

[reaction: see text] Chiral beta-syn-alkoxyhomoallylic alcohols derived from alkoxyallylboration of aldehydes upon oxidation provided the corresponding chiral ketones. Chelation-controlled nucleophilic addition to these ketones occurred in a highly stereoselective manner to afford anti-homoallylic tertiary alcohols. This methodology has been applied for the synthesis of the C(1)-C(11) subunit of C(8)-epi-fostriecin.     

Infrared Study of Solid Dispersions of β-Cyclodextrin with Naphthalene Derivitaves

The inclusion complexes of β-cyclodextrin (β-CD) with naphthalene and some of its derivatives in the solid state have been studied by infrared spectroscopy. Digital subtraction, deconvolution and curve fitting have been used to investigate the interactions between the naphthalene derivatives andβ-CD. Several preparation methods for the solid dispersions have been tested, using FTIR as an effective tool to evaluate the interactions at the molecular level. The effects of temperature and humidity on the spectra have been also analyzed. A carbonyl moiety in the guest molecule can increase the stability of the complex by establishing specific interactions with the hydroxyl groups of the CD cavity rims. The stability of the complexes is higher for 2-naphthylacetate than that for 1-naphthyl acetate, andso is the degree of association of its carbonyl groups. On the other hand, 2-acetylnaphthaleneforms very stable inclusioncomplexes although its carbonyl groups appear to be significantly less associated.     

Use of highly efficient Draper-Lin small composite designs in the formal optimisation of both operational and chemical crucial variables affecting a FIA-chemiluminescence detection system

A new formal strategy in the multidimensional optimisation of the experimental variables affecting the chemiluminescence (CL) detection in flow injection analysis (FIA) is proposed here. The strategy implies several steps, being the most significant: selection of the variables to be studied and their experimental domain; use of a screening design to detect significant variables and interactions into the experimental region; study of the main effect of variables and second-order interactions; and finally application of a Draper-Lin small composite design (orthogonal) to obtain the optimum values of the significant variables. The methodology is applied to the determination of methylamine by FIA based on the use of the peroxyoxalate CL (PO-CL) reaction. Considering the high number of experiments required due to the different chemical and instrumental variables to be taken account and their adequate compatibility to obtain maximum sensitivity, the methodology offers a rigorous study of the main effects and interactions, achieving a reduction of experimental work.     

Copper(II) tetrafluoroborate as an extremely efficient catalyst for 1,3-dithiolane/dithiane formation from carbonyl compounds under solvent-free conditions at room temperature

Copper(II) tetrafluoroborate hydrate is a new and extremely efficient catalyst for 1,3-dithiolane/dithiane formation from aromatic, heteroaromatic and aliphatic aldehydes and cyclic saturated ketones in 1-5 min under solvent-free conditions at room temperature. The reaction is compatible with other functionalities such as ether, ester, hydroxyl, halide, nitro and cyano groups and exhibits excellent chemoselectivity. α,β-Unsaturated aldehydes/ketones lead to selective formation of 1,3-dithiolanes instead of Michael addition products. For substrates bearing an aldehyde and a ketone carbonyl group, chemoselective dithiolane formation takes place with the aldehyde.     

Synthesis of 2,3,8,9-tetramethoxy-11-phenyl-5,6-dihydrodibenz[2,3;7,8]indolizine

2,3,8,9-Tetramethoxy-11-phenyldibenz[2,3;7,8]indolizine was obtainedinhighyieldfrom (6,7-dimethoxyisoquinolin-1-yl)-(3,4-dimethylphenyl)phenylcarbinol by cyclization in the presence of formic acid. The behavior of (6,7-dimethoxyisoquinolin-1-yl)-(3,4-dimethoxyphenyl)methylcarbinol and (6,7-dimethoxyisoquinolin-1-yl-(3,4-dimethoxyphenyl)carbinol was studied under these same conditions. 2,3,7,8-Tetramethoxy-11-phenyl-5,6-dihydrodibenz[2,3;7,8]indolizine was obtained by hydrogenation on rhenium heptasulfide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1233–1238, September, 1993.     

New butenolides in plantlets of Virola surinamensis (Myristicaceae)

A phytochemical investigation in plantlets of the Brazilian medicinal tree Virola surinamensis resulted in the isolation and structural determination of four new compounds: 3-hydroxy-4-methyl-2-(11'-piperonyl-n-undecyl)-butenolide; 3-hydroxy-4-methyl-2-(7'-piperonyl-n-heptyl)-butanolide; 9'-(3,4-methylenedioxy-phenyl)-nonanoic acid and 13'-(3,4-methylene-dioxyphenyl)-tridecanoic acid. Thirteen compounds previously isolated from seeds and adult plants were also reported.     

Surface tension measurements in the study of molecular complexes

Surface tension measurements can be used to investigate molecular complex formation in liquid solutions for strong and weak complexes. The association constant and epthalpy for triethylamine-iodine, hexamethylbenzene-tetracyanoethylene and ethanol-iodine in cyclohexane are 4·55×10³, 218 and 0.93M⁻¹ at 25° C and 12·5, 7·7 and 5·1 kcal/mol respectively. These values compare well with those reported in the literature by other methods.     

High Performance Varistor Discs Obtained from Chemically Synthesized Doped Zinc Oxide Powder

The ceramic microstructure, the chemical homogeneity of specific dopants and the mechanical integrity of a varistor disc are critical parameters in determining the transient voltage suppression features of these devices. The material properties and overall quality of the starting ceramic powders used to produce such components are essential in achieving the desired properties. The present work describes a novel chemical method developed to produce doped zinc oxide powders and an industrial scale manufacturing process for the production of final varistor blocks for surge arrester applications. The results are compared with those obtained when using standard varistor powder made by the mixed oxide route is used. All the fundamental electrical properties of the discs have been determined and correlated with the relevant manufacturing steps.