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.     

Régiospécificite et stéréosélectivite de la cycloaddition de l'oxyde de benzonitrile sur la phényl-5 A-3-pyrazoline

An example of stereospecific and stereoselective reactions is described concerning the cycloaddition of benzonitrile oxyde with 1,2-dimethyl-5-diphenyl-3-pyrazoline. The structure of the two epimeric 5,6-dimethyl 3,4-dimethyl[4,3-d]pyrazolidinoisoxazo-lines-2 was proved by the means of chemical and physical methods. The conversion of one epimeric product to another more stable is achieved and discussed.     

Catalyseurs Ziegler-Natta supportés sur MgCl2 pour la polymérisation du propène. I. Etude de la réaction entre le triéthylaluminium et le benzoate d'ethyle

In this article we describe a study of the reaction between triethylaluminium (TEA) and ethylbenzoate (BE) in a heptane solution by Fourier transform, infrared (IR), and ultraviolet (UV) spectroscopy. These compounds were chosen as a model of the cocatalytic solution used with a Ziegler-Natta catalyst supported on MgCl₂ for the stereospecific polymerization of propene. In the polymerization concentration range a 2 TEA:1 BE yellow complex was added to the solution and no free BE could be detected at a AI/BE molar ratio above 2: the solution contained only free and complexed TEA. The complex decomposed spontaneously to a colorless aluminium alcoholate. The rate of decomposition remained slow at room temperature and the reaction was enhanced by heating or by a high AI/BE ratio or high AI concentration. The decomposition was inhibited in the presence of an olefin.     

Reaction de redistribution entre le tripropylbore et ses produits d'oxydation: Etude par résonance du Noyau 11B

A study by B¹¹ NMR of the system tripropylborane–boron trioxide shows that scrambling reactions occur between the alkylborane and its oxidation products; this involves a redistribution of the mono-(? C₃H₇) and difunctional (? O? ) substituents attached to boron, leading to molecules of varying size and structure.     

Etude du mécanisme de la réaction de hantzsch des thiazoles. I. Mise en évidence et détermination des produits intermédiaires et de dégradation

The Hantzsch thiazole synthesis from α-haloketones and thioamides, proceeds via intermediates that can be isolated under certain conditions. These have been identified, mainly by nmr spectroscopy, as thioimidate derivatives. The chain or cyclic structures of these compounds depend upon the nature of the substituents. Their dehydration gives together with the expected thiazole, secondary products which have also been isolated and identified as α-mercaptoketones and α-ketothiolesters.     

Le blocage de la lysine par la réaction de MAILLARD. I. Synthèse de N-(désoxy-1-D-fructosyl-1)- et N-(désoxy-1-D-lactulosyl-1)-L-lysines

The authors describe a specific method for the preparation of N?-(1-deoxy-D-fructosyl)-L-lysine, Nα-(1-deoxy-D-fructosyl)-L-lysine, their formyl derivatives, and Nα-formyl-?-(1-deoxy-D-lactulosyl)-L-lysine, as well as Nα, N?-di-(1-deoxy-D-fructosyl)-L-lysine. After purification by cation-exchange chromatography using volatile pyridine-acetic acid or pyridine-formic acid buffers, these compounds are obtained in the pure state. By thin-layer chromatography and paper electrophoresis these lysine derivatives can be rapidly separated and identified.     

Synthèse de spiro-pyrazolines par cycloaddition du diazométhane sur des sucres insaturés ramifiés. Influence de l'isomérie géométrique sur l'orientation de la réaction Communication préliminaire

The orientation of the cycloaddition of diazomethane on unsaturated branchedchain sugars has been studied. For 3-C-cyanomethylidene-3-deoxy-1,2-O-isopropylidene-α-D-glycero-tetrofuranose the orientation was ‘normal’ and did not depend on the configuration at the double bond. The same situation prevailed with derivatives of 3-deoxy-1,2:5,6-di-O-isopropylidene-3-C-methylidene-α-D-xylo-hexofuranose. For the 3-C-acylmethylidene- and the 3-C-cyanomethylidene-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-ribo-hexofuranoses, the trans-(H–C(3′)–C(2))-isomer gave the ‘normal’ cycloadduct whereas the cis-isomer gave predominantly the αabnormal spiro-pyrazoline. This observation represents the first instance where the regioselectivity of a cycloaddition reaction is affected by the geometrical isomerism of the dipolarophile. The most probable explanation of the phenomenon is the conformational perturbation about the C(4)--C(5) bond of the unsaturated sugars induced by a change in the configuration at C(3). The consequence of that ‘conformational transmission’ of a difference in configuration at C(3) is that the steric crowding on the cis- than in the trans-isomer. Several novel examples of a new series of C-glycosylidenic derivatives, the spiro-pyrazolines, are described.     

