Desulphurative approaches to penem antibiotics. VI. From penam methyl esters to penem acetonyl esters: A fully conservative conversion

A straightforward conversion of penam methyl esters into penem acetonyl esters entailing incorporation of all the elements of the former into the latter is described.     

Specific interactions in blends of poly(ethylene oxide) and poly(bisphenol A-co-epichlorohydrin): FTIR and thermal study

Blends of poly(ethylene oxide) (PEO) of high molecular weight with poly(bisphenol A-co-epichlorohydrin) (PBE) with high epoxy equivalent were studied spectroscopically, thermally and morphologically. As similar systems of low molecular weight, a single T_g was observed for all blends, indicating miscibility. A progressive decrease in the degree of crystallinity and in the size of the PEO spherulites as the PBE is added is also observed. Quantitative analysis from FTIR spectra provided determination of specific interactions between the constituents and their variation with PEO content. Simulations were performed utilising the spectra of the pure polymers to confirm that the observed changes in the experimental spectra of the blends were due to interaction between the polymers.     

Molecular orbital study of hyperfine splitting constants in ethyl and cyclohexadienyl radicals

Hyperconjugated models are used for a m.o. calculation of proton h.f.s. constants in Ethyl and Cyclohexadienyl radicals. A slightly modified Pariser-Parr-Pople SCF method is employed including extensive configuration interaction. The calculated spin densities for the hyperconjugated protons are in good agreement with experiment.

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Zusammenfassung Zur Berechnung von Protonenhyperfeinstrukturkonstanten von Äthyl- und Cyclohexadienyl-Radikalen werden Modelle mit Hyperkonjugation verwendet. Die Rechnung gründet sich auf eine leicht modifizierte Pariser-Parr-Pople-Methode einschließlich ausgedehnter Konfigurationswechselwirkung. Die berechneten Spin-Dichten für die hyperkonjugierten Protonen stimmen mit experimentell ermittelten Werten gut überein.

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Résumé Des modèles tenant compte à la hyperconjugaison sont usés pour le calcul des constantes de structure hyperfine protonique des radicaux éthyl et Cyclohexadiényl. Le calcul se base sur une méthode Pariser-Parr-Pople un peu modifiée et comprenant une interaction de configurations extensive. Les densités de spin calculées pour les protons hyperconjugués sont en bon accord avec des valeurs expérimentales.

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We thank the Italian National Research Council (Chemistry Committee, Research Group IV) for financial support. One of us (P.L.N.) thanks Sicedison S.p.A. for a grant.     

cEST: a flexible tool for calorimetric data analysis

Journal of Thermal Analysis and Calorimetry - The pyrolysis characteristics and kinetics of lignocellulosic biomass (cotton stalk) and seaweed (Gracilaria lemaneiformis) were studied comparatively....     

Novel heterocyclic ligands with tuned hydrophobicity

Heterocyclic azodyes of the pyridylazonaphthol and pyridylazoresorcinol series containing tuned hydrophobic chains have been prepared. Due to their chelating properties, the dyes are suitable candidates for preconcentration and selective separation of transition metal ions. After a discussion on the choice of the best synthetic pathway, physical and spectral uv/visible properties are presented and correlated with the structural features. A detailed analysis of nmr spectra allowed the clarification of currently unresolved signal assignments.     

A chemometric survey of three sites in Muggia Bay (Northern Adriatic Sea): meteorological effects on heavy metal patterns in surface coastal waters

Within research on the quality of the waters of the Gulf of Trieste, this study on patterns of trace metal contents in the inner part of the gulf (Muggia Bay) discusses data of Cu, Pb, Cd and Zn, determined voltammetrically (DPASV), and collected in three sites with a 10-day frequency over the period of one year. Two of the sites lie inside the dam system which protects the harbour of Trieste, while the third one is situated outside for comparison purposes. Principal component analysis pointed out different metal patterns inside and outside the dam system; PC scores were related to meteorological information: rain plays a major role in conditioning the estuarine inner site: wind stirring action was detectable for the outer site. Both univariate graphics and canonical correlation analysis suggest a diffuse source for Pb, probably atmospheric deposition. Received: 1 August 1997 / Revised: 20 November 1997 / Accepted: 23 November 1997     

