ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
1-(Phenylazo)-1-(2-pyridyl)ethyl hydroperoxide, 1, 1-(phenylazo)-1-(2-furyl)ethyl hydroperoxide, 2, phenylazo(2-furyl)methyl hydroperoxide, 3, 1-(phenylazo)-1-(4-anisyl)ethyl hydroperoxide, 4, were synthesized in moderate yield by autoxidation of the phenylhydrazones in benzene. The ionic oxidation of benzyl methyl sulfide in benzene by 1-4 yielded the sulfoxide and the metastable α-azo hydroxides in essentially quantitative yield. The reaction was of the first order in α-azo hydroperoxide and sulfide, respectively. The relative reactivity series found was: 1(1.0) 〈4(1.4) 〈 phenylazo(4-anisyl)methyl hydroperoxide 5 (2·9) 〈2 (3·8) 〈 3 (9·6). α-Methyl substitution was found to slow the rate of oxygen-atom trasfer by a factor of 2 to 2.5. The low relative reactivity of 1 was opposite that expected based on electronic effects. Competitive intramolecular hydrogen bonding of the hydroperoxy proton to the pyridyl nitrogen in 1 accounted for the observed result.
Additional Material:
2 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610010503