Peroxydation du dihydro-2,3 4H pyranne et du dihydro-2,3 furanne. Etude de réactivités

Free radical reactions of unsaturated O-heterocycles with t-butyl hydroperoxide in the presence of cuprous salt gives peroxides. Their analysis leads to the determination of reactivities in H-abstraction. Allylic hydrogen is ten times more reactive than hydrogen in the α position of the heteroatom.     

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.     

La Vitamine B6 et ses Dérivés. I—Attribution des Spectres de Résonance 13C du Pyridoxol,du Pyridoxal et du Phosphate de Pyridoxal. Etude de la Protonation

The existence of two potential sites for protonation in the molecules pyridoxol and pyridoxal produces characteristic effects in their ¹³C nuclear magnetic resonance spectra. The analysis of these effects permits both the confirmation of assignments proposed by others and the establishment of the nature of the species existing in solution as a function of the pH. In particular it appears that, at pH values in the neighbourhood of 7, both substances exist essentially as zwitterions, pyridoxal adopting the hemiacetal form.     

Hétérocyclisations intramoléculaires par réaction d'oxymercuration III. Régiosélectivité et stéréosélectivité de l'oxymercuration intramoléculaire de phénols orthoallyliques

The intramolecular heterocylization of ortho-allylic phenols by oxymercuration has been realized with compounds having different substituents on the allylic chain. In all cases, only the corresponding benzofuran is formed. However, with a substituent at the terminal carbon of the double bond, we also observed the formation of benzopyran. The influence of the solvent and the mercuric salt on the orientation of this reaction has been examined. There is evidence of a molecular rearrangement during the reduction.     

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).     

Sur la réaction de reformatsky : I. Préparation et réactivité des organozinciques issus de divers crotonates d''alcoyles

Lithiation of (Me₃Si)₃CH by methyllithium (ether-THF) yields (Me₃Si)₃CLi and by t-butyllithium (C₅H₁₂-TMEDA) yields (Me₃Si)₂CHSiMe₂CH₂Li. Only starting material is recovered when (Me₃Si)₃CH is allowed to react with n-butyl- lithium (ether-THF and C₅H₁₂-TMEDA) and t-butyllithium (C₅H₁₂ and C₅H₁₂- THF). (Me₃Si)₄C is lithiated by t-butyllithium (C₅H₁₂-TMEDA) to give (Me₃Si)₃- CSiMe₂CH₂Li, but not by methyllithium (ether-THF and ether-THF-TMEDA). The structures of the lithiated compounds are based on the carbonation products. The above results are explained in terms of carbanion stability and steric effects. Spectral data are reported on the α-silylacetic acids.     

Etude thermometrique de la formation des complexes du fer(III), de l'aluminium et du gallium : Oxalates et malonates

Apparatus and experimental techniques are described for the thermometric detection of the stepwise formation of trivalent cation complexes with oxalate and malonate anions. The three iron and aluminium malonates were confirmed by this method but only two of the three oxalates could be found.     

Recherches sur la formation et la transformation des esters LXXXI [1]. Sur la réaction d'isothiocyanates avec l'acide hydrazinoéthylphosphorique,et de l'isocyanate de phényle avec l'acide colaminephosphoreux

