Preparation et oxydation de dialkylgermyl- et stannyltetraphenylporphyrines

Some new organo-germanium and -tin tetraphenylporphyrins were obtained. Their behaviour in solution shows that they are readily oxidized into peroxides by light and oxygen. Some of these derivatives must be prepared under especially mild experimental conditions, indicating a surprising unstability for metal IVB — carbon bonds.     

Synthese et reactivite des F-alkyl sulfures et sulfones actives

In this paper we report syntheses of F-alkyl compounds such as R_FC₂H₄S(O)_nCH₂Z (with n=0,2 and Z=H,Ø(C₆H₅),COØ,COOEt,COCH₃,CN). Using the carbanionic reactivity of these compounds, we would like to use them as precursors of surfactants, grafting hydrophilic functions on the carbons α or α′ to the sulfur atom. The compounds were not very reactive. Alkylation or acylation on this site could only be obtained with a ‘pseudo malonic’ CH₂ (R_FC₂H₄SO₂CH₂Z with Z=COØ, COOEt,COCH₃,CN). Only methyl iodide and acetyl chloride led to positive results.     

Synthese et Comportement Polarographique Des Cis et Trans Azoxycyclohexanes

Abstract

In order to compare the polarographic behaviour of cis and trans aliphatic azoxy compounds, synthesis and polarographic study of cis and trans azoxycyclohexanes are performed. The cis form is a new compound obtained by photoisomerisation of the trans compound. In acid medium the polarographic reduction process is the same for both forms: hydrazocyclohexane is the final reduction product. In alkaline medium the trans azoxy compound is electroinactive and the cis azoxy compound is reducible and leads to a mixture of trans azocyclohexane and hydrazocyclohexane.     

Boronates allyliques,alleniques et propargyliques: Preparations et proprietes

An easy synthesis of linear cyclic 2-unsaturated boronates via organometallic reagents has been achieved. The final structure of the carbon framework is related to the tetracoordinated intermediate. Intermolecular rearrangement, disproportionation and reactions with carbonyl compounds have been studied.     

Tetrahydro-1,2,3,4 pyrimidines et octahydro-1,2,3,4,5,6,7,8 quinazolines dithiones-2,4 et diones-2,4 synthese et etude du mecanisme

A synthesis of tetrahydropyrimidine-dithiones and octahydroquinazoline-dithiones has been realized by direct action, in basic media, of alkyl or aryl isothiocyanates on ketones possessing at least an hydrogen atom in an α-position. The clarification of the complex mechanism of this reaction has been attempted. It is possible to reach corresponding diones by desulphurization of the dithiones.     

Mono et Diglycosylbutadiynes

Mono and Diglycosylbutadiynes Cadiot's dissymmetric coupling of bromoethynylsugar derivatives with therminal acetylenes led in good to excellent yields to the expected mono or diglycosylbutadiynes. In the same way, terminal acetylenic sugar derivatives could be coupled with bromoacetylenic compounds. Symmetric coupling of sugars bearing a bromoethynyl group has also been achieved. (UV., CD., IR., ¹H-NMR.) of these compounds are reported and discussed.     

Annotationes et Errata

Sans résumé     

Solubilite et diastereoselectivite

Organometallics can react with a substrate in the solid state. This can deeply influence the diastereoface selectivity of a reaction.     

Polythioamides aromatiques: Synthese et etude des comportements thermique et ensolution

Aromatic polythioamides are obtained by polycondensation of alkyl and/or carboxymethyl bis(dithioesters) with aromatic or aliphatic diamines in aqueous or organic solvents. We have identified the effect of aromatic rings on the behaviour of polymer in solution and thermal features on these condensation polymers. Their thermal stability is improved over that of aliphatic compounds, especially when the ring and the functional groups are conjugated.     

Etude Electrochimique et Differenciation de Derives des Dibenzodiazepines et des Dibenzothiazepines

Abstract

New psychotropic drugs like Clozapin and Clothiapin were separated and differenciated using D.C., A.C. and D.P.P. polarographic techniques. The mechanism of the electrode reaction is elucidated.     

Fragmentation Sous Impact Electronique de la Pyrrolidine et D'Isoindolines N-Nitrosees et N-Aminees

Mass spectral fragmentations of N-nitroso and N-amino derivatives of pyrrolidine, isoindoline and diphenyl isoindoline have been studied. Medium resolution and site specific deuterium labelling lead us to suggest fragmentation pathways.     

Alcoolyse et glycolyse de derives organozinciques et organocadmiens par des composes chiraux

The reaction between organozinc or organocadmium derivatives and different chiral hydroxy compounds leads to the corresponding alcoholates and glycolates which can be used as initiators in polymerizations.The composition of such initiators is defined by the ratio i_S = R-M-O/O-M-O of the number of alkylalkoxy groups to the number of dialkoxy groups. This ratio depends on the nature of the organometallic and hydroxy compound and on the conditions of reaction used to prepare them.Toward a given hydroxy compound, the reactivity of the organometallic derivatives follows the order: ZnEt₂ > CdEt₂ > CdMe₂.Primary alcohols and 1,2-diols are more reactive than secondary alcohols in the case of organozinc compounds, while in the case of organocadmium compounds the secondary alcohols are more reactive than primary alcohols, but less reactive than 1,2-diols. The kinetics of the reaction can be followed by monitoring the variation of optical activity of the solution.Several compounds having definite stoichiometry have been isolated and identified by their NMR spectra.     

Synthese photochimique et etude structurale d'alcoxy-spirocetals et de trioxa-bis-spirocetals

The spiroketal systems can be obtained easily by a Norrish type II reaction applied to tetrahydropyranic ketoacetals having a carbonyl group in δ position of the acetalic hydrogen. The structures of spirans and bispirans established by IR, NMR (¹H and ¹³C show an axial conformation for the C-O bond of the tetrahydrofuran ring. With the bispirans this anomeric effect requires for some isomers a twist boat conformation of the tetrahydropyran ring.     

Conversion des furfurylalkyl et arylcetones en derives de l'isocoumarine et de l'isoquinoleine

Cycoladducts of furfurylakyl and arylketones with methyl acetylendicarboxylate undergo acid-catalysed rearrangement in high yield to 6-hydroxyphthalates bearing an acetonly or a phenacyl group in the 3-positionl. These phthalic compounds are useful intermediates for the synthesis of polyfunctional derivatives in the isocoumarin and the isoquinoline series.