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8686143 
Journal Article 
The Stereochemistry of 9-Decalyl Free Radicals 
Bartlett, PD; Pincock, RE; Rolston, JH; Schindel, WG; Singer, LA 
1965 
Yes 
Journal of the American Chemical Society
ISSN: 0002-7863
EISSN: 1520-5126 
87 
12 
2590-2596 
English 
cis- and trans-9-carbo-t-butylperoxydecalins undergo thermal decomposition in cumene at 50° at identical rates and with direct formation of decalyl radicals, carbon dioxide, and t-butoxy radicals. The products, cis- and trans-decalins, 1,9- and 9,10-octalins, formed from decalyl radicals in various degassed solvents, are the same from either perester. In the presence of oxygen at 1 atm. in cyclohexane or 1,2-dimethoxyethane, cis-and trans-9-decalyl hydroperoxides are formed (10% cis, 90 % trans from either perester). This same ratio of hydroperoxides is also obtained from trans perester at 600 atm. of oxygen, while at high pressures from cis perester more cis hydroperoxide is formed (e.g., at 545 atm. of oxygen in 1,2-dimethoxyethane, 70 % cis, 30% trans). The results show that two different 9-decalyl radicals exist; one a shortlived (ca. 10-8 H-10-9 sec.) radical from cis source which changes into the same radical obtained from trans source but yields cis product on reaction with oxygen, and the other a more stable radical from trans source which yields both cis and trans products on reaction with oxygen. The products obtained indicate a nonplanar arrangement of bonds at C-9 for the initial radical from cis source and a coplanar arrangement of bonds at C-9 for the more stable radical from both sources. 1965, American Chemical Society. All rights reserved.