Alcoylation par l'iodure de butyle,de l'enolate de tetrabutylammonium de l'acetylacetone; nature de l'entite reagissante

The alkylation of tetrabutylammonium acetylacetonate with butyl iodide was studied in order to specify the nature of the reactive anionic species during the nucleophilic reaction of an ambident anion, under similar conditions to those of phase transfer catalysis. The C/O alkylation ratio changes with neither the solvents nor the enolate concentration; however k_obs, varies with the solvent but does not depend on the énolate concentration. The results and spectrophotometric UV data show that only one reactive species, the ion-pair, is involved.     

Polymerisation purement thermique de l'acide acrylique en masse et en solution

The thermal polymerization of acrylic acid in bulk is faster than that of styrene. The conversion curves exhibit auto-acceleration and the product contains a significant fraction of syndiotactic polymer. The overall activation energy is 14 kcal/mol. The rate of the thermal polymerization decreases sharply when the monomer is diluted with toluene. In 50% monomer solutions, the conversion curves are linear and the overall activation energy is 29.8 kcal/mol. With 75 and 90% monomer solutions, the Arrhenius diagrams showed breaks caused by a change in the type of auto-association of the monomer. A comparison of these results with earlier findings obtained in the radiation polymerization of acrylic acid makes it possible to estimate the activation energies of the thermal initiation. It is found that E_i is 14.1 kcal/mol in systems where the monomer forms linear oligomeric association complexes and 34.4 kcal/mol if only cyclic dimers are present in the system.     

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.     

Structure cristalline et configuration relative d'un complexe du titanocene presentant une chiralite plane et une chiralite centree sur l'atome de titane

The crystalline structure of the racemic form m.p. 164° C of the compound (h⁵ -3-MeC₅H₃C(Me₂)C₆H₅)(h⁵-C₅H₅)Ti (2,6-Me₂C₆H₃O)Cl has been determined by X-ray diffraction to establish the relative configuration of the two chiral moieties. This compound may be used further as a reference for studies on dynamic stereochemistry around the titanium atom. A systematic absolute nomenclature is proposed for this type of structure.     

Etude de l'equilibre entre l'oxyde de nickel et l'oxygene. Essai d'interpretation des lois de variation de la conductivite electrique en fonction de la temperature

In a previous paper we have shown that at 740°C and under an oxygen pressure less than 1,3 torr the electrical conductance G of a NiO powder reaches rapidly an apparently stabilized signal G_i which sharply decreases after a sufficiently long time to a G₀ value independent of P_O2.From this observation we have studied the influence of the temperature successively on the electrical conductance G_i and G₀. The Arrhenius law is only verified for the G₀ = f(T) curve. G₀ appears as the representative value of the gas-solid equilibrium.     

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.     

Pre´paration chimique et structure cristalline de l'iodate d'argent AgIO3

A new chemical preparation of silver iodate AgIO₃ is given. The crystal structure has been determined by single-crystal X-ray diffraction methods and refined to a finalR value of 0.051 for 1280 independent reflections. The unit cell is orthorhombic witha = 7.265(2), b = 15.17(4), c = 5.786(2)A?,Z = 8. The space group isPbc2₁. IO₃ groups and AgO₆ octaedra form a compact bidimensional framework perpendicular to theb axis.     

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.     

Nombre de transport et conductivité cationique dans l'oxyde de nickel: NiO

Ionic transport number measurements have been made on single crystals of NiO over the temperature range 900–1300°C and for oxygen partial pressures varying from 10^?8 to 1 atm. At 1000°C and in air, t_Ni ～ 2 × 10^?7. The variation in cationic conductivity as a function of oxygen partial pressure suggests that V′_Ni is the dominant defect at high temperature and low oxygen pressure and that V″_Ni is the dominant defect at low temperature and high oxygen pressure.     

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.     

Structure cristalline d'un dihydrogeno-sulphato-iodate de potassium

The iodato-sulfate K₄H₂(S₂I₂O₁₄) is monoclinic, $\text{P2}{}_1\text{n}$ with a unit cell: a = 13.84(1) Å, b = 7.173(5) Å, c = 7.443(5) Å, β = 93.16(1)°, and Z = 2. The crystal structure of this salt has been solved using 1956 independent reflections, with a final R value of 0.03. The main feature of this salt is the existence of a finite new heteropolyanion: (I₂S₂O₁₄)^?6.     

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.     

Decomposition thermique des acides peroxybenzoique et peroxydodecanoique en milieu non polaire: role de l'oxygene

A study of the decomposition mechanisms of peroxydodecanoic (RCO₃H) and perbenzoic (φCO₃H) acids in cyclohexane at both reflux temperature and less than reflux temperature (i.e. with and without dissolved oxygene) and comparisons of all the products from these reactions with those obtained from the decomposition of dodecanoyl- and benzoyl-peroxydes under the same conditions, leads to the following conclusions: (a) in both cases there is a radical mechanism, the initiating step being the rupture of the O-O bonds giving RCO₂ and φCO₂, (b) under reflux (i.e. without oxygen) the radical RCO₂ undergoes rapid decomposition and the resulting R- gives rise to a chain reaction leading to the alcohol ROH. The φCO₂ radical undergoes much slower decomposition and through chain transfer with the solvent produces φCO₂H and cyclohexanol. These reactions are fast; (c) at less than reflux temperature (i.e. in presence of dissolved oxygen) R radicals or S (solvent) radicals combine with the oxygen giving peroxy and oxy radicals. These species are electrophilic and therefore do not lead to the breaking of the O-O bond of the peracid. Rather, the acid hydrogen is attacked, giving RCO₃ or φCO₃, radicals. Through a series of reactions involving aldehyde intermediates, the corresponding carboxylic acids are obtained. These reactions are much slower than those at reflux temperature.     

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.     

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.