Reduction of nitrosamines in cosmetic products

Abstract

Summary From initial rate studies of morpholine nitrosation in aqueous media by nitrite ion in the presence of formaldehyde at pH 5-7 and 25 degrees C, four potential pathways are revealed for the concurrent formation of nitrosamine contaminants in cosmetic and toiletry products. Three of the pathways involve conventional electrophilic nitrosation by XNO reagents of both neutral amine and N-hydroxymethylamine compounds obtained by prior reaction with formaldehyde. The fourth pathway involves a nucleophilic reaction by nitrite ion with the iminium ion derived from N-hydroxymethylamine. For morpholine, reaction via XNO reagents is substantial at pH 5 only, whereas the iminium ion pathway is pre-eminent at pH 7. The concurrent formation of nitrosamines by mechanistically different pathways implies that combinations of nitrosation inhibitors are necessary to minimize contamination of cosmetic and toiletry products. For these different pathways, novel inhibitory compounds are described which fulfil the usual acceptance criteria for cosmetic and toiletry materials. The efficacy of these compounds is assessed against N-nitrosomorpholine formation in the presence of formaldehyde. These include erythorbate, ascorbate, pentanedione and pyranone compounds for the XNO pathways (pH 6) and neutral organic and inorganic salts for the iminium ion pathways (pH 7). Preliminary results for both a bath gel and a cream-base formulation deliberately adulterated with morpholine, diethanolamine, nitrite and a preservative which releases low levels of formaldehyde on decomposition show better than 90% inhibition of nitrosamines by selected pairs of inhibitor compounds on storage at 40 degrees C over several months. This novel technology is the subject of a worldwide patent application.