A chemical study of 2-butyne-1,4-diol

Commercial grade 2-butyne-1,4-diol has been used in electroplating for several years. In laboratory experiments, its presence in the electrolyte increases the current efficiency of zinc electro-winning. Its chemical behaviour in solution is not well known. The present paper indicates that the brownish technical grade 2-butyne-1,4-diol contains the monomer, the dimer and some trimer. Pure monomeric 2-butyne-1,4-diol is a white solid obtained by evaporation of the technical grade product. The monomer is slowly transformed into dimer and possibly into a trimer when dissolved in water. Various analytical techniques were used in the study of this system. Factor analysis with column cross-validation was applied to chromatographic data to help in the resolution of the system.     

Hydrazide-catalyzed 1,3-dipolar nitrone cycloadditions

The triflate salts of cyclic hydrazides function as asymmetric catalysts for the [3+2]cycloadditions of nitrones with α,β-unsaturated aldehydes. The camphor-derived hydrazides show a preference for the exo isomers during these reactions, providing a compliment to other organically catalyzed dipolar cycloadditions. Enantiomeric excesses as high as 93% were realized for the exo isomers, while some endo products were obtained in 94% ee.     

Influence de la structure sur l'hydrolyse des N-pyrrolylmethylene-2 anilines

Hydrolysis of the imine function of a series of Schiff bases derived from pyrrole-2-carboxaldehyde and substituted anilines (X = H, p-OCH₃, p-OC₂H₅, p-CH₃, p-Cl, p-Br, m-CN, m-NO₂, p-NO₂) was studied in all of the pH ranges. The hydrolysis curves log k_abs (mn^?1) = f(pH) were established in buffered aqueous methanol by polarography or amperometry. The shapes of the curves obtained for pH > 5 indicates that N-pyrrolylmethylene-2 anilines hydrolyse according to the same mechanism as N-benzylidene anilines. The particular stability of these products for pH < 5 permits one to obtain complete hydrolysis curves in acid media. A very good Hammett correlation (k_obs = + 1,73) has been established from the maxima which appear for strong acidity. This stability is interpreted as due to the specific electron-donating effect of the pyrrole nucleus. The influence of the structural parameter X on the morphology of the curves log k_abs = f(pH) and on the hydrolysis mechanism of the imine function is discussed in all of the pH ranges.     

Iron-catalyzed homo-coupling of simple and functionalized arylmagnesium reagents

Iron-catalyzed homo-coupling of simple and functionalized arylmagnesium reagents is described. The reaction is highly chemoselective (CN, COOEt and NO(2) groups are tolerated). The procedure was used to perform intramolecular couplings. This cyclization reaction is the key step of the total synthesis of the N-methylcrinasiadine.     

Oligothienylenevinylenes incorporating 3,4-ethylenedioxythiophene (EDOT) units

A new series of π-conjugated oligomers based on various combinations of thiophene and EDOT units and double bonds has been synthesized by Wittig-Horner reactions from phosphonate anions carrying EDOT or bis-EDOT units. Optical and electrochemical results evidence the crucial role of the EDOT moiety for modulating the electronic properties of the oligomers. The insertion of bis-EDOT unit in the middle of the molecule leads to a self-rigidification of the conjugated system due to non covalent S?O intramolecular interactions. The strong electron donor effect of the EDOT units explains the determining role of the relative position of the EDOT units on the localization and stabilization of the positive charges in the radical cation or dication states.     

Discriminant of a generic projection of a minimal normal surface singularity

Let (S,0) be a rational complex surface singularity with reduced fundamental cycle, also known as a minimal singularity. Using a fundamental result of M. Spivakovsky, we explain how to describe the equisingularity type of the discriminant curve for a generic projection of (S,0) onto $\text{(}\text{C}{}^2\text{,0)}$ from the resolution of (S,0). To cite this article: R. Bondil, C. R. Acad. Sci. Paris, Ser. I 337 (2003).