Alkyl nitrites methyl nitrite

Alkyl nitrite Methyl nitrite CH3ONO 0 // CH3O-N... 

Organic nitrites C—0—NO Acyl or alkyl nitrites Acetyl nitrite trifluoioacetyl nitrite methyl nitrite... 

Many alkyl nitrites are thermally unstable and may readily decompose or explode on heating [1], Methyl nitrite explodes more violently than ethyl nitrite [2], Lower alkyl nitrites have been known to decompose and burst the container, even in refrigerated storage [3], Individually indexed compounds are f Butyl nitrite, 1658 f fert-Butyl nitrite, 1659... 

Aminopyrazolo[3,4-d]pyrimidines 257 were converted into the corresponding 4-aryl substituted derivatives 259 via treatment with alkyl nitrites and boiling in aromatic solvent. The isomer distribution of 259 prepared by these route was that predicted for a radical intermediate (ortho, meta, and para). The structure of isomers was established by H-NMR. Unusual fragmentation products were isolated these probably result from collapse of the radical intermediate 258 (83JOC4605). Methylation of 257 takes place at either N-1 or N-2. Further methylation affords methylamino derivatives structures of the products were established by C-NMR as well as by chemical methods (75JOC1822). 

Alkyl methyl ketones undergo nitrosation at the reactive methylene group when treated with nitrous acid or an alkyl nitrite [Method (fi)]. The presence of hydrogen on the a-carbon permits tautomeric rearrangement to the oxime of a 1,2-dicarbonyl compound. Acidic hydrolysis of the oxime, which is best carried out in the presence of a hydroxylamine acceptor such as laevulinic acid,143 affords a further useful route to the 1,2-dicarbonyl system. 

Cyclopropyl nitrites are considerably more reactive than other alkyl nitrites and readily rearrange below ice-bath temperatures.117) Thus, the nitrite ester of tetramethylcyclopropanone methyl hemiacetal is easily converted to the (3-propionate radical 149 at — 80 °C and, in the presence... 

Comparison of available solution data with the gas-phase values obtained show that the destabilization of the larger freely rotating transition state by solvent packing forces must be important in these substituted nitrites therefore, the unexpectedly small phase dependence may be attributed to dielectric effects which are opposite in direction but similar (or slightly lower) in magnitude to these steric forces. For methyl nitrite AG 298 >s lower in solution than in the gas phase (AAG 298 = 0.8 kJ mol-1) while for the other primary alkyl nitrites is slightly higher (AAG+298 0.0 to 2.5 kJ mol-1). 

Until relatively recently no kinetic studies on the nitrosation of alcohols had been reported, presumably since the reactions are very rapid and require special techniques. Some kinetic measurements on the reverse reaction, the hydrolysis of alkyl nitrites have been reported here conventional kinetic methods were used. Early workers examined the reactions of the series methyl, ethyl, i-propyl and t-butyl nitrites in an acetic acid-acetate buffer and found a small increase in rate constant along the series (Skrabal et a ., 1939). Later Allen measured the rate constants for the hydrolysis of a number of alkyl nitrites in aqueous dioxan solvent for both acid- and base-catalysed reactions (Allen, 1954). The rate constants for the O-nitrosation of alcohols were determined indirectly by measurement of the overall equilibrium constant for the process, by noting the change in the rate constant for the nitrosation of phenol in the presence of added alcohols. These, combined with the known data for the reverse hydrolysis reaction, enabled the rate constants for the forward reaction to be obtained (Schmid and Riedl, 1967). The reactivity sequence MeOH > EtOH > i-PrOH > t-BuOH was deduced, and attributed to a steric effect. 

Pyrlmidyl aldehydes and ketones are conveniently prepared by the reaction of methyl-substituted derivatives with alkyl nitrites the resulting aldoximes can be converted by hydrolysis to aldehydes, or by dehydration to nitriles, which can be further converted to ketones with Grignardj jea gents, or hydrolyzed and decarboxylated (replacement of -CH by -H). ... 

A potentially serious problem looms in the path of those who would like to give this reaction a try. The problem is that alkyl nitrites such as methyl or ethyl nitrite are not easily purchased. The reason for this is their use in products which were formerly on sale under such names as "Rush," "Locker Room," or "Jock Aroma." Inhaling this class of substances produces an intense head rush, and disorientation. In many states, these substances are now classified as controlled substances. In all cases, this properly necessitates great care on the part of the chemist in handling this material, lest he be overcome. These nitrites are easily made in large... 

Alkyl halides (RX X = Cl, I) are an important source of halogens in the atmosphere. The major tropospheric sinks of these compounds are photolysis (RBr, RI) and reaction with OH radicals. In the case of alkyl iodides (RI) relative kinetic studies of their OH reactions in photoreactors are complicated by fast reactions with the 0( P) atoms generated by the photochemical OH radical sources. Figure 1 below shows a In-ln plot of the kinetic data from an experiment performed in a large photoreactor to determine the OH rate coefficient for the reaction OH + CH3CH2CH2I relative to OH + ethene using the photolysis of methyl nitrite (CH3ONO) as the OH radical source. A recent example of the implementation of the relative kinetic technique for the determination of OH radical rate coefficients in a photoreactor can be found in Olariu et al. (2000). 

Grant et al. (1960) suggest that all assignments of resonance peaks to isomers, except in methyl nitrite at low temperature, should be reversed. These workers have measured the dielectric constants of alkyl nitrites over a range of temperatures. If this is correct, the reciprocals of the figures in Table 6 should be taken for the corresponding isomer ratios. 

Several 1,3,5-triazine mono- and dialdoximes 5 can be prepared by the base-catalyzed condensation of the corresponding methyl-1,3,5-triazines 4 with alkyl nitrites. The formation of either the mono- or the dialdoxime is dependent on the reaction conditons used. Hydrolysis of the oximes to 1,3,5-triazinecarbaldehydes 6 can only be achieved for 4,6-diaryl-l, 3,5-triazine 2-al-doximes. These aldehydes can also be obtained by reaction of 4,6-diaryl-2-methyl-l,3,5-triazi-nes with sodium nitrite in concentrated sulfuric acid.162... 

Alkylation with methyl iodide or trialkyloxonium fluoborate occurs with some difficulty by analogy with 5-amino-l,2,4-thiadiazoles,74 the products are formulated as N4 quaternary salts. The 5-methyl group (in 392) readily undergoes condensation with aromatic aldehydes to 5-styrylthiadiazoles (393). The action of carboxylic acid esters gives ethoxalyl derivatives (394) and that of isoamyl nitrite produces the oxime (395).287... 

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