Hydroxy nitrate

Products identified from the reaction of 2,2,4-trimethylpentane with OH radicals in the presence of nitric oxide included acetone, 2-methypropanal, 4-hydroxy-4-methyl-2-pentanone, and hydroxy nitrates (Tuazon et al., 2002). 

Nichols and co-workersstudied the formation of j8-hydroxy nitrate esters via the acid-catalyzed ring-opening of epoxides with nitrate anion. Reactions were conducted in aqueous media using solutions of ammonium nitrate is nitric acid and under nonaqueous conditions using solutions of pure nitric acid in chloroform. 2-Nitratoethanol (32) is formed in 58 % yield from ethylene oxide (30) using either of these methods. ... 

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. ... 

Cavdar and Saracoglu reported the ring opening of chemically equivalent diepoxides with Bi(N03)3-5H20 to give di-(5-hydroxy nitrates [108]. However, we... 

Bis jetzt sind nur drei Hydroxysalze anorganischer Sauren mit un-geordneter Doppelschichtenstruktur erhalten worden, ein Zink- und ein Kobalthydroxynitrat und ein Kobalthydroxysulfat. Die Hydroxy-nitrate enthalten noch Hydroxylionen in variabler Menge in der Zwi-schenschicht die Formeln der Tabelle 8 entsprechen der Idealzusam-mensetzung. 

Sodium Azide/Ammonium Cerium(IV) Nitrate. Silyl enol ethers give a-azido ketones on treament with sodium azide and anhydrous ammonium cerium(IV) nitrate in anhydrous acetonitrile (see Eq. 97).297 325 33i With a glycal, the 2-azido-1-hydroxy nitrate derivative is formed.332 Low yields due to hydrolysis of the silyl enol ether may be improved by use of the triisopropylsilyl (TIPS) derivatives,331 although with a sterically encumbered taxane-derived enol ether the TMS derivative gives higher yields than the TIPS derivative.325 The mechanism is believed to involve addition of an azide radical to the double bond. 

This nitroxyperoxy radical can react with N02 to form a thermally unstable nitroxyperoxynitrate compound react with itself to form a nitrox-yalkoxy radical, hydroxy nitrate, and nitroxy-aldehyde/ketone or react with NO to form a nitroxyalkoxy radical or dinitrate. The nitroxyalkoxy radical can decompose to form an aldehyde/ketone and NOz, or can react with Oz to form a nitroxy aldehyde/ketone. 

Isoprene and the terpenes may be attacked by OH, NO3 and O3. The rate coefficients at room temperature for reaction with isoprene are of the order of 10 , 10 and 10 cm molecule" s , respectively. In the case of attack by OH, and in the presence of oxygen, a peroxy-hydroxy radical is formed up to six isomers may be produced. Product studies indicate that the initial addition is to one of the terminal carbon atoms. The peroxy-hydroxy radical may then either react with NO or with other RO2 radicals (including HO2) to form a variety of products, as indicated in Fig. 11. Under conditions where the peroxy-hydroxy radical reacts exclusively with NO, approximately 50 % of the carbon balance is accounted for by three main products methacrolein, methyl vinyl ketone and formaldehyde. Other carbonyl products and hydroxy-nitrates are thought to make up the carbon balance although there is presently no clear indication of the exact identity of these compounds or their yields. 

This high reactivity towards the important atmospheric photo-oxidants, probably valid also for similar isoprene oxidation products like unsaturated hydroxy carbonyls, hydroxy nitrates or hydroxy hydroperoxides, is an indication that these reactions need more consideration in laboratory experiments as well as photooxidation models. 

The action of NO containing traces of at room temperature causes a cleavage of epoxide rings [30, 31]. The reactions proceed in a highly stereoselective manner with the formation of hydroxy nitrates in 91% yield ... 

As can be seen in Reaction Scheme 7.4, the main products of the oxidation reaction of isoprene by OH are methacrolein (CH2 = CH(CH3)CHO, MACR) and methyl vinyl ketone (CH3C(0)CH = CHj, MVK) (Karl et al. 2(X)6). Besides them unsaturated hydroxycarbonyl compounds and hydroxy nitrate are formed as characteristic products. 

In recent field observations in the foothills of Sierra Nevada, United States, using a chemical ionization mass spectrometer (CIMS) and TD-LlF method, many organic nitrates, including hydroxy nitrates from isoprene and other BVOCs, are detected, and their ratio is reported amounting to two thirds of total organic nitrates (Beaver et al. 2012). Oxidation reactions of isoprene and other BVOCs in the... 

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