Plumbyl esters

Organolead peroxides, mainly of the type R3Pb—OOR, are relatively well known (4,236, 256). The same is true for the various types of plumbyl esters of carboxylic acids (52). 

In the following reactions, the alkoxides R3Pb—OR are generally mentioned as examples. But in most cases the hydroxides, R3PbOH, plumboxanes, (R3Pb)20, and also plumbyl esters, i.e., R3PbOCOR should react similarly. 

The first known examples were the addition of a plumbyl ester or hydroxide to ketene (276). 

Kozeschkow and Alexandrow (146) obtained a-plumbylcarboxylic acid esters starting from plumbyl half-esters of malonic acid which de-carboxylate at 180° C. 

The tr-bond cleavage energy for ethylene is reported to be 58 kcal/mole (260) and should be about the same for 1-octene. The addition of a plumbyl radical would be (58 — 31 = 27 kcal/mole) very endothermic and therefore does not take place. Thus it can be explained that acrylonitrile, acrylic esters, and styrene can take part in the hydroplumbation, but not 1-octene. 

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