Nitrate, alkyl

Alkyl nitrates 509 react with chlorosulfonic acid at 15-20 °C to give excellent yields (90-94%) of the corresponding alkyl bisulfates 510 (Equation IbO). This reaction provides a useful synthesis of alkyl bisulfates. 

The absorption cross sections and photochemistry of alkyl nitrates are discussed in Chapter 4.J, where the 

TABLE 6.22 Room Temperature Rate Constants for the Reactions of OH with Some Simple Alkyl Nitrates at 298 K  

Reaction with OH is, however, reasonably rapid as might be expected and is of the same order of magnitude as the OH-alkane reactions. Table 6.22, for example, shows the room temperature rate constants for the reactions of OH at 298 K with some alkyl nitrates. With 2-butyl nitrate as an example, the lifetime with 

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The additives for improving the cetane number, called pro-cetane, are particularly unstable oxidants, the decomposition of which generates free radicals and favors auto-ignition. Two families of organic compounds have been tested the peroxides and the nitrates. The latter are practically the only ones being used, because of a better compromise between cost-effectiveness and ease of utilization. The most common are the alkyl nitrates, more specifically the 2-ethyl-hexyl nitrate. Figure 5.12 gives an example of the... 

We also found N-nitropyridinium salts such as C5HjN N02BF4 as convenient transfer nitrating reagents in selective, clean reaetions. Transfer nitrations are equally applicable to C- as well as to 0-nitra-tions, allowing, for example, safe, acid-free preparation of alkyl nitrates and polynitrates from alcohols (including nitroglycerine). 

Even less dangerous in this respeet are the nitrating systems using alkyl nitrates and sodium ethoxide. Noteworthy examples of the use of these less acidic or basic nitrating systems are found in the pyrrole series. 

Although the term ester used without a modifier is normally taken to mean an ester of a carboxylic acid alcohols can react with inorganic acids m a process similar to the Fis cher esterification The products are esters of inorganic acids For example alkyl nitrates are esters formed by the reaction of alcohols with nitric acid... 

Formation of esters of inorganic acids (Section 15 9) Alkyl nitrates dialkyl sulfates trialkyl phos phites and trialkyl phosphates are examples of alkyl esters of inor game acids In some cases these compounds are prepared by the direct reaction of an alcohol and the inorganic acid... 

Tin(lV) chloride Alkyl nitrates, ethylene oxide, K, Na turpentine... 

Substitution. Substitution products retain the same nuclear configuration as naphthalene. They are formed by the substitution of one or more hydrogen atoms with other functional groups. Substituted naphthalenes of commercial importance have been obtained by sulfonation, sulfonation and alkah fusion, alkylation, nitration and reduction, and chlorination. 

Selenazole, 2-acetamido-nitration, 6, 341 Selenazole, 2-alkyl-nitration, 6, 340 Selenazole, 2-amino-bromination, 6, 341 sulfonation, 6, 341 synthesis, 6, 342... 

Acyl or alkyl nitrates Alkyl perchlorates Aminemetal oxosalts Arenediazo aryl sulfides Arenediazoniiimolates Azo compounds... 

Use of high or low temperature, high pressure, vacuum or possible hazardous reactions (polymerization, oxidation, halogenation, hydrogenation, alkylation, nitration, etc.)... 

Acyl or alkyl nitrites Acyl or alkyl nitrates... 

Nitrogen Oxides a criteria air pollutant, compounds NO, NO, NO3, NjO, alkyl nitrates, etc. 

The reactivity of Ce, C7, Cg aromatics is mainly associated with the benzene ring. Aromatic compounds in general are liable for electrophilic substitution. Most of the chemicals produced directly from benzene are obtained from its reactions with electrophilic reagents. Benzene could be alkylated, nitrated, or chlorinated to important chemicals that are precursors for many commercial products. 

The US Air Force has studied the encapsulation of liq monoproplnts such as alkyl nitrates in polymer films to form small spheres much like ball powder for use as gun proplnts (Refs 6, 8 9). Suspension coating techniques were used, and microcapsules were made with gelatin,... 

A range of transformation products has been identified from simulated reactions of alkanes. These include alkyl nitrates by reactions that have already been given, but also include a range of hydroxy-carbonyls that are summarized in Table 1.2 (Reisen et al. 2005). 

Products formed by reaction of NO3 radicals with a-pinene have been identified and include pinane epoxide, 2-hydroxypinane-3-nitrate, and 3-ketopinan-2-nitrate formed by reactions at the double bond, and pinonaldehyde that is produced by ring fission between C-2 and C-3 (Wangberg et al. 1997). These reactions should be viewed in the general context of odd nitrogen to which alkyl nitrates belong (Schneider et al. 1998). 

Schneider M, O Luxenhofer, A Deissler, K Ballschmiter (1998) Cj-C, alkyl nitrates, benzyl nitrate and bifunctional nitrates measurements in California and South Atlantic air and global comparsion using C2Cj4 and CHBrj as marker molecules. Environ Sci Technol 32 3055-3062. 

Effects of chain length and substitution. Comparing the stabiiity of alkyl nitrates or aliphatic nitrated derivatives, in spite of instability to the extent of making it hazardous to handle them, stability increases rapidly with the number of alkyl groups. So nitroethanes, especially nitropropanes and nitrobutanes, are commonly used industrial raw materials. 

The transformations (1) lead to unstable alkyl nitrates, which can detonate very easily. The reactions (2) lead to more or less complete oxidations of the organic molecule. The formation of aldehydes is purely theoretical since they are more oxidisable than alcohols and therefore are not part of the oxidation process by nitric acid. On the other hand, a ketone can form with a secondary alcohol. With tertiary alcohols, carboxylic acid is the only possible outcome of the partial oxidation, which is caused by the breaking of C-C bonds. When the oxidation is out of control, it is likely to have a complete oxidation. Finally, with heavy metal... 

When alkyl nitrates and in particular methyl and ethyl nitrates are added to acids (H2SO4, SnCl4, BF3) they give rise to a very violent reaction with the formation of large quantities of gas. The presence of impurities, nitrogen oxid, transition metal oxides increases the sensitivity of these mixtures to detonation. 

Alkyl nitrates become spontaneously explosive if they contain nitrogen oxides. 

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