76552-05-1Relevant academic research and scientific papers
ADDITION OF ACETIC ACID TO 2-VINYLBICYCLOHEPTANE, 5-VINYLBICYCLOHEPT-2-ENE, AND 1-VINYLTRICYCLO2,6>-HEPTANE
Bobyleva, A. A.,Belikova, N. A.,Kalinichenko, A. N.,Baryshnikov, A. T.,Dubitskaya, N. F.,et al.
, p. 1397 - 1403 (2007/10/02)
The addition of acetic acid to 2-vinylbicycloheptane, 5-vinylbicyclohept-2-ene, and 1-vinyltricyclo2,6>heptane was investigated, and the reaction rate constants were determined.The main direction in the transformations of the former is ring enlargement and the formation of acetates of the bicyclooctane series.Direct addition of the nucleophile and hydride shift with subsequent Wagner-Meerwein rearrangement occur to a lesser degree.The addition of acetic acid to 5-vinylbicyclohept-2-ene occurs exclusively at the intracyclic double bond; the effect of the stereochemical orientation of the vinyl group on the direction of the reaction was investigated.With acetic acid 1-vinyltricyclo2,6>heptane gives 1,4-addition products, i.e., acetates of E- and Z-6-ethylidenebicycloheptan-exo-2-ols; the 1,2-addition product, i.e., the acetate of 1-(α-hydroxyethyl)tricyclo2,6>heptane, is formed intermediately.
EFFECT OF SOLVENT ON THE DIRECTION AND RATE OF ADDITION OF MERCURIC ACETATE TO UNSATURATED HYDROCARBONS
Lermontov, S. A.,Belikova, N. A.,Skornyakova, T. G.,Pekhk, T. I.,Lippmaa, E. T.,Plate, A. F.
, p. 1982 - 1989 (2007/10/02)
The direction of the addition of mercuric acetate to 5-methylenebicyclohept-2-ene and 5-ethylidenebicyclooct-2-ene depends on the nature of the solvent.In weakly polar media (acetic acid, THF) 1,2-addition occurs at the double bond inside the ring, whereas in strongly polar media (methanol, THF-water) addition occurs at the semicyclic double bond.The oxymercuration rates depend on the characteristics of the medium and change radically with change in the nature of the solvent.The conditions required for 1,4- or 1,5-addition of mercury salts to diene hydrocarbons are discussed.
