The autoxidation of optically active 1-bromo-2-methylbutane
作者:
J. A. Howard,
J. H. B. Chenier,
D. A. Holden,
期刊:
Canadian Journal of Chemistry
(NRC Available online 1977)
卷期:
Volume 55,
issue 9
页码: 1463-1467
ISSN:0008-4042
年代: 1977
DOI:10.1139/v77-205
出版商: NRC Research Press
数据来源: NRC
摘要:
(+)-1-Bromo-2-methylbutane undergoes autoxidation at 1 atm of oxygen and 30 °C to give, after reduction with triphenylphosphine, 1-bromo-2-methyl-2-butanol with a (+) to (−) enantiomer ratio of 1.9 ± 0.2. The optically active 1-bromo-2-methyl-2-butyl radical is, therefore, partially trapped by oxygen at this pressure before it has time to completely racemize. The half-life for racemization of the preferred conformation is approximately 2 × 10−8s−1at 30 °C. At 100 atm of oxygen the yield of (+)-CH3CH2COH(CH3)CH2Br is >90% and the reaction appears to proceed with retention of configuration. A small percentage of (−)-1-bromo-2-methyl-2-butanol is, however, still produced, presumably by inversion of configuration.
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