REACTION OF O-1(2) WITH STRAINED OLEFINS .3. PHOTO-OXIDATION OF VINYLCYCLOPROPANES

被引:18
作者
FRIMER, AA
ROTH, D
机构
[1] Department of Chemistry, Bar-Ilan University, Ramat-Gan
关键词
D O I
10.1021/jo01336a028
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The reaction of O2 with 1, 1-dicyclopropylpropene (13) and its 2-methyl analogue (12) yields two “ene” products corresponding to the abstraction of an allylic hydrogen from either the methyl or the cyclopropyl group. In the latter case an alkylidenecyclopropane is formed despite a resulting 11.4 kcal/mol increase in strain energy. This indicates that 402 is insensitive to any strain that might develop in the final product. In contradistinction, 2-cyclopropyl-3-methyl-2-butene (14) yields no alkylidenecyclopropane product, but this is explicable in terms of conformational analysis. 1, 1-Dicyclopropylethylene (15) yields only the corresponding ketone and polymer by what is most probably a free-radical process. Kinetic data indicate that the unperturbed vinylcyclopropane double bond is not particularly electron rich. The question of mechanism for the ene mode of O2 attack is discussed in light of this study. © 1979, American Chemical Society. All rights reserved.
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页码:3882 / 3887
页数:6
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