Nitric acid esters alcohols

A. Kekule prepd in 1869 an unstable liquid (known now as Kekule Oil) when he passed ethylene thru a cooled nitric-sulfuric acid mixture, which he designated as ethyleneglycol nitrate-nitrite. Later, Wieland Sakeilarios (Ref 2) showed that this product was a mixt of ethyleneglycol dinitrate and and the nitric acid ester of 2-NitroethyI Alcohol (See also Ref 4)... 

The use of nitrogen dioxide for the selective oxidation of polysaccharides to polyuronic acids was introduced by Kenyon and his coworkers13,63 in 1941. By this means extensive oxidation of the primary alcohol groups in cellulose was obtained, through the mechanism of preferential nitration followed by decomposition of the nitric acid ester with carboxyl forma-tion.68(0< > Apparently some undissociated nitration products also were formed, since infrared absorption studies54 indicated the presence of nitrate radicals in the polyuronic acid. Side reactions produced carboxyl,... 

The simultaneous presence of nitric acid and alcohol in the ether extract must be avoided as explosive oxidation might occur during evaporation of the ether. Furthermore, the presence of alcohol may lead to contamination of the product with traces of the acid ester. 

Phenol is liable to undergo extensive oxidation during nitration so that carefully controlled conditions are required it forms 40% o- and 13% p-nitrophenolA solvent like chloroform or acetic acid is recommended. The nitration of p-cresol is carried out in benzene and acetic acid solution at 0°, the product being 3-nitro-4-hydroxytoluene (77%). The nitration of ra-cresol is discussed under method 491. Benzene is oxidized and nitrated (oxynitration) to 2,4-dinitrophenoI (72%) or to picric acid (2,4,6-trinitrophenol) by the action of mercuric nitrate in nitric acid. Aromatic alcohols like / -phenylethanol are nitrated as the esters to avoid oxidation products... 

Gun Cotton.—As nitric acid esters of poly-hydroxy alcohols, the two important explosives nitro glycerol and gun cotton are exactly analogous not only in character but also in the fact that each is the... 

Pentaerythritol (10 to 20 mg t.i.d.), a nitric acid ester of a tetrahydric alcohol, is indicated in the relief of angina pectoris and pain associated with coronary artery disease. It is not intended to abort the acute anginal episode but is widely regarded as useful in the prophylactic treatment of angina pectoris (see Figure 69). 

Nitrate esters are prepared by the reaction of nitric acid and alcohol ROH -h HNOa RONOa 4- HaO... 

Esters of nitrous and nitric acids give alcohols and salts of these acids when hydrolyzed by a base. 

Without additional reagents Nitric acid esters from alcohols... 

Tri-n-butyltin hydridejazodiisobutyronitrile Reductive generation of alkoxyl radicals Alcohols from nitric acid esters... 

Alcohols from nitric acid esters ONOg OH... 

Oxidation of Alcohols, Aldehydes, and Esters. Nitric acid oxidizes alcohols and aldehydes to the corresponding carboxylic acids. For example, l-chloro-3-propanol is oxidized to 3-chloropropanoic acid in 78-79% yield. 3-Chloropropional-dehyde affords the same product. Primary alcohols protected as esters are oxidized to the carboxylic acids (eq 11). In a two-phase solvent system (for example dimethyl ether and water), the oxidation of benzyl alcohols can be controlled so that aldehydes are obtained. ... 

The oldest class of clinically used NO donors are the organic nitrates (R-ONO2) (Fig. 20.3), which are nitric acid esters of mono and polyhydric alcohols, including glyceryl trinitrate (GTN A.l), pentaerithrityl tetranitrate (PETN A.2), isosorbide dinitrate (ISDN A.3), and isosorbide-5-mononitrate (ISMN A.4). Metabolites of GTN, viz., glyceryl mononitrate (GMN) and glyceryl dinitrate (GDN), are pharmacologically active, but less potent than GTN. 

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