Dinitrates, from epoxides

A suspension of thallium (III) nitrate in hexane reacts with epoxides to give the corresponding -hydroxy nitrate esters in good yield. The same reagent in acetonitrile has been used to synthesize a-nitratoketones from substituted acetophenones, 1,2-dinitrate esters from alkenes, and 1,3-dinitrates from ring-opening nitration of cyclopropanes. ... 

R" may be alkyl or aryl. For dialkyl ethers, the reaction does not end as indicated above, since R OH is rapidly converted to R OR by the sulfonic acid (reaction 0-16), which in turn is further cleaved to R 0S02R" so that the product is a mixture of the two sulfonates. For aryl alkyl ethers, cleavage always takes place to give the phenol, which is not converted to the aryl ether under these conditions. Ethers can also be cleaved in a similar manner by mixed anhydrides of sulfonic and carboxylic acids733 (prepared as in 0-33). p-Hydroxy alkyl perchlorates734 and sulfonates can be obtained from epoxides.735 Epoxides and oxetanes give dinitrates when treated with N2Os,736 e.g.,... 

Vicinal dinitrate esters from the reaction of epoxides with dinitrogen pentoxide... 

In many cases almost quantitative yields are reported for the formation of v/c-dinitrate esters from the reaction of simple alkyl and dialkyl epoxides with dinitrogen pentoxide (Table 3.2). Some of the products formed include ethylene glycol dinitrate (2) (96%), 1,2-propanediol dinitrate (8) (96 %), 2,3-butanediol dinitrate (94 %) and 1,2-butanediol dinitrate (96 %). Reaction times are of the order of 5-15 minutes. 

As seen in Reaction Scheme 7.3, in the NO3 and alkene reactions epoxy alkanes (also called epoxides or oxiranes), hydroperoxy nitrates, carbonyl nitrates and dinitrates are produced characteristically (Bandow et al. 1980 Kwok et al. 1996a Calvert et al. 2000), and some of them have been detected in the polluted atmosphere (Schneider et al. 1998). Recently, reactions of NO3 with alkenes are interesting from the view point of organic aerosol formation (Gong et al. 2005 Ng et al. 2008). 

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