0000000000958882
AUTHOR
Malika El Messaoudi
Experimental and theoretical push-pull Chemo- and regioselectivity in 1,3-Dipolar cycloaddition reactions: the case of benzotriazepin-5-one with mesitylnitrile oxide
A novel heterocyclic compound 3-mesityl-5-methyl-4,5,11,11a-tetrahydro-6H-[1,2,4]oxadiazolo [5,4-b][1,3,4]benzotriazepin-6-one 4 has been synthesised by a 1,3 dipolar cycloaddition (13DC) reaction of 1,3,4-benzotriazepin-5-one 1 with mesitylnitrile oxide 3. The reaction, beside its synthetic interest, has shown to be completely chemo- and regioselective. The structure of the compound was determined by X-ray crystallography and analysed by spectral methods (NMR and mass spectrometry). The molecular mechanism for the reaction has been studied using quantum mechanical calculations at the B3LYP/6-31G* theory level. Two mechanisms are possible for the formation of the cycloadduct 4. The first on…
High chemoselectivity of CS dipolarophile in 1,3-dipolar cycloaddition of nitrilimines and 1,2,4-triazepin-5-one derivatives: experimental, theoretical and X-ray study
Substituted 2,7-dimethyl-3-thioxo-3,4,5,6-tetrahydro-2H-[1,2,4]triazepin-5-one reacts as a dipolarophile with several N-aryl-C-ethoxycarbonylnitrilimines, in equimolar quantities, to give, in all cases, two types of products: diethyl 3-(p-aryl)-2-[N′-(p-aryl)-N′-(2′,7′-dimethyl-5′-oxo-5′,6′-dihydro-2H-[1,2,4]triazepin-3′-yl)-hydrazino]-2,3-dihydro[1,3,4]thiadiazole-2,5-dicarboxylate (3a–3c in 20–25% yield) and ethyl 4-(p-aryl)-5-imino-1,4-dihydro[1,3,4]thiadiazole carboxylate (4a–4c in 45–50% yield). When 1:2 stoichiometry was used, the formation of product 3 (50%) was favoured. The reaction is entirely chemo- and regioselective. The structures of the compounds obtained, where aryl stands f…