97567-50-5Relevant academic research and scientific papers
Transmetalation and Reverse Transmetalation on Ortho-Activated Aromatic Compounds: A Direct Route to o,o'-Disubstituted Benzenes
Eaton, Philip E.,Martin, Ronald M.
, p. 2728 - 2732 (2007/10/02)
Mercury Substitution ortho to appropriately activated benzenes was achieved by using the reagent lithium tetramethylpiperidide (LiTMP)/ mercuric chloride.LiTMP provides for lithiation ortho to the activating group; HgCl2 functions as an in situ trap effecting mercury-for-lithium transmetalation.Ortho, ortho'-dimercuration was also observed; this occurs by iteration of the transmetalation process.The effects of major variables on these reactions were studied by using primarily N,N-diethylbenzamide as the activated substrate.Isopropyl benzoate, 2-phenyl-4,4-dimethyloxazoline, etc. were found to behave similarly.The mercurated aromatics could be converted to the corresponding haloaromatics in excellent yield, providing, for example, a good synthesis of o,o'-diiodo-N,N-diethylbenzamide, otherwise difficultly accessible.Reverse transmetalation methodology was employed to prepare o,o'-dilithiated-N,N-diethylbenzamide, which was characterized by its reactions with electrophiles.
DILITHIATED SYNTHONS OF TERTIARY BENZAMIDES, PHTHALAMIDES, AND O,O'-ARYL DICARBAMATES
Mills, R. J.,Horvath, R. F.,Sibi, M. P.,Snieckus V.
, p. 1145 - 1148 (2007/10/02)
Dilithiated species 1, 2, and 3, generated by metal-halogen exchange and directed ortho metalation, undergo reaction with electrophiles to afford, in high yield, polysubstituted aromatics 6, 7, and 8 respectively; 9 is formed via a bis anionic Fries rearr
