L'extraction des lanthanides et des actinides par les oxydes d'alkylphosphine: Tome 1. l'extraction de l'acide nitrique par l'oxyde de tri-n-butylphosphine

The distribution of TBPO, water and nitric acid has been measured between an aqueous phase and various inert diluents at 25°. This study allowed the determination of the apparent stability constants for two molecular complexes, TBPO . HNO₃ (K₁=17.5±1.3 (M/l)^-2 (benzene); 20.1±0.8 (M/l)^-2 (toluene); II±2(M/l)^-2 (n-hexane) and TBPO . 2HNO₃.H₂O (K₂=(2.9±0.3) 10^-3(M/l)^-2 (benzene)).     

L'extraction des lanthanides et des actinides par les oxydes d'alkylphosphine : L'extraction de L'acide nitrique par les oxydes de tri-n-hexylphosphine,de tri-cyclohexylphosphine et de tri-n-octylphosphine

The distribution of nitric acid between an aqueous phase and a solution of THPO, TcHPO and TOPO in benzene was measured at 25°. The apparent stability constants K₁' were found to be 17.2±1.0 (M)^-2 for THPO.HNO₃, 7.0±0.8 (M)^-2 for TcHPO.HNO₃ and 15.2 ± I.I (M)^-2 for TOPO.HNO3. The stoichionetry of the last complex was confirmed in n-octane solution at constant ionic strength in the aqueous phase.     

L'extraction des lanthanides et des actinides par les oxydes d'alkylphosphine : L'extraction del'acide nitrique par quelques dioxydes de diphosphine

The distribution of nitric acid between an aqueous phase of constant or variable ionic strength and a benzene solution of diphosphine dioxide can be explained by the following reactions H⁺_a+ NO_3^-a+ DiPO₀ ? D1PO·HNO₃₀ H⁺_a+ NO_3^-a+ DiPO·HNO₃₀ ? DiPO·2 HNO₃₀ At constant ionic strength, the stability constants K₁″ were determined for the complexes 1,1-DiPO·HNO₃ (98 ± 01 (M)^-1), 1,4-DiPO·HNO₃(44±3 (M)_-1) and 1,5-DiPO·HNO₃ (51 ± 1 (M)^-1). The constants K₁₁″ for the complexes 1,1-DiPO·2 HNO₃ and 1,5-DiPO.2 HNO₃ are respectively 035±001 (M)^-1 and 62 ±0.05 (M)^-1 at 25°. With an aqueous phase of variable ionic strength, values of K₁'=54±7 (M)^-2 for 1,5-D1PO.HNO₃ and K_II'=65 ± 04 (M)^-2 for 1,5-DiPO·2 HN0₃ were obtained     

Degradation bactérienne de l'acide dehydroabiétique par Flavobacterium resinovorum

Flavobacterium Resinovorum was grown on dehydroabietic acid 1a as sole carbon and energy source. Slowly growing cultures were obtained either by omission of nitrogen, Fe²⁺ and Mg²⁺ ions or in the presence of an inhibitor (α,α′-dipyridyle). Under these conditions, different intermediates of the metabolic pathway were accumulated. Diphenol diketone 6a has been isolated. The unique behaviour of bacterial attack at C-3 before the degradation of the cyclic system is confirmed.     

Etude de la complexation des lanthanides trivalents par les six isomères de l'acide diaminocyclohexane-tétraacétique

The stability constants of the 1:1 complexes of the trivalent lanthanides with the cis-1,2 cis1,3 trans-1,3 and cis-1,4 isomers of diaminocyclohexane-N,N,N′,N′-tetraacetique acid are reported for an ionic strength of 1 mol 1^-1 (KCl) at 25°C; the values were obtained by coulometric titration with potentiometric detection. The interrelationships between the molecular structure of the chelating agents and the stability constants are discussed, and the importance of stereochemical factors is emphasized.     

