Marcel Miocque

Cyclisation par amination intramoléculaire dans la série de la pyrazine.

Abstract An original one-pot ayntheais of 4,7-diazaindoles is achieved by metalation of methylpyrazines or methylquinoxaline wich are then condensed with an aromatic nitrile: an intermediate imine-enamine is formed which leads, by intramolecular cyclization, to diazaindoles.

Reactions selectives de l'o.chlorobenzontrile : SNAr

Abstract O.Chlorobenzonitrile reacts with carbanions from methylpyrazine in liquid ammonia, affording selectively arylmethylpyrazine derivatives.

Selective N-prop-2-ynylation of heterocycles induced by solid–liquid phase transfer catalysis without solvent and use of solid inorganic supports

Complementary processes promote the N-prop-2-ynylation of heterocycles: solid-liquid phase transfer catalysis without added solvent in the presence or absence of alumina or titanium dioxide and alkylation on ‘basic’ alumina in ‘dry media’.

Nesting inclusion compounds : the X-ray structure of the 15-crown-5 sodium diphenylethyl diphenylmethyl cyanoacetonate complex

The action of sodium cyanide ongem -diphenyl-chloropropanone under phase transfer conditions in the presence of 15-crown-5 yields the title compound as a minor product. The crystal structure of this complex reveals that, in the solid state, the [15-crown-5-Na+] guest species is found within a loose cage of diphenylethyl diphenyl cyanoacetonate molecules with one open side of the cage blocked by an adjacent 15-crown-5 molecule. Colourless crystals of the compound belong to the monoclinic space groupP21/n witha = 12,255(2) Å,b = 13,005(1) Å,c = 23,433(2) Å, β = 95,92(1) ° andDc = 1.23 g cm−3 forZ = 4.

Synthese de tetrahydrodibenzofurannes : creation d'un carbone quaternaire par transposition de claisen.

Abstract A new route to tetrahydrodibenzofurannes is described. It is based upon Claisen transposition of an aryloxycyclohexene to o .hydroxyphenyl cyclohexene which is, in turn, cyclized by palladium acetate. In the studied example, an overall yield of 45 % is obtained in two steps. The isolation of an unexpected minor isomeric transposed compound sets a problem of mechanism.

Effect of an antihypertensive hydrazine derivative on Ca2+ current of single frog cardiac cells

The effects of MP 518, an acylated 2-chlorobenzylidene hydrazidone derivative with antihypertensive properties were investigated on the Ca current, ICa, recorded under whole-cell patch-clamp in single frog ventricular cells. MP 518 (1-100 microM) had no effect on ICa under control conditions. However, at 10 microM it significantly increased the beta-adrenergic stimulated ICa, an effect similar to that of isobutylmethyl-xanthine (IBMX), a non-specific phosphodiesterase inhibitor. The effects of MP 518 and IBMX were not, however, additive. This positive effect was also observed with both compounds, MP 518 and IMBX, when a submaximal dose of cyclic AMP was intracellularly perfused. In the presence of IBMX or at a high concentration (100 microM), MP 518 had a negative effect on beta-adrenergic stimulated ICa. It was thus considered that the main effect of MP 518 is an antiphosphodiesterase activity, since the increase in ICa induced by low concentrations of MP 518 could be related to inhibition of cAMP degradation; however, at higher concentrations, MP 518 antagonizes beta-adrenergic stimulation, possibly at several levels. Such an antiphosphodiesterase activity can account for the vasorelaxant effects as well as the tachycardic effects of MP 518.

Enehydrazines derivees de la pyrazoline

Abstract Two cyclic enehydrazines are synthesized from acetylenic epoxides : one of them is stable, the other one, not isolable, duplicates to a tricyclic spiran whose structure is discussed.

Passage of allophanoyl-gamma-lactones through the kidney

SummaryIn order to establish if allophanoyl-γlactones (B compounds) can pass through the kidney or if only the corresponding 6-hydroxybarbiturates (A compounds), formed by intramolecular alcoholysis, are able to do so, nine experiments were performed to study the urinary excretion of four different allophanoylγ-lactones B after administration to dogs. Excreted compounds were extracted, identified and quantised. From the amounts of unmodified administered lactones that were recovered, it is concluded that B compounds can pass through the kidney before isomerisation into the corresponding barbiturates A.

A new synthesis of 1-hydroxyisoindoles

Heteroarylmethylation of halogenobenzonitriles in the presence of air (O 2 ) gives 1-hydroxy-3-oxo-1-aryl-1H,3H-isoindoles in liquid ammonia. A one-pot or two-step synthesis is described and a mechanism is proposed

Modified Cyclodextrins; Substitution at O3 and Complexation of Metals

Chemical modification of 2,6-O-Dimethyl-β-Cyclodextrin leads to 3-O-Allyl,2-6-O-Dimethyl-β-Cyclodextrin, I; 3-O-Epoxypropyl,2,6-O-Dimethyl-β-Cyclodextrin, II; and 3-0-(1-Dimethylamino-2-Hydroxypropyl),2,6-Dimethyl-β-Cyclodextrin, III. The stereochemistry of these compounds was studied using the SYBYL Molecular Graphics program and by 500 MHz NMR which showed the 2-O-Methyl protons in II to be highly sensitive to solvent effects. Reaction of I with RhCl3 leads to a compound proposed as cyclodextrin dimer containing Rh coordinated to olefinic groups.