Synthesis and Polymerization of Some Chiral Vinyl Monomers. Part I. Preparation of Vinylbenzyl Esters of Amino Acids

Abstract

In this study we are interested in the synthesis of vinylbenzyl esters of amino acids. A method previously described in the literature has some disadvantages. We tried to find a better one. Three methods were tested and four amino acids were used. The best one consists of alkylation with an alkyl halide. The yield for this synthesis reached 96%. In all the case the products obtained were characterized by IR, NMR, and mass spectroscopies. The optical purity of the products was determined by polarimetry or by an NMR shift study. The ability of this type of monomer to polymerize and copolymerize was tested.     

Binding and Ionophoric Properties of Polyamide Compounds. Lead Selectivity

The extraction and transport properties of macrocyclic dioxa-, dithia- and diazatetralactams are reported along with those of open-chain analogous compounds. The preference of three of them for lead over alkali, alkaline-earth or other heavy metal cations is discussed.     

Nouvelle synthese de precurseurs phenoliques des lignines utilisant les sels d'iminium des acides p-hydroxy cinnamiques

4-Hydroxy cinnamic esters, thiolesters, aldehydes and alcohols, or related compounds, implied in the biosynthesis of lignins are easily synthesized in good yields from iminium salts of coumaric $\text{1a}$, ferulic $\text{1b}$ and sinapic $\text{1c}$ acids. No prior protection of the phenol group is needed in this method.     

Stéréochimie de β-diols et de leurs dérivés cycliques—VII. Calcul empirique des déplacements chimiques en série dioxannique. Application a l'analyse conformationnelle de dérivés alkyles

The empirical calculation of chemical shifts of methyl-1,3-dioxans leads to consistent results. Deviations from the experimental value are correlated with ring deformation. This method is applied to 4 or 6-ethyl, -isopropyl and tertiary butyl-1,3-dioxans. With no substituent at C5, the 4-tertiary butyl group causes no more deformation than at the 2 or 5 position. Interactions of this group with one or two methyl groups at C5 are examined.     

Continuous X-ray induced Auger microprobe analysis and microscopy: First results

X-ray induced Auger electron spectroscopy can be applied to the chemical analysis of thin samples with a spatial resolution in the 10 μm range. The first experimental results obtained with various anode materials and various samples are reported. The signal intensities (in the range of 10³ counts/s) are similar to those obtained by using a conventional electron spectrometer with a resolution in the millimeter range. Theoretical considerations together with the results obtained make it possible to evaluate the sensitivity of this technique and suggest how the spatial resolution can be improved further (20 μm at present, 2–3 μm in the near future). The radiation damage and sample thickness constraints of this new technique and of conventional Auger electron spectros- copy are compared. Application of X-ray induced Auger analysis to biological objects is suggested and the effect of the present results on scanning X-ray radiography and characteristic X-ray absorption microanalysis is also pointed out.     

NMR of some benzodiazepine drugs: Structure elucidation with lanthanide-induced shifts of N-1 substituted benzodiazepinones

Two 1,4-benzodiazepinones of psychopharmacological interest, pinazepam (2) and prazepam (3), were studied in solution by ¹³C and ¹H NMR. ¹H variable-temperature experiments showed that the seven-membered ring exists in a simple pseudo-boat form at room temperature, but the energy barrier is higher in 3 (ΔG_405°c = 82.8 kJ mol^?1) than in diazepam (1). Moreover, upon addition of LSR, the boat conformation is retained in the lanthanide ion-substrate complex, as with 1 in the solid state. Using a concentration-dependent shift technique and a computer-assisted LIS method, the conformations of the N-branched side-chain were investigated. Two preferred orientations were found for the propargyl group of 2, while three unequally populated conformations of the cyclopropyl moiety of 3 are distributed preferentially in the sterically unhindered space around the complex.     

Dilactones macrocycliques chirales derivees d'aminoacides. Synthese assistee par les organostannes ; proprietes complexantes

Three chiral macrocyclic dilactones containing L-glutamic or L-cystine moiety are synthetised by a simple method based on a tin “template-driven” process. Complexing properties are examined.     

Detection limits in Auger electron spectroscopy

The sources of background noise in Auger electron microanalysis are analyzed in order to evaluate the minimum detectable concentration x_m and the minimum number of detectable atoms y_m that can be reached. The best choices of operating conditions (the energy E₀, intensity I₀, and spot size d₀ of the incident electron beam, and the duration of the experiment t_e) are deduced for bulk and thin film analysis. The main results are: (i) The choice of E₀ is not very stringent, at least when E₀ ? 5E_i(A), where E_i(A) is the ionization energy, (ii) For a given electron dose received by the sample, x_m is improved by the use of the largest incident spot size while y_m is improved by the use of the finest spot size. The results also hold for other microanalytical techniques such as electron energy loss spectroscopy or electron probe microanalysis. (iii) Chemical identification of a single atom will be possible on samples able to tolerate very large electron doses by using incident electron beams 10 nm or less in diameter. The expected performance of a coincidence technique first suggested by Wittry is also discussed.