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控制反应条件,热分解三苯氧基膦臭氧加成物(Ⅱ)产生单线态分子氧,其产率由70％提高到98％,同单线态氧的探针化合物α-蒎烯反应,得到单一的“ene”型产物,松香芹醇(pinocarveol)。同6-羟基-1,4-顺,顺-环辛二烯(Ⅰ)反应占优势的过程也是“ene”反应,分离出还原产物5,8-二羟基-1,3-顺,顺-环辛二烯(Ⅲ),以及(Ⅲ)的热重排产物6-羟基-4-顺-环辛烯酮(Ⅳ),这同用光敏氧化的方法氧化(Ⅰ)得到的结果相一致。通过构型分析,说明了化合物(Ⅰ)同单线态氧作用,通过协同的“ene”反应进行,使分子轨道相互作用不利的[_π4_s+_π2_s]加成过程被抑制。
Under the controlled reaction conditions, the thermal decomposition of triphenoxyphosphine ozone adduct (II) produces singlet molecular oxygen, the yield of which increases from 70% to 98% and is reacted with α-pinene, a probe compound of singlet oxygen. A single “ene” type product, pinocarveol. The process of the reaction with 6-hydroxy-1,4-cis, cis-cyclooctadiene (I) is also an “ene” reaction and the reduction product 5,8-dihydroxy- Cyclooctadiene (III), and the thermal rearrangement product 6-hydroxy-4-cis-cyclooctenone (IV) of (III), consistent with the results obtained by the oxidation of (I) by the photooxidation method. The configuration analysis shows that the compound (Ⅰ) acts as a singlet oxygen and is coordinated by the “ene” reaction so that the addition of [_π4_s + _π2_s], which is unfavorable to molecular orbital interactions, is inhibited.