Cinetique complexe de l'halogenation de cetones en milieu acide—I : Iodation des enols

The kinetics of the iodination of acetone, diethylketone and di-isopropylketone in aqueous media ([H₂SO₄] = 0·1 to 1·0 N; [I₂]_a^o = 10^?7 to 10^?5M) have been studied by couloamperometry under irreversible conditions. At these concentrations the rates of formation of the enol and of its iodination are similar. The general equation, which assumes the steady state approximation for the enol, is applicable, and is used to separate the rate constants of enolisation (k₁) and the apparent enol iodination rate constant (k_II^I₂ = K_Ek₂^I₂). For acetone, the value given by Schwarzenbach for the enol equilibrium constant (K_E = 2·5 x 10^?6) leads to an elementary rate constant for the addition of iodine to the enol (k₂^I₂ = 6·5 x 10⁶ M^?1s^?1). This value is not, however, consistent with k_I2 = 1·5 x 10⁸ M^?1s^?1, the rate constant for the iodination of the corresponding ether 2-ethoxypropene.     

Alcaloïdes des Homalium: Structure de l'homaline,de l'hopromine,de l'hoprominol et de l'hopromalinol

L'étude chimique de quatre alcaloïdes: homaline, hopromine, hoprominol et hopromalinol, isolés de l'Homalium pronyense Guillaum., aétéeffectuée. La structure du principal d'entre eux, I'homaline, est démontrée commeétant celle du butylène 5-5′ di(méthyl-1 phényl-2 oxo-4 diaza-1,5 cyclooctane)-(2S,2′S). Ces quatre bases constituent un nouveau type d'alcaloïde. La présence dans leur molécule deséléments de la spermine permet de les rattacher au groupe des “Alcaloïdes macrocycliques dérivés de la spermine et de la spermidine?d.¹³     

Composes heteroorganiques—XLVII: Les arylsulphonamides de l'acide ethane-ethoxy-thiophosphonique

The synthesis, structure and properties of arylsulphonamides of éthane-éthoxy-thiophosphonic acid 1–6 are described. The compounds exist mainly in the amidothione form. In CCI₄ an equilibrium between monomers and molecules associated through hydrogen bonding is present. Thermodynamic functions of the equilibrium reaction have been determined and the results suggest that the associated molecules are cyclic dimers. The pK-values of 1–6 obey a combination of the Ismajlow-Hammett equations.     

Etude de la complexation des lanthanides trivalents par les isomères de l'acide diaminocyclohexanetétraacétique: Partie 2. Les Constantes d'Acidité et les Constantes de Formation des Complexes 1:1 avec l'Acide trans-1,4-Diaminocyclohexane-N,N,N′,N′-Tétraacétique

(Study of the complexation of trivalent lanthanides by the six isomers of diaminocyclohexanetetraacetic acid. Part 2. Acidity constants and formation constants of the 1:1 complexes of trans-1,4-diaminocyclohexane-N,N,N′,N′-tetraacetic acid)Potentiometric measurements of the acidity constants of trans-1,4-diaminocyclohexane-N,N,N′,N′-tetraacetic acid (trans-1,4-DCTA) and of the stability constants of its 1:1 complexes with the trivalent lanthanides are reported for an ionic strength of 1 (KCl) at 25°C. The behaviour of this ligand is similar to that of monoaminodiacetic acids, suggesting that only one N(CH₂COO^?)₂ group participates in chelation. The selectivity of trans-1,4-DCTA for the lanthanides is better than that reported for the monoaminodiacetic acids.     

Étude de la vindolinine—III: Hémisynthèse de l'andranginine

Thermolysis of Δ¹⁸-tabersonine 3 in methanol solution affords, (±)andranginine 5, (±) épi-andranginine 9a and optically active 6.     

Étude d'équilibres en solution à l'aide des échangeurs d'ions : I Dissociation du perchlorate d'argent et de l'acide nitrique dans les mélanges eau—acide acétique—acide perchlorique ou acide nitrique

A theoretical relationship postulated between the distribution coefficient of a monovalent element and the parameters upon which it depends (acid concentration in solution, dissociation constants of the acid and the salt, selectivity coefficient of exchanged ions) has been verified for the dissociation of silver perchlorate in water—acetic acid—perchloric acid mixtures. The dissociation constants found have been compared with the experimental values obtained by potentiometric measurements. The relationship established has been employed for the determination of nitric acid dissociation constants in water—acetic acid-nitric acid mixtures containing less than 25 % by weight of water. From the results the pK value for nitric acid in pure acetic acid has been evaluated by extrapolation. The theoretical relationship might be used to determine an acid dissociation constant when the dissociation constant of a salt is known and vice versa.     

