1092 THE BELL SYSTEM TECHNICAL JOURNAL, OCTOBER 1951 



the C — C bond attaching the ethyl group having been broken. The decom- 

 position of tertiary butyl hydroperoxide has been shown similarly to proceed 

 by the following reactions:^®- ^^ 



CH3 CH3 



I I 



CH3— C— OOH -^ CH3— C— O- + OH -> 



I I 



CH3 CH3 



CH3 



I 

 C=0 + CH3- + -OH 



I "• 

 CH3 



Here again a carbon-to-carbon bond has been broken. The impHcation of 



this work for a substituted polyethylene, for example, is quite clear. If 



oxidation occurred at a tertiary hydrogen as it most probably would,^^' ^^" ^^ 



the decomposition of the resulting tertiary peroxide would be as follows (the 



unaffected portions of the polyethylene chain being represented by the 



letter P): 



CH3 CH3 



I I 



P— CH2— C— CH2— P -> P— CH2— C— CH2— P -^ 



! I 



OOH O + OH 



P— CH2— C— CH3 + •CH2— P + OH 



II 



o 



Thus the polyethylene chain would be cut. 



The course of events is less clear for secondary peroxides. Here at least 

 two paths are possible: 



P— CH2— C— CH2— P 



O 



If the decomposition proceeds according to the top arrow, no chain scission 

 results, whereas if it takes the lower course the polymer is divided. The alde- 

 hyde is subsequently oxidized to acid. The fact that short fatty acids are 

 produced in the oxidation of straight chain hydrocarbons such as octadecane 



