130405-84-4

Upstream product

• 130380-91-5 C₁₃H₂₁⁽²⁾HO₂ 
• 130380-90-4 <6-2H>-bicyclo<3.2.1>oct-endo-6-yl-(p-brombenzolsulfonate) 
• 130380-92-6 C₁₁H₁₉⁽²⁾HO 
• 130380-79-9 1,4,4-trimethylbicyclo<3.2.1>octan-6-on-(p-toluolsulfonylhydrazone) 
• 33315-89-8 1,4,4-trimethylbicyclo<3.2.1>octan-6-one 
• 130380-92-6 C₁₁H₁₉⁽²⁾HO 
• 98-58-8 4-bromobenzenesulfonyl chloride 

Relevant academic research and scientific papers

Rearrangements of 1,4,4- and 2,2,5-Trimethylbicyclooct-6-yl Cations

1,4,4-Trimethylbicylooct-6-yl cations (18) are generated from the tosylhydrazone 7, by nitrous acid deamination of the amines 6 and 8, and by acetolysis of the brosylates 21 and 24.The product distributions are but slightly affectted by the configuration (exo vs. endo) of the leaving groups.The predominantly product, 1,4,4-trimethylbicyclooctan-exo-6-ol (11) is formed without significant redistribution of a 6-2H label.The degenerate Wagner-Meerwein rearrangement of the parent bicyclooct-6-yl cation is virtually eliminated by the presence of two methyl groups at C-4.Enhanced conformational strain, raising the barrier to ring flipping, accounts for these observations.Minor products (12, 13) arise from a 7,6-hydride shift of 18, followed by Wagner-Meerwein rearrangement.When the 2,2,5-trimethylbicyclooct-6-yl cation (19) is generated directly from the tosylhydrazone 17, the tertiary alcohol 13 is obtained as the major product.The conformational barrier to Wagner-Meerwein rearrangement is compensated by the incipient stabilization of the tertiary carbocation 20.Key Words: Bicyclooct-6-yl cations / Wagner-Meerwein rearrangements / Alkyl-bridged ions / Conformational effects