Dégradation bactérienne de l'acide déhydroabiétique par un Pseudomonas et une Alcaligenes

Two new strains: Pseudomonas sp. and Alcaligenes Eutrophus were isolated by aerobic enrichment at 28° in a medium containing dehydroabietic acid 1a as only source of carbon and energy. Study of isolated intermediates suggests that both species use the same degradative pathway. Attack at C-7 is followed by hydroxylation of the aromatic ring before cleavage of ring B. The outlines of the degradative pathway of dehydroabietic acid by these two species in comparison with Flavobacterium Resinovorum are discussed.     

Constantes d'acidite de l'acide pyrophosphorique et constantes de stabilite des complexes avec le potassium et le sodium: en|The acidity constants of pyrophosphoric acid and the stability constants of complexes with potassium and sodium ions

(The acidity constants of pyrophosphoric acid and the stability constants of complexes with potassium and sodium ions)The effect of potassium and sodium ions on the acidity constants of pyrophosphoric acid is studied by potentiometry at 25°C and at an ionic strength of 0.5 mol l^-1. Comparison of the results obtained in potassium chloride or sodium chloride medium with those found in tetramethylammonium chloride medium provides evidence of the formation of potassium and sodium complexes of the type MHP₂O^2-₇ and MP₂O^3-₇. Stability constants of these complexes are calculated and distribution diagrams of the species as a function of pH are given for the three different media utilized.     

Étude de la complexation des lanthanides trivalents par les six isomères de l'acide diaminocyclohexane-tétraacétique : Partie 3. Relation entre les Constantes d'Acidité et la Structure Moleculaire des Chélatants

(Study of the complexation of trivalent lanthanides by the six isomers of diaminocyclohexanetetraacetic acid. Part 3. Relationship between the acidity constants and the molecular structure of the ligands.)Potentiometric measurements of the acidity constants of the six isomers of diaminocyclohexane-N,N,N′,N′-tetraacetic acid (DCTA) are reported for an ionic strength of 1 mol l^?1 (KCl) at 25°C. The values of the two constants K_a3 and K_a4 are correlated with the maximum N—N distance for each ligand. Ethylenediamine-N,N,N′,N′-tetraacetic acid (EDTA) and some homologous ligands, including specially synthesized, 1,8-diaminooctane-N,N,N′,N′-tetraacetic acid and 1,10-diaminodecane-N,N,N′,N′-tetraacetic acid, are studied under the same conditions. It is proved that there is a relationship between the molecular structure and the affinity for protons.     

Étude cristallographique et vibrationnelle de complexes metalliques de l'acide aminométhylphosphonique

The crystalline structure of the complex between Zn(II) and aminomethylphosphonic acid [Zn(AMPh)₂· 4H₂O] is described. This complex crystallizes as an orthorhombic system (space group Pca2₁, a = 10.001 ± 0.002, b = 12.140 ± 0.002, c = 10.281 ± 0.002 Å; Z = 4). Zinc is tetrahedral and coordinated with 4 oxygen atoms of 4 phosphonic groups. The IR spectra of this complex and its N-deuterated derivative in the solid state are analysed in relation to its structure. By comparison, a vibrational study of two other complexes showed Mn(II) gives the same type of coordination as Zn(II), but Cu(II) binds with both phosphonic and amino groups.     

