REACTION OF SINGLET OXYGEN WITH 4-METHYL-2,3-DIHYDRO-GAMMA-PYRANS
REACTION OF SINGLET OXYGEN WITH 4-METHYL-2,3-DIHYDRO-GAMMA-PYRANS
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DOI：
10.1021/ja00466a033
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发表时间：
1977-01-01
影响因子：
15
通讯作者：
JEWETT, JG
中科院分区：
文献类型：
--
作者：
FRIMER, AA;BARTLETT, PD;JEWETT, JG
4-Methyl-1, 3-dihydro-7-pyran (1) reacts with singlet molecular oxygen to yield both a dioxetane 2 and an allylic hydroperoxide 3, each of which is converted by heat into a single product stable under conditions of vapor chromatography. The product composition from 1 and from\-4-d has been determined in benzene and in acetonitrile, the ratio 2/3 being 26 times greater in the latter solvent. The tritium kinetic isotope effects at the a, ß, andy positions indicate that for both products in both solvents the transition state has a weakened-O'bond, a strengthened HO bond, and an HO bond whose strength is not appreciably altered. Possible interpretations of these effects are discussed with respect to the detailed mechanism of at-tack of singlet oxygen on this enol ether, which is also compared with 4, 4-dimethyl-1, 3-dihydropyran (4).