Hydrazinoethyl phosphoric monoester has been prepared by reacting hydrazinoethanol with polyphosphoric acid, and isolated as di-sodium salt. Sodium hydrazinoethyl phosphate reacts with phenylisothiocyanate (in H₂O+ethanol) to yield mainly the derivative thiocarbamoylated at the substituted nitrogen atom. This derivative, heated for one night at 100° in 0.5 N HCl, is cyclized to 3-amino-2-phenylimino-thiazolidine in 62% yield. Sodium hydrazinoethyl phosphate reacts with o-methoxycarbonylphenyl isothiocyanate (in H₂O+dioxane) at the unsubstituted nitrogen atom to yield mainly the corresponding quinazoline derivative (IV, X = OPO₃Na₂). This derivative, heated for one night at 100° in 0.5 N HCl, is cyclized to 2-o-carboxyphenylamino-dihydro-δ²-1, 3, 4-thiadiazine (Va) in 55% yield (hydrolysis of the lactamic function as well). Aminoethyl phosphorous monoester (colaminephosphorous acid) reacted with phenylisocyanate (in H₂0+dioxane) in slightly alkaline medium (one equivalent of NaOH) yields sodium N-phenylcarbamoylaminoethyl phosphite. Refluxed for 20 minutes in 1N NaOH, this carbamoyl derivative is not cyclized but only hydrolyzed to the open-chained N-phenyl-N′-hydroxyethylurea (VII).     

Substitution électrophile aromatique dans l'anhydride sulfureux liquide. Influence de la concentration en bromure et rôle du solvant sur la réactivité des anisoles au cours de la réaction de bromation

Electrophilic Aromatic Substitution in Liquid Sulfur Dioxide. Kinetic Dependance of Rate on the Bromide Concentration and Influence of the Solvent during the Course of the Reaction On the reported data for bromination of anisole and eleven of its derivatives in liquid SO₂, it was shown that, with a large excess of bromide, the rate of reaction, obeys a first-order law. Rate constants thus obtained do not discriminate between the two different forms of bromide, e.g. Br₂ and Br^?₃ present as the A⁺Br^?₃ form, and corrections were made by use of the apparent equilibrium constant K′ for tribromide formation. The variations of rate constants with initial concentration of bromide has been studied and the effect results in a retardation of the bromination rate. Moreover, the ratio [Br₂] [A⁺Br^?]_T, which is constant during an experiment, varies with initial bromide concentrations, this variation affecting the total rate. To account for the bromide effect on the reactivity, variations of k^o,p_g {1 + K′[A⁺Br^?]_T}VS[A⁺Br^?]_T were studied over a 0.01 to 1M range of bromide concentration. The mechanism proposed shows that liquid SO₂ helps the reactive intermediate to be deprotonated and because of solvation of reactive species this step would probably be rate determining. Bromination by molecular bromine is more sensitive to substituent effects in liquid SO₂ than in water. This result is ascribed to the +M effect of the methoxy group which increase the conjugation of ortho-substituted derivatives (p⁺_p = ?7.83; p⁺_o= ?10.47).     

Les Amines Biogènes (Phénol- et Catéchol-Amines): Attribution des Spectres de Résonance 13C et Etude de la Deprotonation

A number of phenol- and catechol- amines has been studied in aqueous solutions at acidic and alkaline pD by means of ¹³C NMR. Resonance assignments are achieved for the fully protonated forms and the influence of the side chain on the aromatic carbons is studied. The shielding effects associated with the various types of side chain tend to follow an additive relationship. The pD dependence of the ring and side chain carbon resonances in phenolamines is accounted for by considering the sum of two separate and opposite effects related to ring and side chain deprotonations. Such a simple model fails to apply to the catechol derivatives. This difference is discussed in terms of the orientational dependence of the deprotonation shifts. It is shown that the protonated amino group is the less acidic group in phenol- and catechol-amines.     

Diénamines hétérocycliques. III. Réexamen de la réaction de la base de Fischer avec le tétracyanoéthylène

Heterocyclic dienamines III. A re-examination of the reaction of Fischer's base on tetracyanoethylene Depending on the order of addition, Fischer's base 5 (1,3,3-trimethyl-2-methylidene-indoline) reacts 1:1 with tetracyanoethylene to give either the tricyanovinylation product 6 or the spiro compound 7 . A skeletal rearrangement of a zwitterionic intermediate can explain the formation of the spiro compound. The latter undergoes a thermal isomerization yielding by ring expansion the tetrahydroquinoléine 8 . On reaction with LiAlH₄ or CH₃ONa 7 and 8 lead both to triazatetracycles. All structures are assigned on the basis of spectral data.