The Reaction of 3-Arylpropylamines with Nitrous Acid

Citation

Fort, Arthur W. (1955) The Reaction of 3-Arylpropylamines with Nitrous Acid. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/PCT4-DB71. https://resolver.caltech.edu/CaltechETD:etd-12122003-161659

Abstract

3-Phenylpropylamine-1-C¹⁴ reacts with nitrous acid in aqueous solution to give hydrocinnamyl alcohol, benzylmethylcarbinol and allylbenzene in the ratio 2.5:1.6:1.0. Under similar conditions, 3-(p-methoxyphenyl)-propylamine-1-C¹⁴ gives p-methoxyhydrocinnamyl alcohol, p-methoxybenzylmethylcarbinol and p-methoxyallylbenzene in the ratio 2.1:1.4:1.0. No evidence was found for the presence of other isomeric alcohols or olefins.

A sample of each product from 3-phenylpropylamine-1-C¹⁴ was oxidized to benzoic acid, which was found to be inactive in each case. Likewise, anisic acid obtained from each of the products from 3-(p-methoxyphenyl)- propylamine-1-C¹⁴ was found to be inactive.

The number two carbon atom of each of the six products was shown to contain less than 0.5% of the total C¹⁴ activity of the product except in the case of benzylmethylcarbinol-C¹⁴, where the activity at C-2 was found to be 0-3%.

These results eliminate the symmetrical carbonium ions having structures A and B as intermediates in the reactions studied.

[chemical formulae omitted]

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