Oscillations chimiques lors de l'oxydation de dicétones par le bromate en présence d'un catalyseur (Réaction du type Belousov-Zhabotinsky)

New ketonic compounds have been found to generate temporal chemical oscillations in Belousov-Zhabotinsky – type reactions: fluorinated acetylacetone, acetonylacetone (2,5 hexanedione) and, acetone itself.     

Etude par RMN du proton de la complexation du triéthylaluminium par l'éther diéthylique

The complex between triethylaluminium and diethylether has been studied by ¹H NMR; separate signals have been observed for free and bonded triethylaluminium. From the area ratios, a 1:1 stoichiometry is demonstrated. At higher ether concentrations, chemical shift measurements prove that other complexes do not appear.     

Recherches sur le benzofuranne. LVI. Synthèses dans la série de l'Euparone par acétylation de benzofurannes acétylés et méthoxylés sur l'homocycle

Unsubstituted benzofuran derivatives acetylatcd and methoxy-lated on the benzenoid moiety can be further acetvlated either on the benzene or on the furan ring - with or without demethylation depending upon the different cases. A series of new isomers of Euparone (2,5-diacetyl-6-hydroxybenzofuran) and its corresponding ether has thus been formed.     

Étude thermodynamique de la complexation de l''argent par quelques pyrazines substituées

Stability constants of silver complexes with the substituted ligands 2-methyl-2,5-dimethyl-, 2,6-dimethyl-, 2-chloro- and 2-amino-pyrazines are determined by means of a potentiomeric method, using metal complex electrodes at 25°C and 0.1M KNO₃ as an ionic strength in aqueous medium.

Standard enthalpies of the two steps of complexation observed are obtained by a direct calorimetric technique (except for the Ag-2-aminopyrazine system whose complexes are not sufficiently soluble) under the same experimental conditions. The corresponding standard entropies are calculated.

The discussion of the thermodynamic functions takes into account the nature and the position of the substitutents to interprete the coordination ability of each amine.     

Etude par spectrométrie de masse du cyclopentanediol-trans-1,2

The electron impact induced fragmentation of trans cyclopentane-1, 2-diol has been investigated using derivatives specifically labelled with deuterium and high-resolution mass spectral data. The elimination of the elements of water from the molecular ion involves at least three mechanisms whose relative importance has been evaluated. A fragmentation scheme based upon metastable peaks and labelling is presented.     

Etude par RMN du Proton de la Stéréochimie de Composés Ethyléniques Trisubstitués. Calcul Empirique et Calcul par Incréments de la Constante d'Ecran

The Pascual and Tobey approaches for evaluating the chemical shift of an olefinic proton have been tentatively applied to the case of substituents which often cause difficulties in signal assignment. The empirically calculated values of the differential shielding between olefinic protons in both Z and E configurations are compared to the experimental values of the chemical shifts in a series of 2-arylpropene nitriles. The Z configuration is proved to correspond to the less shielded nucleus and the observed solvent effects are consistent with this assignment. When the Z configuration predominates its nature has been unambiguously established by studying also the corresponding E isomer of which a very small quantity could be isolated. The results offer a good way for the computation of new substituent additive parameters (NH₂, OH, ONa).     

Etude par spectrométrie de masse du diaza-2,5 dioxa-1,6 thia-6a λ IV pentalègne et de ses analogues séléniés et tellurés

The mass spectra of 2,5-diaza-1,6-dioxa-6a-λ-IV-pentalenes and of its selenium and tellurium analogs are recorded. The spectra show strong stability of these compounds under electronic impact and a rather good reproductibility for their fragmentations independently of thenature of the heteroatom (s, Se or Te).     

Etude de la fragmentation par impact électronique de dérivés du benzothiazole

Study of Electron-Impact Fragmentation of Benzothiazole Derivatives The mass spectra of eighteen substituted benzothiazoles are reported and discussed. All these compounds are thermodynamically stable and give an intense molecular ion, which undergoes different types of fragmentation depending on the nature of the substituent which is rarely eliminated directly. β-Cleavage with respect to the heterocyclic double bond is often observed. Specific ²H-, ¹³C-, ¹⁵N- and ³⁴S-labelling have been used in order to confirm the fragmentation patterns.     

