Abstract
Thermolysis of 1-(4-methoxyphenyl)- and 1-(4-fluorophenyl)heptamethoxycarbonyl-3a,7a-dihydroindazoles at 135–140 °C resulted in the elimination of hexamethyl benzenehexacarboxylate and in the generation of 1-aryl-3-methoxycarbonylnitrilimines, which were trapped by alkenes and dienes to give the corresponding (1) pyrazolines via 1,3-dipolar cycloaddition and (2) 2-oxoalken-1-oic acid hydrazones via allylic proton migration to the nitrogen atom. The reaction with tetramethylethene unexpectedly yielded substituted 5-(1-hydroxy-1-methylethyl)- or 5-acetylpyrazolinecarboxylates as the main products. The formation of the latter compounds suggests initial abstraction of the H atom from tetramethylethene and probable participation of a water molecule that supplies one more oxygen atom to the reaction products.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1651–1659, August, 2011.
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Tomilov, Y.V., Platonov, D.N., Okonnishnikova, G.P. et al. Generation of 1-aryl-3-methoxycarbonylnitrilimines and their reactions with unsaturated hydrocarbons. Russ Chem Bull 60, 1677–1684 (2011). https://doi.org/10.1007/s11172-011-0251-3
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DOI: https://doi.org/10.1007/s11172-011-0251-3