Organomelemental fragmentations : I. Direct and retro fragmentations in organometallic benzyl compounds. Aromatisational metallation |
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Authors: | V.A. Nikanorov V.I. Rozenberg R.I. Gorbacheva Yu.G. Bundel O.A. Reutov |
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Affiliation: | Institute of Organo-Element Compounds of the Academy of Sciences of the USSR, Varilova, 28, Moscow, 117312 U.S.S.R.;Chemistry Department, M.V. Lomonosov Moscow State University, Moscow B-234 U.S.S.R. |
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Abstract: | Organometallic benzyl compounds are known to react with eletrophilic agents via two paths, viz., by direct substitution of the metal by the agent, and by attack of the ortho- and para-positions of the ring. The latter reaction leads to expulsion of the metal and formation of unstable triene intermediates (1-methylene-2,4-cyclohexadienes and 1-methylene-2,5-cyclohexadienes). By attributing these processes to electrophilic fragmentations (referred to as FE) a new process may be predicted to occur, electrpohilic addition of metal salts to the exo-methylene site of trienes of this type. This process can be regarded as the reverse of the fragmentation reaction. The FE representation proposed here forms the basis for a new organometallic synthesis, aromatisational metallation. It is shown that interaction of 1-methylene-6-ethyl-2,4-cyclohexadiene and 1-methylene-4-ethyl-2,5-cyclohexadiene with mercury dichloride in ether results in the formation of o- and p-ethylbenzylmercury chlorides, respectively. |
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