Dérivés C-glycosyliques VIII. Synthèse de C-glycosyl-3-pyrazoles à partir d'une nitrilimine dérivée de l'anhydro-2,5-D-ribose. Compétition entre cyclo-additions dipolaires-1,3 et cyclisations non concertés

Several 3-(2,5-anhydro-ribosyl)-pyrazoles of potential medicinal interest have been synthesized by reacting alkynes or alkynylmagnesium bromides with the p-nitrophenylhydrazone of 2,5-anhydro-ribonyl bromide. From a mechanistic standpoint, it has been shown that the sugar-nitrilimine used in these studies reacts more readily as an electrophile than as a dipole. Thus, the hydrazonyl bromide gave exclusively the corresponding phenylethynylhydrazone when treated with phenylethynylmagnesium bromide and led to a 1:1 mixture of phenylethynylhydrazone and pyrazole when reacted with phenylacetylene. This proves that nucleophilic additions onto nitrilimines are much faster than Huisgen's 1,3-dipolar cycloadditions.     

Action du cyanure mercurique sur quelques halogénures de désoxy-3-trifluoroacétamido-3-D-ribofurannosyle. Note de laboratoire

Reactions of Some 3-Deoxy-3-trifluoroacetamido-D -ribofuranosyl Halides with Mercuric Cyanide The expected 2,5-anhydro-D -allononitrile 11 was obtained when the 2-O-benzoyl-3-deoxy-3-trifluoroacetamido-D -ribofuranosyl bromide reacted with mercuric cyanide, whereas the isomeric 1,2-O (1-cyanoethylidene) derivative was formed from the 2-O-acetylated halide; no reaction occurred when the halide was 2-O-p-nitrobenzoylated.     

Etudes photochimiques en série hétérocyclique. V. Mise en évidence d'oxazoles par photooxydation de thiazoles

Formation of oxazoles as by-products of photooxydation of thiazoles In the presence of air, light (high pressure mercury lamp) and iodine as sensitizer, benzene solution of arylthiazoles 2 , 3 and 13 (see scheme 1) were converted into a mixture of photoisomers and aryloxazoles (see scheme 2). Upon shorter times of irradiation under oxygen in chloroform containing methylene blue as a sensitizer 2,4,5-triphenylthiazole (7) is converted in 2,4,5-triphenyloxazole. Under usual photooxidation conditions, in methanol as solvent, most of arylthiazoles studied gave a mixture of nitriles, amides, acids esters and diketones. In the case of thiazole 7 , the corresponding oxazole was also found. A possible mechanism for the photochemical oxidation of arylthiazoles to aryloxazoles, via 2,5- and 4,5-endo-peroxides, may be proposed (see schemes 5 and 6).     

Etude par RMN du Proton et du Carbone-13 de Pyrimidines Substituées. I—Effets de Substituant dans les Dérivés Méthylés et Aminés

Substituent effects of methyl and amino groups on the chemical shifts of pyrimidine have been investigated by ¹H and ¹³C n.m.r. and compared with similar data obtained for benzene and pyridine. Taking into account pairwise interactions, the chemical shifts calculated by using an additivity relationship are in very good agreement with the experimental results, except for some hindered pyrimidines. This study enabled us to assign the ¹³C n.m.r. spectra of some trisubstituted pyrimidines.     

Etude par spectrométrie de masse de la fragmentation du cyclopentènediol-3,5-trans

The decomposition modes of trans cyclopentene-3, 5-diol under electron impact have been studied on deuterium labelled analogues. Fragmentation mechanisms are proposed.     

