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31.22.1.1.2.1 Variation 1: Of Tertiary Arylamines

DOI: 10.1055/sos-SD-031-01513

Rück-Braun, K.; Priewisch, B.Science of Synthesis, (2007311326.

A broad range of nitrosoarenes bearing a tertiary amino group in the para position can be synthesized in good to excellent yields by nitrosation of the corresponding tertiary arylamines. Often a solution of an equimolar amount of sodium nitrite in water is gradually added at 010°C to the arylamine in hydrochloric acid,[‌24‌] but in some cases the addition of an alcohol as a cosolvent may be necessary. The concentration of hydrochloric acid should be high enough to ensure precipitation of the 4-nitrosylated arylamine as its hydrochloride salt (Scheme 10),[‌25‌‌31‌] from which the free amine 13 may be subsequently liberated by the addition of a base such as ammonium hydroxide or aqueous sodium hydroxide.[‌25‌,‌26‌] Nitrosation of tertiary arylamines may also be effected using alkyl nitrites or nitrosonium ethyl sulfate, generated in situ from ethyl nitrite and sulfur trioxide, as nitrosating reagents.[‌27‌,‌28‌] Alternatively, nitrosyl chloride can be generated in situ from sodium nitrite and tin(IV) chloride pentahydrate in dichloromethane and this allows nitrosations to be carried out in non-alcoholic organic solvents.[‌29‌] Substituents ortho to the tertiary amino group impede nitrosation (see HoubenWeyl, Vol.10/1, p1042), and para-substituted tertiary amines also do not normally undergo ring nitrosation.[‌32‌]

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