Jean-Marie Catel

SYNTHESE ET ETUDE ELECTROCHIMIQUE DE POLY(ALKYL-3 SELENOPHENES)

Abstract Synthesis of 3-alkyl selenophenes via chloromethyl ketones and acetylenic chlorhydrins is described. The electropolymerisation yields electroactive and soluble polymers with high conductivity in the doped state.

Redox chemistry of thiophene, pyrrole and thiophene-pyrrole-thiophene oligomers

Abstract Electrochemical properties of oligopyrroles and thiophene-pyrrole-thiophene oligomers, which are key-step intermediates in electropolymerization processes, have been investigated by means of fast electrochemistry, flash photolysis and pulse radiolysis techniques. From this studies, conclusions have been drawn concerning the reactions involved in the polymer formation, π-dimerization, carbon-carbon bond formation, deprotonation and the nature of coupling positions,

A critical survey on the preferred conformations of diphenyl disulphone, dimethyl- and diphenyl-dichalcogenides, bis(3-thienyl)-disulphide and -disulphone

Abstract A detailed analysis of the dipole moments of diphenyl disulphone as a benzene solute showed that the compound in solution exists as an equimolecular mixture of ψ -enantiomers characterized by a (O 2 )S–S(O 2 ) rotational angle of ψ =118° in modulum, whilst in the crystal phase the molecules exhibit the s- trans structure ( ψ =180°) (C.H. Kiers, A. Vos, Rec. Trav. Chim. Pays-Bas 91 (1972) 126). Also from a dipole moment analysis, the preferred conformations in solution of dimethyl- and diphenyl-dichalcogenides, R 2 X 2 with X=S, Se or Te, are determined and the results compared with previous studies. The actual structures of all these compounds in the non-condensed phase can be explained on classical grounds, at least qualitatively. The 1 H and 13 C NMR spectra of various 3-thienyl sulphides and sulphones, disulphides and disulphones including bis(3-thienyl)-disulphide and -disulphone, two novel compounds, were recorded and analysed in terms of the sulphur or sulphonyl mesomeric effect. Rotational isomerism for these compounds is also discussed, in the light for the sulphones of a molecular modelling for bis(3-thienyl) disulphone.

SYNTHESE DIRECTE DE METHYL-3 ET DE DIMETHYL-2,4 SELENOPHENES ET TELLUROPHENES

Abstract 3-Methyl and 2,4-dimethyl selenophenes and tellurophenes can be prepared in a convenient synthesis from acetylenic chlorohydrins without the need for hydrogen selenide and telluride.

Conducteurs Organiques: Synthèse, structure et études physiques de sels de l'anion radical du tétracyanoquinodiméthane avec des cations dithiole-1, 2 ylium et disélénole-1, 2 ylium

Abstract New TCNQ anion radical salts with various 1.2-dithiolylium and the bi(3.5-dimethylamino) 1.2-diselenolylium cations have been prepared. The conductivity values, determined on compacted powder are about 10−1 - 10−4 (Ω cm)−1 for 1 : 1 stoichiometry salts and about 0,5 (Ω cm)−1 for complex salts whose optical spectra exhibit a peak around 3000 cm−1 characteristic of monodimensional organic conductors. Optical conductivity, from reflectivity measurements, for bi(3,5-dimethylamino)-1,2-diselenolylium-TCNQ 1 : 2 is equal to 385 (Ω cm)−1. RX structures of 5-t-butyl-3-methylthio-1,2-dithiolylium-TCNQ 1 : 2 and 3-p-methoxyphenyl-1,2 dithiolylium-TCNQ 2 : 3 show segregated stacks for counterion and TCNQ molecules with zig-zag chains for 1 : 2 salts and triadic chains for 2 : 3 salt. The room temperature value of stack axis conductivity of 5-t-butyl-3-methylthio-1,2-dithiolylium-TCNQ 1 : 2 is 4 (Ω cm)−1. The temperature dependence of the conductivity of simple crystal correspond to a semi-conductor material...

Organic conductors: TCNQ ion Radical Salts with Alkylchalcooenouronium and 1. 2-Dithioliuw Cations

Abstract Some complex ion radical salts of TCNQ with S and Se-alkylchalcogenouronium cations and 1. 2-dithiolium cations were prepared. The optical spectra determined by diffuse reflectance and absorption show four bands for all conducting salts. Electrical conductivity of compacted powders are measured at room temperature and for some salts on single crystals.

Synthese Et Etude Electrochimique De Disulfures Thiopheniques

Unsymmetrical and cyclic disulfides with thiophene units have been prepared. Electrochemical studies show the alteration of their behavior versus thiophene parents due to the second oxydation site. Polymerization of some of them leads to electroactive materials. A new efficient synthesis of the dithieno[3,2-c:2′,3′-e][1,2] dithiine is described.

SYNTHÈSE ET ÉTUDE ÉLECTROCHIMIQUE D'ALCOOLS ET D'ESTERS DÉRIVÉS De 3-ALKYL THIOPHÈNES

Abstract Starting from 3-bromothiophene, ω-(3-thienyl)alkan-1-ols and ω-(3-thienyl)alkyl esters are obtained. Electrochemical characteristics and polymerization are described and discussed.

METHYLTHIODITHIOLYLIUM REACTIONS WITH 2-BUTENE NITRILES DERIVATIVES

Abstract The 3-methylthio-1. 2-dithiolylium including at 5 position a donor substituent, in acetic acid in the presence of pyridine, the 2-methylthio-1. 3-dithiolylium ions in methylene chloride-triethylamine, react with the 2-butene nitrile derivatives and lead to the (A) and (B) corresponding 4-dithiolylidene-2-butene nitriles. In contrast ring opening reaction of the 1, 2-dithiole is observed when 2-cyano-3-phenyl-2-butene nitrile reacts with the 3-methylthio-4-aryl-1. 2-dithiolylium ions in 3 and 5 positions, in methylene chloride-triethylamine. The nucleophilic attack on the 5 position of the dithiolylium ion leads to a 2-cyano-3-phenyl-3 (4-aryl-5-methylthio-2-thienyl) propene nitrile (C), meanwhile the attack on the 3 position leads to a 2-cyano-3-phenyl-3-(4-aryl-3-mercapto-2-thienyl) propene nitrile (D). The proposed structures are established by means of physical methods (IR, NMR, and Mass Spectrometry) and by non ambiguous synthesis. The reactivities of the various sites are explained in functi...