Electron impact mass spectrometry of 3-hydroxy-3,4,5,6-tetrahydro-2H-[1]benzoxocines. A comparison with the behaviour of isomeric 2-hydroxymethyl-2,3,4,5-tetrahydro-[1]-benzoxepines and 1,2-epoxy-5-(2-hydroxyphenyl)pentane

The mass spectrometric behavior of 3-methyl-3-hydroxybenzoxocines has been studied in detail by means of linked scans and mass analyzed ion kinetic energy spectrometry. The structure of the molecular ion and the fragmentation processes are strictly related to the structure of the neutral moieties. The possible isomerization of 3-hydroxy-10-methoxy-3-methyl-3,4,5,6-tetrahydro-2H-[1]benzoxocine to 2-methyl-2-[3-(3′-methoxy-2′-hydroxy)phenyl]pentyloxirane and to 2-hydroxymethyl-9-methoxy-2-methyl-2,3,4,5-tetrahydro[1]benzoxepine is investigated.     

Synthesis of stereo-defined α-trifluoromethyl (Tfm)-malic units

Aldol reactions of titanium enolates of N-acyl-1,3-oxazolidin-2-ones with ethyl trifluoropyruvate occurred with low to good stereoselectivity depending on the steric properties of the N-acyl group. Attempts to transform the resulting aldols into peptidomimetics incorporating stereo-defined α-trifluoromethyl (Tfm)-malic units are described.     

31P NMR spectroscopy as a powerful tool for the determination of enantiomeric excess and absolute configurations of alpha-amino acids

An easy method for the determination of the enantiomeric excess (ee) of mixtures of alpha-amino acids, and also for the elucidation of the absolute configuration of each component of the mixture, is reported. The method is based on the formation of diastereoisomers by reaction of the enantiomerically pure acetylacetonate derivative [Pd(acac-O,O')(P(2)-dach)]ClO(4) (4) [P(2)-dach = (1R,2R)-C(6)H(10)(NHPPh(2))(2)] with d,l-mixtures of alpha-amino acids AaH (Pd:AaH = 1:1 molar ratio, refluxing MeOH). The reaction occurs with protonation of the acac ligand and N,O-coordination of the amino acidate group, giving the corresponding [Pd(Aa-N,O)(P(2)-dach)]ClO(4) complexes l-5 and d-6. The composition of these mixtures of amino acidate complexes was analyzed by integration of the corresponding peaks (four doublets, two for each diastereomer) in their (31)P((1)H) NMR spectra. A series of 14 alpha-amino acids was studied (a, alanine; b, 2-aminobutyric acid; c, valine; d, phenylalanine; e, proline; f, leucine; g, isoleucine; h, norleucine; i, serine; j, threonine; k, methionine; l, aspartic acid; m, glutamine; n, cysteine), and excellent agreement between the expected values of ee and those obtained from integration of the (31)P((1)H) NMR spectra was obtained. Moreover, the position of the signals of each isomer is diagnostic, in such a way that the outer doublets are always due to the l-derivatives 5a-l, while the inner ones are due to the d-derivatives 6a-l, allowing the assignation of absolute configurations to each isomer in the mixture.     

Surface tension and density of mixtures of 1,3-dioxolane+alkanols at 298.15 K: analysis under the extended Langmuir model

Surface tensions (sigma) for [1,3-dioxolane+methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and 1-pentanol] and excess molar volumes (v(E)) for [1,3-dioxolane+methanol, ethanol, 1-propanol, 2-propanol, and 2-butanol] at the temperature 298.15 K and normal atmospheric pressure have been determined as a function of mole fractions. The magnitude of these experimental quantities is discussed in terms of the nature and type of intermolecular interactions in binary mixtures. In order to analyze the surface tension behavior, the extended Langmuir (EL) model was used and the results obtained for the systems containing 1,3-dioxolane were compared with those of other formerly published series: [1,4-dioxane+alkanes] and [1,4-dioxane+alcohols].     

Synthesis,Structure and Reactivity of [1, 2‐Bis(diphenylphosphinite)ethane]bromotricarbonylmanganese(I) with Reactions of Phosphites,Phosphonites. and Phosphinites

The manganese carbonyl complex [MnBr(CO)₃ L ] ( 1 ), where L = Ph₂POCH₂CH₂OPPh₂, was prepared by reacting [MnBr(CO)₅] with the bidentate ligand 1, 2‐Bis(diphenylphosphinite)ethane. From this compound and the appropriate phosphite, phosphinite or phosphonite ligands were synthesized the complexes [MnBr(CO)₂ LL ′], where L ′ = P(OMe)₃ ( 2 ) or P(OEt)₃ ( 3 ) and [MnBr(CO)₃ L ′₂], where L ′ =PPh(OEt)₂ ( 4 ) or PPh₂(OEt) ( 5 ). The obtained compounds have been characterized by elemental analysis, mass spectrometry, IR and NMR (¹H, ¹³C and ³¹P) spectroscopies and X‐ray diffractometry for the complexes 1 , 4 and 5 .     

Molecular ion rearrangements of benzenesulfonylhydrazides

The mass spectra of a series of substituted benzenesulfonylhydrazides are discussed. The main fragmentation mode of these compounds corresponds to rearrangement of the molecular ion with subsequent loss of N₂H˙ and/or N₂H₂. These fragmentations are confirmed by mass analysed ion kinetic energy spectra. Simple cleavage of the S? N bond with retention of the charge on nitrogen is observed for all the hydrazides studied but is favoured by electron withdrawing substituents. This latter fragmentation could not be confirmed by mass analysed ion kinetic energy spectra as it is probably very rapid and occurs mainly in the source.     

Optimization of 1D photonic crystals to minimize the reflectance of silicon solar cells

This paper presents a process to easily fabricate photonic crystals (PCs) on silicon to increase the efficiency of solar cells by reducing the sunlight reflection in the front surface of the cell. The process, based on laser interference lithography (LIL) and reactive ion etching (RIE), allows creating nanostructures over large areas with different shapes and dimensions. The reflectance of the resulting surface depends on the height, pitch, width and shape of the created PC. In this work, these parameters have been optimized by computer simulation and the best PC so far found has been fabricated on silicon. We obtain a normal reflectance under 10% in the spectral region between 500 and 900 nm without any other material employed as antireflecting coating.     

The Benzylperoxyl Radical as a Source of Hydroxyl and Phenyl Radicals

The benzyl radical ( 1 ) is a key intermediate in the combustion and tropospheric oxidation of toluene. Because of its relevance, the reaction of 1 with molecular oxygen was investigated by matrix‐isolation IR and EPR spectroscopy as well as computational methods. The primary reaction product of 1 and O₂ is the benzylperoxyl radical ( 2 ), which exists in several conformers that can easily interconvert even at cryogenic temperatures. Photolysis of radical 2 at 365 nm results in a formal [1,3]‐H migration and subsequent cleavage of the O?O bond to produce a hydrogen‐bonded complex between the hydroxyl radical and benzaldehyde ( 4 ). Prolonged photolysis produces the benzoyl radical ( 5 ) and water, which finally yield the phenyl radical ( 7 ), CO, and H₂O. Thus, via a sequence of exothermic reactions 1 is transformed into radicals of even higher reactivity, such as OH and 7 . Our results have implications for the development of models for the highly complicated process of combustion of aromatic compounds.