6-nitrate 1.6- dinitrate ester

Alkenes can react with nitric acid, either neat or in a chlorinated solvent, to give a mixture of compounds, including v/c-dinitroalkane, jS-nitro-nitrate ester, v/c-dinitrate ester, /3-nitroalcohol, and nitroalkeneproducts. Cyclohexene reacts with 70 % nitric acid to yield a mixture of 1,2-dinitrocyclohexane and 2-nitrocyclohexanol nitrate. Frankel and Klager investigated the reactions of several alkenes with 70 % nitric acid, but only in the case of 2-nitro-2-butene (1) was a product identified, namely, 2,2,3-trinitrobutane (2). 

Alkenes react with dinitrogen pentoxide in chlorinated solvents to give a mixture of /3-nitro-nitrate, vic-dinitro, vic-dinitrate ester and nitroalkene compounds. At temperatures between -30 °C and -10 °C the /3-nitro-nitrate is often the main product. The /3-nitro-nitrates are inherently unstable and readily form the corresponding nitroalkenes." Propylene reacts with dinitrogen pentoxide in methylene chloride between -10 °C and 0°C to form a mixture of l-nitro-2-propanol nitrate (27 %) and isomeric nitropropenes (12 %). The same reaction with cyclohexene is more complicated." ... 

Synthesis of vicinal dInItrate esters from the ring opening nitration of epoxides with dinitrogen pentoxide (Ref. 75) ... 

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. ... 

Solutions of nitric acid in chlorinated solvents can add to some alkenes to give nitrate esters. Some tertiary nitrate esters can be prepared in this way isobutylene (49) reacts with fuming nitric acid of 98.6 % concentration in methylene chloride to give ferf-butyl nitrate (50). However, the products obtained depend on both the substrate and the reaction conditions /3-nitro-nitrate esters, vic-dinitrate esters, /3-nitroalcohols and nitroalkenes have been reported as products with other alkenes. Oxidation products like carboxylic acids are also common, especially at elevated temperatures and in the presence of oxygen. The reaction of alkenes with fuming nitric acid is an important route to unsaturated nitrosteroids, which assumedly arise from the dehydration of /3-nitroalcohols or the elimination of nitric acid from /3-nitro-nitrate... 

Canfield and Rohrback ° reported on the reaction of some electron-deficient difluo-roaminoalkenes with dinitrogen pentoxide in chloroform at subambient temperatures. Contrary to previous work that the /3-nitro-nitrate ester should be the main product, the corresponding vtc-dinitrate esters were isolated from these reactions l,4-bis(iV,iV-difiuoroamino)-2,3-butanediol dinitrate (55), 3,4-bis(iV,iV-difluoroamino)-l,2-butanediol dinitrate (56) and 3-(iV,iV-difluoroamino)-1,2-propanediol dinitrate (57) were isolated in 30 %, 27 %, and 55 % yields respectively, from the parent alkenes. 

A suspension of thallium (III) nitrate in pentane at room temperature can react with alkenes to give vtc-dinitrate esters. Cyclohexene reacts with this reagent to give 1,2-cyclohexanediol dinitrate (85 %) (as a mixture of isomers) and 15 % cyclopentanecarboxaldehyde (hydride shift in the dethallation step). Some alkenes react extremely slowly with this reagent e.g. isomeric 5-decenes. 

Dihydroxylation of the allyl groups of (70) with hydrogen peroxide and catalytic osmium tetroxide, followed by 0-nitration of the product (72), yields the hexanitrate ester (73). Similar treatment of the mono-allyl ether (74) affords the pentanitrate ester (76). Evans and Callaghan also 0-nitrated the hydroxy groups of (70) and (74) to yield the dinitrate and trinitrate esters, (71) and (75), respectively. The dinitrate ester (71) may find use as a monomer for the synthesis of energetic binders. 

NHTPB [Structure (4.18)] is a liquid polymer, whose viscosity can be varied by changing the percentage conversion of double-bonds to dinitrate ester groups. It is made by conversion of a percentage of the double bonds in HTPB to epoxide groups and then to nitrate-ester groups by the reaction with... 

Pujo Boileau (Ref 1) studied the action of nitrogen peroxide on epoxides and found that the reaction did not yield nitro derivs, as expected, hut nitrate-nitrite esters metha-nolysis converted the esters to alcohol nitrates. Nitration with sulfuric-nitric acids (50/50) yielded dinitrate derivs and with... 

Diethanolamine dinitric ester nitrate (diethanolamine trinitrate)... 

It has been reported by Cauquil and Barrera 83 that treatment of Oyclohexene oxide with two molar equivalents of silver perchlorate leads to the formation of metallic silver and a diperchlorate enter formulated as shown in Eq. <431). Similar unsaturated dinitrate esters, which are extremely explosive, wen reported to be formed with silver nitrate.2 8... 

Hydrazine nitrace Fluoiine nitrate Mcthylamine nitrate Tetramethylammonium nitrate Guanidine nitrate Properties Manufacture Urea nitrate Thiourea nitrate Ethylene diamine dinitritc Hexamethylenetetramine diniirate Nitrates of ethanolamine nitric esters Ethanolamine nitric ester nitrate (ethanolamine dinitrate) Diethanolamine dinitric ester nitrate (diethanolamine trinitrate) Trictham amine trimtnc ester nitrate (triethanolamine tetranitrate) Oxontum nitrate Literature... 

Since it was first synthesized in 1847 [2], nitroglycerin as a main component in liquid explosives, has been tremendously investigated and widely used in mining and other industrial blasting, as well as in military, such as propellant powers. Later, a series of liquid explosives of nitrate ester, such as dinitrate esters, with better explosive property and safety were developed [3-5]. In recent years, the United States has launched studies of high power and low characteristic signal propellants to continuously expand the application range of liquid nitrate esters [6]. 

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