7214-64-4Relevant academic research and scientific papers
Alkane reaction with a mixture of nitric acid and acetic anhydride
Svetlakov
, p. 1081 - 1084 (2007/10/03)
Alkanes C6-C10 at 15-20°C react with a mixture of concentrated HNO3 and acetic anhydride to afford nitrates of secondary alcohols in the yield up to 70%. Acetates of secondary alcohols, acetates and nitrates of β-nitroalcohols form in small quantity. Isooctane reacts under milder conditions to give a nitrate of β-nitroalcohol.
Direct Oxidation of Methyl Ethers to Carbonyl Compounds with a Combination of Nitrogen Dioxide and Water in the Presence or Absence of Ozone
Suzuki, Hitomi,Takeuchi, Toyomi,Mori, Tadashi
, p. 3111 - 3115 (2007/10/03)
A combination of nitrogen dioxide and water has been found to provide a new agent for the transformation of various alkyl methyl ethers 1 (R = Me) to carbonyl compounds 2 under mild conditions. The oxidation can be achieved successfully in dichloromethane, but hexafluoro-2-propanol was found to be most satisfactory as the solvent. The reaction was generally clean, and simple evaporation gave the expected oxidation product 2 in moderate to good yield. In the presence of ozone, but without water, the similar oxidation was observed only after prolonged reaction time, suggesting that some initial minor reaction with a strong oxidant, possible nitrogen trioxide, afforded an acidic promoter, which then worked as a catalyst similar to that involved in the reaction with a nitrogen dioxide and water system.
Electroorganic chemistry; 145: Coupling reaction of an olefin with a radical NO.3 generated by anodic oxidation of NO-3
Shono,Chuankamnerdkarn,Maekawa,Ishifune,Kashimura
, p. 895 - 897 (2007/10/02)
When NO-3 is electrochemically oxidized in the presence of a variety of terminal and 1,2-disubstituted olefins 1 in a mixed solvent system (MeCN:H2O:Et2O = 10:2:1), a radical NO.3 is generated from NO-3 and nitrate esters 3 are formed by a new coupling reaction of the olefin with the radical. The products 3 can be further transformed into the corresponding alcohols 4 and alkyl iodides 5. Under the same reaction conditions, 1,1-di- and 1,1,2-trisubstituted olefins 6 do not give nitrate esters but afford oxazoline derivatives 7. (1S,5S)-(-)-β-Pinene (13) is diastereoselectively transformed into (1S,2R,5S)-(-)-myrtanol (14) by this technique.
Proton Acidity and Chemical Reactivity in Molten Salt Hydrates
Franzyshen, S. K.,Schiavelli, M. D.,Stocker, K. D.,Ingram, M. D.
, p. 2684 - 2688 (2007/10/02)
Molten Ca(NO3)2*4H2O has been used as a model system for studies of proton acidity and chemical reactions (including ester hydrolyses and aromatic nitrations) in molten salt hydrates.Increases in proton acidity caused by addition of acidic hydrates such as AlCl3*6H2O and Cd(NO3)2*4H2O or of aqueous HNO3 can be quantified in terms of changes in Hammett acidity H0, but usually not by the downfield shifts observed in the NMR spectrum.The rates of hydrolysis of selected primary esters (e.g., n-octyl acetate) were found to be linearly dependent on nitric acid concentration, indicating that the acidity of these melts can be changed with little change in water activity.The measurement of kinetic parameters is complicated, however, by side reactions between the organic substrates and HNO2, NO2 (or NO2+) and other species originating from the nitrate ions in the melt.
Alkyl Nitrate Formation from the NOx-Air Photooxidations of C2-C8 n-Alkanes
Atkinson, Roger,Aschmann, Sara M.,Carter, William P. L.,Winer, Arthur M.,Pitts, James N.
, p. 4563 - 4569 (2007/10/02)
The yields of alkyl nitrates formed in the NOx-air photooxidations of the homologous series of n-alkanes from ethane through n-octane have been determined at 299 +/- 2 K and 735 torr total pressure for two different chemical systems.Alkyl peroxy radicals were generated by reaction of the n-alkanes with OH radicals (generated from the photolysis of methyl nitrite in air) or Cl atoms (from photolysis of Cl2 in air).The alkyl nitrate yields obtained from the two systems, corrected for secondary reactions, were in agreement within the experimental errors and increased monotonically with the carbon number of the n-alkane, from x-air photooxidations of the large n-alkanes.
