Alkylamines reaction with nitrous acid

Figure 22 5 shows what happens when a typical primary alkylamine reacts with nitrous acid Because nitrogen free products result from the formation and decomposition of diazonium ions these reactions are often referred to as deamination reactions Alkyl... 

Af-Alkylarylamines resemble secondary alkylamines in that they form (V-nitroso compounds on reaction with nitrous acid. 

Azetidines are thermally stable and less reactive than aziridines. They behave in their reactions almost like secondary alkylamines. The value of azetidine is 11.29 and so it is more basic than aziridine (pAT = 7.98) and even dimethylamine ( Ka = 10.73). Azetidines unsubstituted on the N-atom react with alkyl halides to give 1-alkylazetidines which can react further to give quaternary azetidinium salts. With acyl halides, they produce acylazetidines and with nitrous acid, they give 1-nitrosoazetidines. 

Deamination of short-chain primary alkylamines with nitrous acid has long been known to give not only an enhanced (25-30%) yield of olefin compared with the analogous 5i,l reactions of halides, but also rearranged products absent from the latter. The proportion of rearranged alcohols falls with increasing homology (Table 1) and... 

Primary arylamines react with nitrous acid, HNOg, to yield stable arenediazo-nium salts, Ar—N=N X , a process called a diazotization reaction. Alkylamines also react with nitrous acid, but the corresponding alkanediazonium products... 

Nitrous acid reacts with 1 ° alkylamines and arylamines to form diazonium salts. This reaction is called diazotization. 

Proceeding via diazohydroxide (126), the nitrous acid deamination is subject, in principle, to the ramifications discussed in Section 4.3.3. In aqueous nitrous acid reactions the role of the counterion is poorly defined. Secondary alkylamines give alcohols with predominant inversion of configuration155). An 180 study on the deamination of cyclohexylamine has shown that most of the oxygen atoms of the alcohol are derived from the solvent156. ... 

---