Spiro(bicyclo[3.3.1]-3,4-benzononane-2,1′-cyclohexane)の橋上置換体の反応

概要

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Acidic dehydration of spiro (bicyclo[3.3.1.]-3,4-benzononan-9-ol-2,1'-cyclohexane)(2a) and the Bamford -Stevens reaction of tosylhydrazone of spiro(bicyclo[3.3.1]-3,4-benzononan-9-one-2,1'-cyclohexane)(3) were investigated. Dehydration reaction of 2a was accompanied by shift of a C-C bond to afford a mixture of spiro(2,3,4,5-tetrahydro-1H-benz[e]indene-5,1'-cyclohexane)(8), spiro(3,3a, 4,5-tetrahydro-2H-benz[e]indene-5,1'-cyclohexane)(9), and a small amount of spiro(2,3,3a, 4-tetrahydro-9H-benz[f]indene-9,1'-cyclohexane)(10). This result clearly showed that nucleophilic shift of C-C bond adjacent to the benzene ring was less easy than other C-C bonds. The Bamford -Stevens reaction of 3 yielded spiro (tricyclo[4.3.0.0^<2,9>]-4,5-benzononan-3,1'-cyclohexane)(11) as a product of insertion reaction of carbene intermediate.
公益社団法人日本薬学会の論文
1975-05-25