Dérivés propargyliques,XII et dérivés de la décahydroquinoléine,II Alkynyl-4, alkényl-4 et alkyl-4-décahydroquinolinols-4 N-substitués

The authors describe the synthesis of decahydro-4-quinolinones and N-substituted 4-alkynyl-, 4-allyl- and 4-alkyldecahydro-4-quinolinols and discuss the stereochemical problems of this compounds.     

Etude de l'oxydation de tétrahydroisoquinoléinols-4 diméthoxylés en 6,7 ou 7,8, et sur la réactivité du carbonyle de la tétrahydroisoquinolone-4 diméthoxylée en 6,7

Preparation of the tetrahydroisoquinolin-4-ols indicated in the title and their oxidation by different reagents (chromic anhydride, NBA, dimethylsulfoxide, Oppenauer oxidation) is reported. Only the last reaction led to the title compounds, while the other reagents (except NBA) yielded 1,2,3-trioxotetrahydroisoquinoline. Furthermore, the reactivity of 6,7-dimethoxytetrahydroisoquinolin-4-one was examined towards different carbonyl reagents.     

Etude par spectrométrie de masse de l'ionisation de benzonitriles,de phénylacétonitriles et de N,N-diméthylanilines substitués

Molecular ionization potentials for series of compounds of the type X? C₆H₄? CN, X? C₆H₄CH₂? CN and X? C₆H₄? N(CH₃)₂ have been measured using the retarding potential difference technique (RPD. technique). The effect of the various substituents X is better correlated through the electrophilic Brown σ_p⁺ constants than through Hammett's σ_p values. No meta-para orientation effect is observed. For all the disubstituted phenyl compounds studied, the effect of the second substituent is affected by the electron-releasing power of the original substituent. Ionization potentials calculated by using the semi-empirical method of equivalent orbitals are in good agreement with the experimental values.     

Etude de composés d'addition d'acides de Lewis,XXXIV [1] Composés d'addition de benzoquinone-1, 4 avec TiCl4

The adduct 1,4-benzoquine · TiCl₄ has been prepared in CH₂Cl₂ solution at about ?60°. Its IR. spectrum has been recorded at the same temperature. The experimental study of the vibrational frequencies has been completed by the calculation of the fundamental vibrations in the molecular plane, using Wilson's FG method, with slightly simplified models of 1,4-benzoquinone · TiCl₄ (13 masses) and 1,4-benzoquinone · 2 TiCl₄ (14 masses); analysis by use of internal and symmetry coordinates. An assignment of most of the observed bands is proposed and the conclusion is reached that the complex, when solid, is (1,4-benzoquinone · TiCl₄)_n. The force constants F(C? O) are 9,85 · 10⁵ dyne/cm for the quinone and 8,8 · 10⁵ dyne/cm for the disturbed carbonyl bond of the polymerized complex in the model proposed. At ordinary temperature in benzene solution of the components the adduct 1,4-benzoquinone. TiCl₄ · benzene precipitated; with the help of the models, the fundamental vibrations of its IR. spectrum have been assigned.     

Synthèse énantiospécifique de la (+)-(R)-éthyl-6-dihydro-2,3-méthyl-2-4H-pyranone-4, phéromone de la mite Hepialus hecta L

Enantiospecific Synthesis of (+)-(R)-6-Ethyl-2,3-dihydro-2-methyl-4H-pyran-4-one, Sex-pheromonal Component of the Male Swift Moth Hepialus hecta L . A new synthesis of (+)?(R)-6-ethyl-2,3-dihydro-2-methyl-4H-pyran-4-one ((R)- 8 ), sex-pheromonal component of the male swift moth Hepialus hecta L., has been performed from (?)-(R)-1-(1,3-dithian-2-yl)propan-2-ol with an enantiomeric excess of ? 97%.     

Sur la composition de l'arôme de thé

A gas-chromatographic investigation of black tea aroma has revealed, besides 19 known components, the presence of 4 new substances: 1-penten-3-ol, trans-2-hexen-1-ol, α-terpineol and β-ionone. The fragmentation pattern of 1-penten-3-ol has been determined by means of high resolution mass spectrography.     

Préparation de quelques 4-nitroisoxazoles à partir de pseudonitrosites de cétones éthyléniques du type chalcone

The Synthesis of some 4-Nitroisoxazoles from Pseudonitrosites of Chalcones The action of dinitrogen trioxide with α,β-unsaturated ketones of the chalcone type leads to pseudonitrosites (Table 1) which are cyclized to 4-nitro-3,5-diarylisoxazoles (Table 2).     

Transfert d'Hétéroatomes (Cl,Br, OH) lors de la Fragmentation d'Acétyléniques δ-Fonctionnalisés

The mass spectra of three δ-functionalized alkynes provide evidence for the migration of chlorine, bromine and hydroxyl towards the unsaturated portion of the molecules. The strong resemblance between these spectra and those of the isomeric allenes suggests that an acetylene→allene isomerization occurs after electron impact.     

Isomerisation,déshydration et réduction du méthyl-4 dioxa-1,6 spiro[4,5]decanol-4. Obtention de précurseurs ou d'isomères de phéromones de guêpe

The Lewis acid isomerisation of a dioxaspirodecanol mixture, obtained by photochemical means, preferentially gives the cis isomer while acetylation mainly leads to the trans isomer. The theromolysis of the acetates 2 or the xanthates 5 yields a furan compound 4, enventual precursor of a dioxaspirolactone. 6. The xanthate reduction provides an easy access to th e methyl-4 dioxaspirodecane isomers of wasp pheromones.     

Réactions de cyclisation de pentynyl-2 pyrimidones-4

Acetylenic amindines HC≈?C·(CH₂)_n·C(?NH)NH₂ give, by condensation with β-ketoesters, pyrimidones substituted on carbon 2 by an acetylenic chain. Two types of evolution are observed when compounds are heated without any catalyst. The minor route is a cyclization by attack on a triple bond by the amidic nitrogen atom. The main reaction is a cycloaddition involving the non activated triple bond and an azadienic system, leading to non isolated tricyclic intermediates which retrocyclize to stable bicyclic compounds.     

Structure des bases de schiff dérivées de 4-acylisoxazolin-5-ones

The nmr and ir spectra show that Schiff bases of 4-acylisoxazolin-5-ones exist as chelated enaminones type forms. The effects of steric factors on such structures are discussed.     

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.