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α-Arylamino Diazoketones: Diazomethane-Loading Controlled Synthesis, Spectroscopic Investigations, and Structural
Laura Castoldi, Laura Ielo1, Wolfgang Holzer
1Department of Chemical, Biological, Pharmaceutical and Environmental Sciences , University of Messina , Viale Annunziata , 98168 Messina , Italy.
Abstract:
Primary and secondary α-halomethyl diazoketones generated via Arndt-Eistert chemistry with minimum loading of diazomethane efficiently alkylate aromatic amines in the presence of calcium oxide to furnish the corresponding α-arylamino diazoketones under full chemocontrol. Such a simple inorganic acid scavenger fully neutralizes the hydrohalic acid formed during the nucleophilic displacement which otherwise would immediately react to produce the corresponding α-haloketone. The methodology can be further exploited in analogous acylation-type processes on secondary arylamino diazoketones. In depth spectroscopic (1H, 13C, and 15N NMR ) and crystallographic analyses document interesting structural features of these previously unknown diazo derivatives.
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