Diazoalcanephosphonates. Etude par RMN du proton de la configuration de Δ1-pyrazolines dérivées du norbornadiène

The NMR spectra of eleven pyrazolines 1 to 11 derived from norbornadiene are interpreted and discussed. The configurations are deduced from the vicinal P?C?C?H₁₀ coupling: this is ～20 Hz in the anti derivatives and ～6·0 Hz in their syn epimers. The long-range P,H₉ coupling is stereospecific, being maximum for a syn configuration.     

Réactions induites par les halogénures de pyridinium. XXIV. Sur la synthése de dibenzofurannes à partir de diméthoxy-2,2′ biphényles

Dibenzofurans were obtained by the cyelization of 2,2′-dihydroxybiaryls using pyridinium bromide. The 2,2′-dihydroxy-biaryls were obtained by demethylation via pyridinium chloride from 2,2′-dimethoxybiaryls. The dealkylation which is followed by cyelization into the dibenzofurans with pyridinium bromide is complicated by indirect transmethylation. Acyl derivatives of 2,2′-dimethoxybiaryles lose their acyl group when dealkylated by pyridinium halides, whether or not cyelization follows this process.     

Résonance magnétique nucléaire du noyau 14N par Transformée de Fourier

¹⁴N-NMR. measurements using the Fourier Transform technique are presented and compared to C. W. experiments. The F. T. technique is especially advantageous for relaxation time measurements. However, since ¹⁴N-nuclei may have widely different relaxation times, it is often not possible to have optimal gain in sensitivity (as compared to C. W. measurements) in a single F. T. experiment for different ¹⁴N-nuclei contained in the same sample. Different experiments have to be performed, optimizing the spectrometer parameters for each ¹⁴N-resonance of appreciably different linewidth. The technique is applied to three different problems. ¹⁴N-relaxation in symmetrical ammonium salts is shown to arise from reorientation of the water dipoles. The use of a double spin-probe, ¹³C-¹⁴N, allows the determination of the electric field gradients in cyclic ammonium salts. The electronic distribution is especially distorted from tetrahedral symmetry in the highly strained N, N-dimethyl-aziridinium cation. Finally, electric and dynamic effects in ion pairing may be studied as shown on the case of tetrabutylammonium iodide in water and in benzene.     

Détermination de constantes de stabilité de chélates par résonance magnétique nucléaire du proton

In a solution containing an excess of two metal ions in regard to a ligand (e.g. NTA) a competitive equilibrium is established. The measure, by proton NMR. spectroscopy, of the individual concentrations of both chelates, and eventually of the free ligand, allows to determine the ratio of the stability constants of the two complexes. As an illustration the ratios of the stability constant of the 1:1 nitrilotriacetate chelates of Pb and Zn, respectively Mo and W, were determined.     

Spectrométrie de Masse d'Hétérocycles. VIII—Edude de Dérivés du Dioxasilolanne-1,3,2

The fragmentation mechanisms of 1,3-dioxasilolane have been investigated. These fragmentations lead principally to ‘silyl’ ion formation, or involve cleavage of the bonds α and β to the silicon as for hydrogen migrations.     

Etude par Résonance Magnétique Nucléaire du carbone 13 de complexes du cobalt (III) et de la diméthylglyoxime

From a carbon magnetic resonance study of several alkylcobaloximes RCo(DMG)₂B (DMG = dimethylglyoximate monoanion), it was possible to estimate the α, β and γ effects of the Co(DMG)₂B group on the chemical shifts of the carbon atoms of various alkyl groups R. The chemical shifts of the carbon atoms belonging to the equatorial ligands and to the axial base B are not significantly affected by structural modification of the R groups. Values of δ in benzylcobaloximes XC₆H₄CH₂Co(DMG)₂B agree with a donor effect of the ? CH₂Co(DMG)₂B radical. Values of ¹J(¹³C? H) coupling constants, measured in ¹³C enriched methylcobaloximes, do not vary appreciably when B is changed (J(¹³C? H) = 137 ± 1 Hz) and are close to the value obtained for methylcobalamine.