144271-75-0Relevant academic research and scientific papers
Mercuration of Schiff bases of substituted benzylideneanilines
Ding, Kuiling,Wu, Yangjie,Hu, Hongwen,Shen, Lianfang,Wang, Xin
, p. 3849 - 3856 (2008/10/08)
As part of an effort to investigate substituent effects on the intramolecular coordination between N and Hg, the mercuration of 36 substituted benzylideneanilines was studied. The structure characterization of the products by IR, 1H NMR, 13C NMR, and MS indicates that for all of the reactions examined, the mercury is directed to the ortho position of the N-phenyl ring or the para position of the N-phenyl ring when these sites are not occupied by a substituent. The position of the HgCl group in the mercurated product of N-(4-nitrobenzylidene)-β-naphthylamine has been confirmed by single-crystal X-ray determination, which also provided circumstantial evidence for the existence of the N→ Hg intramolecular coordination with a four-membered ring. The possible mechanism of the reaction was proposed, in which the mercuration at the ortho position of the N-phenyl ring was facilitated by the imino moiety upon formation of a coordination complex with Hg(OAc)2 in the first step, followed by a subsequent electrophilic substitution at the ortho position of the N-phenyl ring. This reaction is different from the metalation of benzylideneanilines by transition metals, in which the metal atom is usually directed to the ortho position of the C-phenyl ring, and provides a new example of the so-called cyclometalation reaction.
