Cyclopropylamines deamination

It is known that the structure of the amines is the major factor determining the configuration of the products in aqueous deaminations. Kirmse s work included the following amines exo-norbornyl-2-amine (7.48), trans-4-(rerr-butyl)cyclohexyl-amine (7.49), (+)-(5)-l-methylpropylamine (7.50), (2i ,35)-l,2-dimethylbutylamine (7.51), cyclopropylamine (7.52) and its 2,2,3-trideuterated derivative (7.53), 4,4-dimethyladamantyl-2-amine (7.54) and its G 2r/-isomer. ... 

Benzocyclopropenium ions, only very recently predicted to be stable, have been observed on dissolving 1,1-dihalogenobenzocyclopropenes in fluorosulphonic acid. Further results on the deamination of cyclopropylamines have been reported by Kirmse and Seipp and complete details of the ozonolysis of 7-phenylnorcaranes (reported partially in 1972) have appeared. ... 

Difluoroamine functions as an efficient and direct deaminating agent for aliphatic and ar. prim, amines and certain sec. amines.—E Difluoroamine condensed in a flask containing cyclopropylamine by means of a methylcyclo-hexane slush bath, and the stirred mixture allowed to warm to room temp. 

The deaminations of fra 5-2-phenyl- and frans-2-methyl-cyclopropylamine hydrochlorides in acetic acid solution have been examined. The relative amounts of the various products are shown in (26)-(29) and (30)-(33), respectively. The most remarkable feature of these results is the formation of considerable quantities of ring-opened chlorides, which are scarcely formed in deaminations of related open-chain compounds. The addition of chloride ion led to a marked increase in the amount of chloride product. These and other results are interpreted in terms of the formation of a cyclopropyl-diazonium-chloride tight ion pair. The reactions were successfully modelled by ab initio calculations at the B3LYP/6-31G level, including a reaction-field solvent-effect calculation using the dielectric constant of acetic acid. 

The products of deamination of hydrochlorides of cyclopropylamines in AcOH are influenced by added ions the amount of chloride products is increased by added chloride ion and decreased by LiC104. Ab initio calculations at the B3LYP/6-31G level reveal that for rrani-2-methylcyclopropyldiazonium ion, the ion pair with one chloride ion (positioned over the ring) leads to crotyl chloride whereas the ion triplet gives methallyl chloride, in keeping with the experimental results. 

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