Bromination of adamantane and bicyclo(2.2.2)octane with liquid bromine

✍ Scribed by Eiji Ōsawa

• Publisher: Elsevier Science
• Year: 1974
• Tongue: French
• Weight: 142 KB
• Volume: 15
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)82150-x

✦ Synopsis

The direct bromination of adamantane with elemental bromine to give lbromoadamantanel, one of the most versatile intermediates in the derivative n chemistry of adamantaneL, has long been believed to proceed only slowly for no obvious reason, refluxing for three to four hours in neat bromine being the standard procedure. lb, 3

The presumed slow rate of reaction is even used as a criterion of qualitative estimation of bridgehead reactivity of bicyclo-(3.3.1)nonane4 and diamantane5 relative to adamantane.

We found that adamantane could be brominated much more rapidly:

Adamantane (0.31 g) was stirred in 3 ml of liquid bromine at room temperature for two hours. Glc analysis at this point revealed essentially single product and no trace of adamantane.