Tertiary hydroperoxides, structural production

Novel functionalized peroxides which may be used as UPR curing agents as well as initiators for polymerization reactions and as monomers for polymerizations to form peroxy-containing polymers were elaborated [162]. Initiators may be prepared by reacting hydroxy-containing tertiary hydroperoxides with diacid halides, dichloroformates, phosgene, diisocyanates, acid anhydrides and lactones to form the functionalized peroxides. These reaction products may be further reacted, if desired, with dialcohols, diamines, aminoalcohols, epoxides, epoxy alcohols, epoxy amines, diacid halides, dichloroformates and diisocyanates to form additional fimctionalized peroxides. The use of monoperoxyoxalates of the structure (Scheme 24) as initiators... 

C(C=0)C1 group to the precise structure (primary, secondary or tertiary) of the alkyl groups to which it is linked. However, our subsequent work with NO showed that its products are also sensitive to the alkyl structure yet in addition NO reacts with oxidized polymers to give distinctly different products from alcohol and hydroperoxide groups (see below). Consequently the COCl2 products were not explored further. 

Terpenic hydrocarbons are stable in the absence of air, but are easily oxidised in air, especially at higher temperatures. Their autoxidation proceeds by similar mechanisms as autoxidation of unsaturated fatty acids and depends greatly on the hydrocarbon structure. The primary autoxidation products are hydroperoxides. In branched hydrocarbons, the hydroperoxyl group mainly occurs in the secondary or tertiary carbon adjacent to the quaternary carbon of the double bond. The final autoxidation products are usually epoxides, alcohols and ketones. The primary site of attack in olefins is the carbon adjacent to the double bond, as in monounsaturated... 

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