Conducteurs organiques ternaires: Nouvelle methode de synthese d'ions radicaux entre sels de se ou p et tcnq

New ternary radical ions salts have been prepared by reaction of triiodides of trimethyl selenonium and tetramethyl phosphonium with Li TCNQ in alcohol.     

Arylation catalytique d'organophosphorés. Produits de l'arylation,catalysée par les sels de nickel (II), de composés du phosphore tricoordiné.

Analysis of the products from the nickel (II) bromide catalysed arylation of tricoordinated phosphorus compounds R₂P-Z (Z  H, Cl, SR, NR₂ pointed out that this arylation always takes place on phosphorus resulting at first in formation of pseudophosphonium salts. Only the aminophosphonium salts are stable under reaction conditions; the other salts undergo several transformations which can be brought together in a general reactivity scheme to account for all the side products. On regard to other heteroatoms these results point out a particular ability of phosphorus to be arylated under nickel (II) catalysis.The reaction with secondary phosphines can be applied to synthetise diarylphosphonium salts.     

Reaction des lithiens avec les organophosphores. Reaction d'addition du t-butyllithium sur le noyau benzenique des sels de phenylphosphoniums

A new reaction of organolithium compounds with phosphonium salts is described; reaction of t-butyllithium with dibenzylaminophosphonium or tetraphenylphosphonium bromides takes place through addition of the t-butyl group on a benzene ring at the position para to the phosphorus atom, the ylid formed reacts in a characteristic Wittig reaction with p-tolylaldehyde.     

Sels de pyrylium—XVII: Réactivité des sels de dialcoxy-2,4 pyrylium avec des agents nucléophiles. Formation et propriétés de sels d'amino-2 et de diamino-2,4 pyrylium; sels de dialcoxy-2,4 pyrylium,agents d'alcoylation

Secondary amines react with 2,4-dialcoxy 6-méthyl pyrylium salts to give two new series of 2-amino and 2,4-diamino pyrylium cations. 2,4-Dialkoxy pyrylium salts react as alkylating reagents. A comparison with 1,3-dialcoxy carbonium cations reactivity is reported.     

Note sur quelques complexes entre nicéthamide (N,N-diéthyl-nicotamide) et/ou de la pémoline (phényl-5-imino-2-oxazolidone-4) et divers sels,particulièrement de sels calciques de monoesters aminoalkylphosphoriques

Note on some complexes between nikethamide and/or pemoline with various salts, especially calcium aminoalkylphosphates A number of binary and ternary complexes of nikethamide and/or pemoline with various calcium salts, particularly calcium aminoalkylphosphates, have been prepared in order to assess their pharmacological properties. The formation of such complexes has been established by IR. spectroscopy.     

Nouvelle synthese de sels d'alcadien-1,3 yl phosphonium

A new synthetic route to alcadien-1,3 yl phosphonium salts is given.     

Effets de sels dans la reaction de trialkylaluminium avec le benzaldehyde

Tetra-n-butylammonium halides and, to a lesser extent alkali fluorides, enhance the addition/reduction ratio in the reaction of trialkylaluminium with benzaldehyde in ether, and lower the reactivity of the organoaluminium compounds. These results are consistent with the existence of complexes between salts and organoaluminium compounds [MX•R₃ Al (1/1) and MX•2R₃ Al (1/2)]. The more stable the complex, the more important are the effects I⁻ Br⁻ Cl⁻ F⁻ and NaF KF Bu₄ NF. The 1/1 complexes are more stable and less reactive than their corresponding 1/2 complexes.     

Effets de complexation de l'ester lors de la catalyse par l'eau ou les sels de l'hydrolyse alcaline des esters maloniques: etude cinetique,spectroscop

When water or salts are added, catalytic effects on alkaline hydrolysis of malonic esters in methanol are observed; they are definitely greater than those observed with monoesters. Kinetic data in the presence of salts suggest that ester-M⁺ complexation phenomena is predominant and prevails over HO^-, M⁺ ionic association. Infrared and Raman spectra of esters in water-alcohol mixtures, with or without added salts, indicate the formation of 1:1 and 1:2 complexes with each carbonyl of the diester and one proton donor molecule as well as with Li⁺.Ab initio calculations of these diesters and of their complexes allow the estimation of the positive charge density at the carbonyl group carbon as well as the LUMO energy levels; they lead to an interpretation of these entities reactivities according to perturbation theory. Only orbital control of alkaline hydrolysis of esters gives an account of the relative reactivities of mono- and diesters with or without added salts. The only consideration of charges at the carbonyl carbon is, on the other hand, inadequate for justifying all the observed phenomena.     

