Nitro nitrates

Certain features of the addition of acetyl nitrate to olefins in acetic anhydride may be relevant to the mechanism of aromatic nitration by this reagent. The rapid reaction results in predominantly cw-addition to yield a mixture of the y -nitro-acetate and y5-nitro-nitrate. The reaction was facilitated by the addition of sulphuric acid, in which case the 3rield of / -nitro-nitrate was reduced, whereas the addition of sodium nitrate favoured the formation of this compound over that of the acetate. As already mentioned ( 5.3. i), a solution of nitric acid (c. i 6 mol 1 ) in acetic anhydride prepared at — 10 °C would yield 95-97 % of the nitric acid by precipitation with urea, whereas from a similar solution prepared at 20-25 °C and cooled rapidly to —10 °C only 30% of the acid could be recovered. The difference between these values was attributed to the formation of acetyl nitrate. A solution prepared at room... 

Indole, l-methyl-2-sulfonamido-tautomerism, 4, 200 Indole, l-methyl-3-sulfonamido-tautomerism, 4, 200 Indole, (methylthio)-synthesis, 4, 368 Indole, 3-(methylthio)-synthesis, 4, 338, 368 Indole, l-methyl-3-vinyl-oxidation, 4, 280 Indole, nitro-rearrangement, 4, 297 Indole, 3-nitro-nitration, 4, 211, 213 reduction, 4, 362 synthesis, 4, 210, 363 Indole, 5-nitro-synthesis, 4, 211, 363 Indole, nitroso-rearrangement, 4, 297 Indole, 1-nitroso-reduction, 4, 362 Indole, 3-nitroso-reduction, 4, 362 Indole, nitrovinyl-... 

Pyridine, 2,6-dimethoxy-3-nitro-nitration, 2, 188 Pyridine, 2,3-dimethyl-synthesis, 2, 479 Pyridine, 2,4-dimethyI-acylation, 2, 333 alkylation, 2, 333 synthesis, 2, 479... 

Pyridine, 2-(dimethylamino)-5-nitro-nitration, 2, 189 Pyridine, 3,5-dinitro-conformation, 2, 110 Pyridine, 3,5-diphenyl-synthesis, 2, 0... 

Pyrrole, 2-methyoxycarbonyl-1 -methyl-formylation, 4, 45 Pyrrole, nitro-rearrangement, 4, 297 Pyrrole, 2-nitro-nitration, 4, 211 photolysis, 4, 203 radical methylation, 4, 260 synthesis, 4, 210, 362 Pyrrole, 3-nitro- N NMR, 4, 13 nitration, 4, 211 synthesis, 4, 49, 210, 362 Pyrrole, nitroso-rearrangement, 4, 297 Pyrrole, 2-nitroso-reactions... 

Quinoline, 5-nitro-oxidation, 2, 210 synthesis, 2, 318 Quinoline, 6-nitro-nitration, 2, 318 Quinoline, 7-nitro-nitration, 2, 318 synthesis, 2, 318 Quinoline, 8-nitro-... 

Addition of nitrogen dioxide to l, 2, 2 -tnfluoroslyrene gives a mtro-nitnte or nitro-nitrate adduct, which affords l -nitro-l, l -difluoroacetophenone [6] (equation 6). 

By addition of nitrogen dioxide, nitrosates (II) (nitroso-nitrates) or dinitro compds (III) or dinitrites (IV) are obtained. Nitrosates (II) can be oxidized to nitro-nitrates (Ila), viz ... 

This mixt, as well as other nitro-nitrates of aryl-substituted polyhydric alcohols, was recommended for use in expls, either alone or with appropriate additives, eg, in proplnts, primer compns, detonators, etc... 

Nitro-nitrate mit endstandiger Nitro-Gruppe liefern bei dcr Reduktion mit 3,5 Mol-Aquivalenten Natriumboranat4 die sonst nur schwierig zuganglichen terminalen Nitro-alkane. 

Nitration of furfuryl alcohol (2-furylmethanol) in acetic anhydride yields the nitro-nitrate 57 which possesses both a reactive methylene group able to undergo aldol reactions, etc., and also a nitrate ion leaving group for nucleophilic substitutions.137 Detailed studies of the nitration disclose various products resulting from the addition of one or even two acetic acid residues to the furan nucleus in competition with the nitrations.138,139... 

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). 

The reaction of fuming nitric acid with 2-methyl-2-butene (3) is reported to yield 2-methyl-3-nitro-2-butene (4). The reaction of alkenes with fuming nitric acid, either neat or in chlorinated solvents, 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 esters. Temperature control in these reactions is important if an excess of oxidation by-products is to be avoided. 

Mixed acid has been reported to react with some alkenes to give /3-nitro-nitrate esters amongst other products. ... 

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." ... 

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. 

The nitro substituents are generally classihed according to the nature of the atom to which they are attached carbon, nitrogen or oxygen. - Accordingly, in the previous chapters, the introduction of C-nitro, iV-nitro (nitramine) and O-nitro (nitrate ester) functionality into organic compounds has been discussed. 

Addition of Cl2 and S03 to alkenes 5-40 Addition of N204 to alkenes (nitro nitrites, nitro nitrates)... 

Reaction with nitrogen tettoxide produced very unstable nitro-nitrates. On two occasions violent explosions took place in USRubberCo Laboratory at Passaic, NJ Note [n view of remarkable instability of nitrated derlvs of silanes and obvious force of detonation, it. is suggested to use mono-, di-, tri-, and tetra-allylic silanes and nitrogen tetroxide in liquid rocket propellants. It is also likely that vinylsilanes will exhibit similar behavior... 

When two or more different primary plosophores are present in a single molecule, the compd is called hybrid (eg nitrate aliphatic nitro, nitrate aromatic nitro, nitramine aromatic nitro). It was established that hybrids are as powerful (or more) as pure types, although they tend to exhibit somewhat greater variability. This property of hybrids is of importance, because it extends enormously the synthetic possibilities for expls... 

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