Cinetique complexe de l'halogenation de cetones en milieu acide—II : Controle par la diffusion des vitesses d'halogenation des enols-consequences

The kinetics of the bromination and chlorination of acetone, diethylketone and di-isopropylketone (bromination only) have been studied at [X₂]_a^o ≈ 10^?7 to 10^?5 M; the apparent rate constants k_II^X₂ = K_Ek₂^X₂ (where K_E is the keto-enol equilibrium constant) for iodination, bromination and chlorination are approximately equal. This result is attributed to diffusion-controlled kinetics. The order of magnitude of such a limiting rate constant, 10⁹ M^?1s^?1 calculated from Smoluchowski's equation, leads to new values for K_E in solution (1·5 x 10^?8 for acetone) much smaller than those in the literature. The rate constants derived for enol ketonisation are then in good agreement with those from proton addition to the corresponding enol ethers.     

Headspace solid-phase microextraction applied to the simultaneous determination of sorbic and benzoic acids in beverages

A new analytical procedure was developed using headspace solid-phase microextraction (HS-SPME) for the simultaneous determination of sorbic and benzoic acids in beverages. The sample were processed depending on their nature, either only diluted with water, or treated with a NaOH solution and filtered through a 0.45-μm membrane filter. The samples were heated in a vial in the presence of sulfuric acid and anhydrous sodium sulfate and the analytes were collected from the headspace by using a 65-μm polydimethylsiloxane-divinylbenzene (PDMS-DVB) coated fiber and determined by gas chromatography with flame ionization detector (GC-FID). To enhance the sensitivity of HS-SPME, the temperature and time of the extraction and desorption, the acidity and salt concentration of the extraction solution were optimized. Linear range of the analytes was found to be between 0.1 and 20 mg/L with regression coefficients (R²) of 0.9998 for sorbic acid and 0.9980 for benzoic acid. Limits of detection (LOD) were 5.83 μg/L and 11.4 μg/L for sorbic and benzoic acids, respectively. Relative standard deviation (R.S.D.) for six replicate analyses within 3 days (two times/day) was found to be lower than 8.62% at three concentration levels (2, 6, 10 mg/L). Recoveries ranged from 81.20% to 108.1% for real samples. The results demonstrate the suitability of the HS-SPME technique to analyze sorbic and benzoic acids in a variety of beverages.     

Etude de la complexation des lanthanides trivalents par les six isomeres de l'acide diaminocyclohexanetetraacetique: Partie 1: synthèses et détermination des constantes d'acidité et des constantes de formation des complexes 1:1 avec les lanthanides trivalents de l'acide trans-1,2-diaminocyclohexane-N,N,N′,N′-tétraacétique

(Study of the complexation of trivalent lanthanides by the six isomers of diaminocyclohexanetetraacetic acid. Part 1. Syntheses, acidity constants of trans-1,2-diaminocyclohexane-N,N,N′,N′-tetraacetic acid, and formation constants of its 1:1 complexes.)The syntheses of five isomers (1,2 cis, 1,3 cis, 1,3 trans, 1,4 cis, 1,4 trans) of diaminocyclohexanetetraacetic acid which are not commercially available are described. For comparison with literature vlaues, potentiometric measurements of the acidity constants of the sixth isomer (1,2 trans) and of the stability constants of its 1:1 complexes with trivalent lanthanides are reported for an ionic strength of 1 (KCl) at 25°C. In contrast to some literature data, the stability constants found, plotted as a function of Z, display only one discontinuity at the level of gadolinium.     

Transpositions a etapes multiples d'epoxydes sesquiterpeniques—I : Action de l'acide formique sur l'epoxyde de cyperene. Correlation entre le cyperene et l'α-cedrene

Cyperene epoxide 2, on treatment with formic acid, gives about ten products of which the two major ones have been isolated and characterised. The allylic alcohol 3 is the product of an allylic rearrangement. The diol 5 is produced by a multistep rearrangement, the mechanism of which is remarkable in that the first elementary step cannot be concerted. The structure of the diol 5 has been confirmed by correlation with α-cedrene.     

Synthèse d'antibiotiques triterpeniques à partir d'acides biliaires—I: Fonctionnalisation en 15 de l'acide apocholique

Allylic oxidation of apocholic acid and some of its derivatives by N-bromosuccinimide in the presence of water and a base is regiospecific leading to 15-keto or 15-hydroxy compounds, depending upon the experimental conditions and the nature of the substrate.