Étude thermochimique des sels de nickel et de cuivre de quelques amino-acides

Standard enthalpies of formation of:nickel and copper salts of several amino acids (α-alanine, valine, norvaline, isoleucine, norleucine);mixed complexes of copper:. Cu(α-alanine) (valine), Cu(α-alanine) (isoleucine), and Cu(valine) (isoleucine) are determined by calorimetry.The variations of enthalpy linked to the transformation of amminated and hydrated salts of the valine and of the isoleucine into the corresponding anhydrous compounds were determined by two different procedures: indirect calorimetry and differential calorimetric analysis.     

Determination coulometrique d'alcaloides et de sels de bases organiques apres precipitation sous forme de tetraphenylborates

A coulometric microdetermination of salts of certain organic bases and alkaloids is described, based on precipitation as the tetraphenylborates and the coulometric determination of the tetraphenylborate content of the precipitate with electrogenerated silver ion. Eleven compounds were determined with satisfactory accuracy.     

Composes organiques du phosphore XIII (1) apercu sur les sels de phosphonium di- et tri-acetyleniques. Nouvelle methode de synthese de sels de phosphonia-4-pyrannes.

In opposition to the di- and tri-acetylenic phosphonium salts bearing phenylethynyl groups which are readily hydrolyzed, phosphonium salts bearing two tert-butylethynyl groups are quite stable in the presence of water.With acetic acid in presence of ammonium acetate, these cations add one molecule of water and yield the 4-phosphoniapyrane salts instead of the corresponding nitrogen heterocycles.     

Etude par analyse thermique des sels de calcium de quelques acides alcanesulfoniques

Calcium salts of some alkanesulphonic acids have been prepared. Most of them are new. Their dehydration and the decomposition of anhydrous salts have been studied by thermogravimetric analysis (TG) and by thermal differential analysis (DTA) under ordinary pressure. In an inert atmosphere the sulphides formed indicate that carbon-sulphur and oxygen-sulphur bonds have been broken. The mechanism of decomposition of the calcium alkanesulphonates seems to be more complicated than that of the corresponding carboxylates.     

Eliminations competitives lors de la decomposition basique de sels de N-alcoxypyridinium—I: Competition entre intermediaires ylure ou anhydrobase et ions hydroxydes dans l'arrachement des protons en α ou β dans la chaine alcoxyle2

A novel mode of base-induced decomposition of N-alkoxypyridimum salts carrying a β-hydrogen in their alkoxy chain is described. In these compounds the N-oxide moiety can act as a leaving group in an elimination reaction yielding an ethylenic derivative, in competition with the classical decomposition to aldehyde and pyridine. This latter is predominant in salts 9 and 10 bearing a methyl group in 2 or 6 positions of the pyridine nucleus, whereas the new mode of decomposition becomes almost exclusive for salts 7 and 8 unsubstituted in these positions. Deuteration studies show that proton abstraction does not occur by transfer to an ylide during the decomposition by hydroxide ion, proton abstraction results from direct attack by hydroxide ion except for the α-proton of salts bearing at least one methyl group in 2 or 6 positions where it occurs by a transfer (essentially intramolecular) to an intermediary anhydrobase.     

Etude par RMN du mecanisme des reactions de transcomplexation entre les sels de chloroiminium (reactifs de vilsmeier) et les amides ou thioamides. Appl

Previous studies have established the existence of an acid-base equilibrium between the Vilsmeier complex (Me₂NCHCl)⁺ B^? and dimethylformamide. It is shown that the behaviour of chloroiminium salts as Lewis acids towards amides or thioamides is a general phenomenon. When the acids and bases are differently substituted, the reaction may have synthetic applications.     

Spectres de vibration de l'acide cyclopropane dicarboxylique-1.1 et de ses sels de potassium en solution aqueuse

Raman and infrared spectra of the cyclopropane-1.1 dicarboxylic acid and its potassium salts in aqueous solution were recorded from 100 to 4000 cm⁻¹. An assignment of the observed lines as fundamentals is proposed. The analysis of the polarization of the Raman lines indicated that the salts belong to the C₂ group. The intramolecular hydrogen bonds which exist in the acid, persist in aqueous solution in both the acid and the acid salt.     

