61847-97-0Relevant articles and documents
The influence of distal substitution on the base-induced isomerization of long-chain terminal alkynes
Mohammad, Innus,Mun, JiYoung,Onorato, Amber,Morton, Martha D.,Saleh, Abdullah I.,Smith, Michael B.
, p. 4162 - 4165 (2017)
When compared to a long-straight chain terminal alkyne, a long chain terminal alkyne with a distal isopropyl unit (isobranched) isomerizes about two times faster when treated with strong base under identical conditions, and appears to follow pseudo first order kinetics. In both cases, equilibration to a 95–97:5–3 mixture of terminal:internal alkyne accompanies isomerization. The difference in rate may be due to an unusual folding of both long-chain alkynes, bringing the distal substituent close to the carbon-carbon-triple bond moiety. The distal isopropyl moiety may provide unanticipated steric hindrance that disrupts such folding, making the propargylic proton more available for reaction with base.
