Hydroquinones unsaturated acetals

The procedure described illustrates a new general synthetic method for the preparation of (E)-3-allyloxyacrylic acids and their conversion to a-unsubstituted y,6-unsaturated aldehydes by subsequent Claisen rearrangement-decarboxylation. Such aldehydes are traditionally prepared by Claisen rearrangements of allyl vinyl ethers. Allyl vinyl ethers are typically prepared by either mercury-catalyzed vinyl ether exchange with allylic alcohols or acid-catalyzed vinylation of allylic alcohols with acetals. The basic conditions required for alkoxide addition to the betaine to produce carboxyvinyl allyl ethers, as described in this report, nicely complements these two methods. In addition, this Claisen rearrangement is an experimentally very simple procedure, since sealed tube and other high pressure vessels are not required. The allyloxyacrylic acids are heated neat (in most cases a small amount of hydroquinone is added) and, by adjusting the pressure at which the reaction is performed, the aldehyde products distill from the reaction mixture in analytically pure form. 

In connection with a study of a number of anticancer compounds which, presumably also act as inhibitors of free-radical polymerization, eight classes of compounds were studied as to their inhibitory properties. The classes studied were unsaturated hydrocarbons, phenolic compounds, quinones, amines, stable free-radicals, sulfiir compounds, carbonyl compounds, and metallic salts. The most effective inhibitors, of those evaluated, were cupric acetate and cupric resinate, followed by /runs-1,3,5-hexatriene, hydroquinone, benzoquinone, and diphenylamine as modest inhibitors. Among the low-activity inhibitors were 2,2-diphenyl-1-picrylhydrazyl, benzene thiol, and crotonaldehyde [70]. 

Hydroquinone -kwi- non [ISV] (ca. 1872) (p-dihydroxybenzene, hydroquinol, p-hydroxyphenol, qui-nol) n. C6H4(OH)2. A white crystalline material derived from aniline, used, as are many of its derivatives, as an inhibitor of free-radical polymerization in unsaturated polyester resins and in monomers such as vinyl acetate. 

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