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ETUDE DE LA REACTIVITE DE LA N-ETHOXYCARBONYL-N-(2,2,2-TRICHLOROETHYLIDENE)AMINE AVEC QUELQUES DIPOLES-1,3

Abdelhak Belaissaoui 1 
1 LCO
LCO - laboratoire de chimie organique
Abstract : The simultaneous presence of an ethoxycarbonyl group on the nitrogen atom and of a C-trichloromethyl group in the N-ethoxycarbonyl-N-(2,2,2-trichloroethylidene)amine, confers some particular properties to the double bond C=N which were highlighted during this work. The cycloaddition reactions of diarylnitrilimines allow to access with good yields to some 1,3-diphenyl-5-trichloromethyl-4-ethoxycarbonyl-∆2-1,2,4-triazoline derivatives. These compounds can be easily transformed in 1,3-diaryl-1,2,4-triazoles. The reactions of arylnitriloxyde precursors present a competition between the 1,3-dipolar cycloaddition leading to 3-phenyl-5-trichloromethyl-4-ethylcarboxylate-∆2-1,2,4-oxadiazoline derivatives, and a nucleophile addition yielding ethyl 1-O-(-chlorobenzaldoximino)-2,2,2-trichloro-ethylcarbamate derivatives. By the way of nucleophile addition, the reaction of ethyldiazoacetate leads to a new diazocompound which then revealed an 1,3-dipolar reactivity towards the acetylenic esters and maleimides. In the case of acetylenic esters , the cycloaddition reaction is accompagnied by an evolution leading to very substituted pyrazoles due to [1,5] sigmatropic transposition. With the maleimides, a diastereospecific cycloaddition reaction is observed which has been rationalized by an endo-anti approach mode of reactants. The diphenyldiazomethane gives a new 2-azabuta-1,3-diene with a good yield. A mechanism has been proposed: it requires thermic opening of an aziridine leading to an azomethine ylure which is stabilized through an elimination of ethylchloroformiate giving a strongly conjugated azadiene. The presence of ester groups and chlorine atoms on the imine seems to play an important role to enable this evolution.
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Abdelhak Belaissaoui. ETUDE DE LA REACTIVITE DE LA N-ETHOXYCARBONYL-N-(2,2,2-TRICHLOROETHYLIDENE)AMINE AVEC QUELQUES DIPOLES-1,3. Chimie organique. Université de Franche-Comté, 1995. Français. ⟨NNT : ⟩. ⟨tel-00923089⟩

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