79368-60-8Relevant academic research and scientific papers
Synthesis and Rearrangement of 1-Substituted Bicyclohexanes
Kirmse, Wolfgang,Sandkuehler, Peter
, p. 1394 - 1406 (2007/10/02)
Starting from 7-oxobicycloheptane-1-carbonyl chloride (3), bicyclohexane-1-carboxylic acid (9) was prepared via Hunsdiecker degradation and Favorskii rearrangement.The conversion of 9 to 1-methoxybicyclohexane (15) via methyl ketone 12 and acetate 13 was complicated by the facile homoketonization of the elusive bicyclohexane-1-ol (14).Similarly, bicyclohexane-1-amine readily underwent hydrolysis whereas N,N-dimethylbicyclohexane-1-amine (17) proved to be more resistant.Thermolysis of methyl bicyclohexane-1-carboxylate (10) revealed a "normal" rate enhancement (ΔEa ca. 6 kcal/mol = 25 kJ/mol).The effects of 1-acetoxy, 1-methoxy and 1-dimethylamino groups on the rate of rearrangement were unexpectedly small.
