Sinthese de copolymeres sequences de l'acetate de vinyle et de l'acrylate d'ethyle par telomerisation

A new two-step procedure for the synthesis of ethyl acrylate - vinyl acetate block copolymers is described : the first stage is the telomerisation of ethyl acrylate with carbon tetrachloride by redox catalysis, the second being another telomerisation of vinyl acetate, using the trichloromethyl end group of the first block as the telogen agent, with peroxydic initiation.     

Dosage de l'hydrogene,de l'azote et de l'oxygene dans le monocarbure d'uranium

A method is described for the determination of hydrogen, oxygen and nitrogen in uranium monocarbide. Hydrogen and oxygen are determined by the classical or modified “Platinum flux” method at 2000° with a coefficient of variation of 10%. Nitrogen is determined at 2000° by the modification of the “Platinum flux” technique. The results obtained are in agreement with those found by Kjeldahl analysis. The coefficient of variation is about 10%. A procedure for the simultaneous determination of the 3 gases is given.     

Enolates de l'acetylacetate d'ethyle. Structure et reactivite du sel de potassium en presence d'ether couronne et de cryptand

It is shown that, through the addition of 18-crown-6 or cryptand (2.2.2) to potassium ethyl acetoacetate enolate solutions in tetrahydrofuran, 1:1 complexes are formed. A single crystal of the 1:1 potassium énolate-18-crown-6 complex has been obtained. Its structure has been determined by X-ray diffraction. The crystal includes entities formed from an enolate anion chelating a potassium cation externally complexed by the crown-ether. The vibrational spectrometry shows that the structure of the entity is kept in solution. In the species formed through the addition of cryptand (2.2.2), the enolate anion has a structure (IR spectroscopy) and a reactivity very close to that of the free anion, observed in a dissociating solvent (DMSO, HMPA). When crown ether is added, a contact ion pair is formed, in which the cation is externally solvated by the crown. On the other hand, the cation encapsulation by the cryptand leads to a released anion with an “ S-trans” or “W” structure. The reactivity and the orientation of the alkylation reactions of these entities have been measured in THF solutions. They are discussed in relation to the structure of the species present in the reaction medium.     

Synthese et etude de l'agregation moleculaire d'amines derivees de l'adamantane

Adamantanealkanamines were prepared by a new method: the wittig reaction of aminophosphonium ylides with 2-adamantanone. Conductance measurements have been employed to examine and compare the aggregation behaviour of these compounds.     

Spectres de vibration et structure d'un cristal d'amidogallate de sodium

Raman spectra (4000-150 cm^?1) of a single crystal of NaGa(NH₂)₄ and infrared spectra (4000-200 cm^?1 ) of a polycrystalline sample have been studied at different temperatures. An assignment of the bands is given. The spectra are discussed assuming S₄ and T_d point group symmetry of the Ga(NH₂)^?₄ ion at low temperature and at room temperature respectively. Metal-ligand and N-H stretching frequencies are compared to those of some other amido metalates.     

Synthese et configuration de l'alnincanone

Alnincanone 1, and its three diastereoisomers at C-20 and C-24, have been synthesized from dipterocarpol. The configuration of the four isomers has been defined by several independent methods; the naturally occurring alnincanone is 20S,24R.     

Structure de l'echitamidine,d'un stereoisomere et de deux regioisomeres

The relative configuration of echitamidine is established by spectral and X-ray crystallographic techniques. Three other isomers are described and a structure is proposed for them.     

Essais d'analyse conformationnelle de cyclopentanols et de germacyclopentanols

The NMR spectra of cyclopentanols and germacyclopentanols have been recorded in the presence of Pr(DPM)₃ and analyzed. Using the induced chemical shifts and the coupling constants, preferred conformations are proposed for the cyclanols.     

Effet de longueur d'onde et controle par la geometrie de l'etat fondamental de la photoisomerisation de derives de l'hexatriene-1,3,5

Irradiations at different wavelengths (313, 254, 229 and 214 nm) of the 4 geometric isomers of 5-phenyl-1,3,5-heptatriene show that the photochemical behaviour of these trienes is mainly controlled by their ground state equilibrium.     

Copolymeres du chlorure de vinyle et de l'acrylate de glycidyle

A study of the radical copolymerization of vinyl chloride (C) and glycidyl acrylate (A) at 60° in dichloroethane solution leads to the following reactivity ratios r_c = 0·14 ± 0·02 and r_A = 7·4 ± 0·3According to the nature of the solvent, the reaction of protonic acids may cause either cationic polymerization of epoxy groups or addition of HCl or water onto the same groups. The HCl addition is observed during the thermal degradation of the copolymers so that HCl evolution is greatly delayed.     

Hydrogenation asymetrique de precurseurs d'aminoacides a l'aide de mono- et diphosphines derivees de sucres

Mono- and di-phosphines derived from sugars are synthesized and used as ligands in asymmetric catalysis. In the presence of a base (triethylamine, KOH…) the cationic complex [Rh(COD)dioxop]⁺ClO₄^?, catalyzes reduction of α-amino acid precursors with high optical yields (78–86%). The influence of the base is discussed.     

Existence d'isomeres e et z d'ylures de cycloimmonium

E and Z isomers of p-nitrobenzoyl, 4-p-tolyl[1-2-4]triazolum methylide 5b and p-nitrobenzoyl, 4-p-phenyl[1-2-4]triazolium methylide 5e, have been characterised.     

Syntheses d'oxazolidines substituees par l'adamantane et de nitroxydes oxazolidines stables derives de l'adamantane

Adamantane oxazolidine derivatives have been prepared. The corresponding mono and biradicals have molecular shapes well suited to the study of the motion anisotropy in solution.     

Spectres de vibration et conformations du propionate et de l'isobutyrate de méthyle

Infrared and Raman spectra (3600–3620cm^?1) of methyl propionate CH₃CH₂-COOCH₃, CH₃CH₂COOCD₃ and methyl isobutyrate (CH₃)₂CHCOOCH₃, (CH₃)₂CHCOOCD₃, in liquid and crystalline states, have been recorded. Rotational isomerism, by rotation around the C-C bond α to the carbonyl group, is detected and the energy difference between the conformers is 1.1 ±0.3 kcal mol^?1 for methyl propionate and 0.5 ±0.1 kcal mol^?1 for methyl isobutyrate. Vibrational assignments in terms of group frequencies are proposed for each conformer, only the more stable being present in the crystal.     

Reactivite du tetraallyletain et d'allyltrialkyletains vis a vis d'aldehydes,de cetones et d'epoxydes

Tetraallytin reacts readily with non activated ketones and exothermically with aldehydes contrary to other allylic organotins such as allytributyltin. Homoallylic alcohols are obtained after acidolysis of the adducts. Upon extended heating, allylic organotins and epoxides form products which correspond to additon products of isomeric carbonyl compounds. However, starting from cis- and trans-1-phenyl-1,2-epoxypropanes, direct regiospecific but non-stereospecific ring opening is observed with poor yields.