Proprietes solubilisantes et structure des solutions aqueuses de sels biliaires dihydroxyles

The solubilizing properties of aqueous solutions of isomeric salts, deoxycholate, chenodeoxycholate and ursodeoxycholate for naphthalene and cholesterol have been studied. For both molecules, ursodeoxycholate micelles have the poorest detergent power. Binding of naphthalene to micelles modifies the chemical shifts of the angular methyl groups of the bile salts as determined by ¹H NMR. A greater pertubation of the C₁₉ methyl signal relative to that of the C₁₈ methyl signal is observed with deoxycholate and chenodeoxycholate but not with ursodeoxycholate. These results suggest a distinct micellar structure for ursodeoxycholate.     

Rôle catalytique de l'eau et des sels lors de l'hydrolyse alcaline des esters en milieu hydro-alcoolique: Mise en évidence par spectrométrie ir des associations ester-solvant et ester-cation

Infrared spectra of esters in water-alcohol mixtures, with or without added salts, indicate the formation of 1:1 or 1:2 complexes through hydrogen bonding between the ester carbonyl group and the proton donor molecules of the solvent, as well as the formation of a donor-acceptor complexes with Li⁺ or Ba²⁺. These complexes facilitate nucleophilic attack at the carbon of the carbonyl group by hydroxyl anions. Depending on the water content of the mixture, the addition of LiCIO₄ increases or decreases the rate constant of the reaction. The displacement of equilibria between different entities explains a higher rate constant in water-tert-butanol than in water-methanol mixtures of the alkaline hydrolysis of ethyl acetate.     

α-Ferrocenylalkylation of 1,5-Disubstituted Tetrazoles and Certain Transformations of Reaction Products

The reaction of -hydroxyferrocenylalkyl derivatives and vinylferrocene with 1,5-disubstituted tetrazoles in methylene chloride-aqueous acid HX (X = BF4, ClO4) two-phase systems gives a mixture of 1,3,5- and 1,4,5-trisubstituted tetrazolium salts, the fraction of the 1,3,5-isomers prevailing. The synthesized salts are readily dealkylated under the action of bases to give the above starting compounds. Heating of 3(4)-(ferrocenylmethylene)-1,5-pentamethylenetetrazolium and 3(4)-(ferrocenylmethylene)-2-methyl-1-phenyltetrazolium tetrafluoroborates in anhydrous methanol or ethanol in the presence of catalytic amounts of alkali gives rise to ferrocenylcarbinol ethers. Other nuclephiles (pyridine, triphenylphosphine, sodium thiocyanate, sodium p-toluenesulfinate, dibenzoylmethane) also react with the above tetrazolium salts, forming ferrocenylmethylation products. Heating of equimolar amounts of 3(4)-(ferrocenylmethylene)-1,5-pentamethylenetetrazolium or 3(4)-(ferrocenylmethylene)-2-methyl-1-phenyltetrazolium perchlorates with mercury(II) perchlorates in anhydrous ethanol results in mercuration of the starting tetrazolium salts, involving hydrogen substitution in the methylene or methyl groups bound to tetrazolium carbon atoms. The condensation of the same salts with p-N,N-(dimethylamino)nitrosobenzene, leading to azomethine formation, occurs under similar conditions.     

La formation de sels augmente-t-elle la fréquence des dédoublements spontanés?

The resolution by entrainment which allows the pure enantiomers to be obtained by direct crystallization of the racemate is possible only when the racemate is a conglomerate (eutectic mixture). Spontaneous resolutions exist to an extent less than 10% of the crystalline racemates. Considering a family of racemic salts formed by a racemic acid or racemic base and a racemic or an achiral counterion, we show by a statistical analysis, which has required the preparation of more than 500 salts, that the probability of finding spontaneous resolution is 2 or 3 times greater than in the family of covalent racemates. The preparation of some phosphonic acids, which could be useful as new resolving agents is described.     

Identification et Etude en Résonance Magnétique Nucléaire du Carbone-13 des Produits de la Réaction de Quaternisation en Série Thiazolo[3,2-d]tétrazolique

We have demonstrated that the compounds obtained by quaternization of thiazolo[3,2-d]tetrazole, and two of its derivatives, 3-phenyl-thiazolo[3,2-d]tetrazole and tetrazolo[5,1-b]benzothiazole, are tetrazolium salts. The quaternization effects are discussed as a function of the ¹³C NMR results.