An intramolecular N-H...(mu-H)Re2 dihydrogen bond and a novel mu 3-eta 2 coordination mode of the pyrazolate anion on a triangular cluster face

The quantitative addition of pyrazole (Hpz) to the 44 valence-electron, triangular cluster anion [Re3(mu 3-H)-(mu-H)3(CO)9]- gives the novel unsaturated anion [Re3(mu-H)4(CO)9(Hpz)]- (1, 46 valence electrons), which contains a pyrazole molecule that is terminally coordinated on a cluster vertex. Solidstate X-ray and IR analyses reveal a rather weak hydrogen-bonding interaction between the NH proton and one of the hydrides bridging the opposite triangular cluster edge (delta H degree = -3.1 kcal mol-1 from the Iogansen equation). Both IR and NMR data indicate that such a proton-hydride interaction is maintained in the major conformer present in CD2Cl2, but also provide evidence of the presence of minor conformers of 1 in which the NH proton is involved in an intermolecular hydrogen bond with the solvent. The mu-H...HN bond length evaluated in solution through the T1 minimum value (2.07 A) and that determined in the solid state by X-ray diffraction (2.05 A) are in good agreement. NMR experiments show that, in acetone, intermolecular N-H...solvent interactions replace the intramolecular dihydrogen bond. At room temperature in CH2Cl2, the pyrazole ligand in 1 is labile and 1 slowly "disproportionates" to [Re3(mu 3-H)-(mu-H)3(CO)9]- and [Re3(mu-H)3(CO)9-(mu-eta 2-pz)(Hpz)]-, with H2 evolution. Slow H2 evolution also leads to the formation of the anion [Re3(mu-H)3-(CO)9(pz)]- (5), in which the pyrazolate anion adopts a novel mu 3-eta 2-coordination mode, as revealed by a single-crystal X-ray analysis. The analysis of the bond lengths indicates that the pyrazolate anion in 5 acts as a six-electron donor, with loss of the aromaticity. The formation of 5 from 1 is much faster in solvents with a high dielectric constant, such as acetone or DMF. Anion 5 was also obtained from the reaction of pyrazole with [Re3(mu-H)3(CO)9(mu 3-CH3)]- through the intermediate formation of two isomeric addition derivatives and following CH4 evolution.     

Gemini pyridinium surfactants: synthesis and conductometric study of a novel class of amphiphiles1

A new series of pyridinium cationic gemini surfactants was prepared by quaternization of the 2,2'-(alpha,omega-alkanediyl)bispyridines with N-alkylating agents, whose reactivity is briefly discussed. Particularly useful was the use of long-chain alkyl triflates (trifluoromethanesulfonates) for both overcoming the sterical hindrance in the pyridines and obtaining higher synthetic yields. Well-known 4,4'-(alpha,omega-alkanediyl)bis(1-alkylpyridinium) structures showed narrow temperature ranges for practical applications, due to their high Krafft points, while the new 2,2'-(alpha,omega-alkanediyl)bis(1-alkylpyridinium) series, accounted for good surface active properties. Due to the Krafft points below 0 degrees C, they could be exploited as solutions in water at any temperature. The characterization of the behavior of the series was performed by conductivity measurements. Some of the proposed structures exhibited unusual surface active behavior, which was interpreted in terms of particular conformational arrangements.     

2‐(4‐methylpyridin‐2‐yl)‐1H‐benzimidazole derivatives. Part I. X‐Ray structural analysis

The X‐ray analyses of some neutral and cationic derivatives of 2‐(4‐methylpyridin‐2‐yl)‐1H‐benzimida‐zole are reported and the structural data tentatively correlated to relative UV‐visible properties. A rotation of the γ‐picoline ring with respect to the benzimidazole moiety may be responsible of the spectral behavior.