Deamination Mechanisms of Open-Chain Amines Substitution Products

Although this reaction does not lead to an alkanediazonium ion, it is obvious that it is another method that is closely related to the deamination pathways discussed in this section. The azoxytoluenesulfonate method is related to the use of N-nitroamides as a source for carbocations because the leaving group is also nitrous oxide (7-10). The A -nitroamide decomposition was used extensively by White and coworkers in the 1960 s and 1970 s (see White and Grisley, 1961 White et al., 1973 White and Field, 1975, and literature cited there). N-Nitro carbamates (7.25, R = OR ) can also be used. 

Baumgarten and Curtis (1982) have reviewed deamination methods in general, including those via nitrosations. 

3 Deamination Mechanisms of Open-Chain Amines Substitution Products 

We have reviewed the early history of primary aliphatic amine deaminations up to the 1950 s in Section 7.1. The mechanisms that were postulated and evaluated until the late 1960 s or mid-1970 s have been discussed by various authors (White and 

Woodcock, 1968 Collins, 1971 Moss, 1971, 1974 Kirmse, 1976, 1979 Whittaker, 1978, p. 617), but surprisingly only rarely later (briefly by Laali and Olah, 1985, more extensively by Manuilov and Barkhash, 1990). March reviews extensively other aliphatic nucleophilic substitutions in his book Advanced Organic Chemistry (1992), but he makes little reference to deamination mechanisms. 

---