Amines cleavage with phenyl chloroformate

Cleavage of tertiary amines.1 Tertiary aliphatic and alicyclic amines can be dealkylated by reaction with phenyl chloroformate in methylene chloride at 10-40°... 

The reaction of phenyl chloroformate with tertiary aliphatic and alicyclic amines to give the corresponding N-carboxylates (pathway a) is an efficient general procedure for cleavage of tertiary amines, and provides a convenient alternative to the weil-known von Braun cyanogen bromide cleavage. The choice of phenyl chloroformate over alkyl esters in this reaction probably results in suppression of the undesired competitive reaction pathway b. 

Reductive C-N bond cleavage has been demonstrated in more complex systems using ethyl chloroformate as a solvent. Chlorination of corticosteroid cyclic ethers has been observed. Tertiary aliphatic and alicyclic amines can be dealkylated. Phenyl chloroformate, however, is usually regarded as the reagent of choice. In summary, deamination, demethylation, debenzylation, and deal-lylation of tertiary amines can all occur on treatment with ethyl chloroformate but the regioselectivities of these reactions are difficult to predict. ... 

Aminotetrazole behaves like a normal primary amine in reactions with chloroform in base,328 phenyl isocyanate,328 p-toluenesulfonyl chloride,328 and aromatic aldehydes,43 and the expected derivatives of the amino moiety are obtained without interference at the tetrazole ring. With acid chlorides and anhydrides acylation of the amino group is accompanied by ring cleavage and yields 2-acylamino-1,3,4-oxadiazoles.43,328 Flash vacuum pyrolysis of 1 -phenyltetrazole at 500° has recently been reported to give phenylcyanamide as the only detectable product.333... 

---