Preparation of the Maleic Anhydride
Nucleus from Dichloro γ-Lactams: Focus on the Role of the
N-Substituent in the Functional Rearrangement and in the Hydrolytic
Steps

Franco Ghelfi; Mariella Pattarozzi; Fabrizio Roncaglia; Andrew F. Parsons; Fulvia Felluga; Ugo M. Pagnoni; Ennio Valentin; Adele Mucci; Franco Bellesia

doi:10.1055/s-2008-1067273

PAPER

Preparation of the Maleic Anhydride Nucleus from Dichloro γ-Lactams: Focus on the Role of the N-Substituent in the Functional Rearrangement and in the Hydrolytic Steps

Franco Ghelfi*^a, Mariella Pattarozzi^a, Fabrizio Roncaglia^a, Andrew F. Parsons^b, Fulvia Felluga^c, Ugo M. Pagnoni^a, Ennio Valentin^c, Adele Mucci^a, Franco Bellesia^a
^a Dipartimento di Chimica, Università degli Studi di Modena e Reggio Emilia, Via Campi 183, 41100 Modena, Italy
Fax: +39(59)373543; e-Mail: ghelfi.franco@unimore.it;
^b Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK
^c Dipartimento di Scienze Chimiche, Università di Trieste, via Licio Giorgieri 1, 34127 Trieste, Italy

Abstract

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Abstract

The preparation of the 3,4-dialkyl-substituted maleic anhydride nucleus, through the functional rearrangement of dichloro γ-lactams, allowed the comparison of various N-substituents in the functional rearrangement step. The 2-pyridyl group proved to be the most appropriate N-substituent for the hydrolysis of the 5-methoxy-1,5-dihydro-2H-pyrrol-2-one intermediate into the 5-hydroxy adduct, and for the hydrolysis of the maleimide nucleus into the maleic anhydride. The oxidation of the 5-hydroxy-1,5-dihydro-2H-pyrrol-2-one into the corresponding maleimide was achieved with manganese(IV) oxide.

Key words

rearrangement - radical reactions - substituent effects - halo compounds - γ-lactams

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