74 nitrosyl chloride, reaction with

Johnston and Leighton studied the effect of adding N2O5 to a mixture of ozone and nitrosyl chloride in the gas phase. The stoichiometry of the reaction is, in fact, 

2-trichloro-l,2,2-trifluoroethane solution between — 10°C and — 30°C N2O5 reacts with NOCI with the stoichiometry  

N2O5 + NOCI = N2O4+NO2CI In the initial stages the rate equation may be expressed as d[NOCl] 

The reaction is a complex one, however, and becomes of second order in the later stages. 

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Toray. The photonitrosation of cyclohexane or PNC process results in the direct conversion of cyclohexane to cyclohexanone oxime hydrochloride by reaction with nitrosyl chloride in the presence of uv light (15) (see Photochemical technology). Beckmann rearrangement of the cyclohexanone oxime hydrochloride in oleum results in the evolution of HCl, which is recycled to form NOCl by reaction with nitrosylsulfuric acid. The latter is produced by conventional absorption of NO from ammonia oxidation in oleum. Neutralization of the rearrangement mass with ammonia yields 1.7 kg ammonium sulfate per kilogram of caprolactam. Purification is by vacuum distillation. The novel chemistry is as follows ... 

Nitrosochloromethane, 0N.CH2.C1 mw 79-49, N 17.62% It yel crysts(bimolecuIar in soln, monomolecular when melted), possessing a sharp lacrimatory irritating smell, mp ca 62°(with blue coloration) decomp vigorously at 65 66° sol in org sol vs insol in w or cold NaOH can be prepd from trimolecular formaldoxime, (H2C NOH)3, but better from formaldehydeoxime-hydrochloride by reaction with nitrosyl chloride in ether under cooling (Refs 1 2)... 

Barton reaction In the Barton reaction " a methyl group in the 7 -position to an OH group is converted into an oxime group. For example, corticosterone acetate (2.45) on reaction with nitrosyl chloride (NOCl) in pyridine forms its 1 l -nitrite 2.46, which on photolysis in toluene gives aldosterone acetate oxime (2.47) in 21% yield. Treatment of 2.47 with nitrous acid (HNO2) gives aldosterone acetate (2.48) (Scheme 2.40). 

The organomercury compounds formed in such reactions are not of great synthetic importance, although they do undergo nitrosation reactions with nitrosyl chloride, NOCl. They can also be used as the organometallic component in certain palladium-mediated coupling processes. 

When in reaction with nitrosyl chloride, the 20j8-isomer 278 furnished the corresponding llj8-nitrite 279 which, upon irradiation in iodine containing benzene, yielded the 19-iodo compound 280. 

Nitrosamines. Nitrosamines are usually prepared by reaction of rec-amines with nitrous acid in water. They can also be prepared by conversion of tbe amine into the sodium amide (NaH, THF) followed by reaction with nitrosyl chloride. jcc-Amines also react directly with nitrosyl chloride in THF if pyridine is added as base. Yields by either method are fair to good. - R. E. Lyle, J. E. Saavedra, and G. G. Lyle, Synthesis, 462 (1976). 

A procedure for intramolecular functionalization of alcohols has been developed in studies carried out primarily with steroid derivatives. The alcohol is converted to a nitrite ester by reaction with nitrosyl chloride. Photolysis effects... 

Mercuric acetate and mercuric trifluoroacetate are the usual reagents. The synthetic utility of the mercuration reaction derives from subsequent transformations of the arylmercury compounds. As indicated in Section 7.3.3, arylmercury compounds are only weakly nucleophilic, but the carbon-mercury bond is reactive toward various electrophiles. The nitroso group can be introduced by reaction with nitrosyl chloride or nitrosonium tetrafluoroborate as the electrophile. Arylmercury compounds are also useful in certain palladium-catalyzed reactions, as discussed in Section 8.2. 

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