Controlled release of volatile aldehydes and ketones from dynamic mixtures generated by reversible hydrazone formation

Delivery systems generated by reversible hydrazone formation from hydrazine derivatives (see Fig. 1) and carbonyl compounds in H2O efficiently increase the long-lastingness of volatile aldehydes and ketones ((RRC)-R-1-C-2=O) in various perfumery applications. The hydrazones are usually obtained in an (E) configuration at the imine double bond (NHN=C) and, in the case of aliphatic acythydrazones R'CO-NH-N=(CRR2)-R-1 (R'= alkyl), as syn and anti conformers with respect to the amide bond (CO-NHN). An average free-energy barrier of ca. 78 kJ/mol was determined for the amide-bond rotation by variable-temperature H-1-NMR measurements (Fig. 2). In the presence of H2O, the hydrazone formation is entirely reversible, reaching an equilibrium composed of the hydrazine derivative, the carbonyl compound, and the corresponding hydrazone. Kinetic measurements carried out by UV/VIS spectroscopy showed that the same equilibrium was reached for the formation and hydrolysis of the hydrazone. Rate constants are strongly pH-dependent and increase with decreasing pH (Table 1). The influence of the hydrazine structure on the rate constants is less pronounced than the pH effect, and the presence of surfactants reduces the rate of equilibration (Tables I and 3). The full reversibility of the hydrazone formation allows to prepare dynamic mixtures by simple addition of a hydrazine derivative to several carbonyl compounds. Dynamic headspace analysis on dry cotton showed that the presence of a hydrazine derivative significantly increased the headspace concentrations of the different carbonyl compounds as compared to the reference sample without hydrazine (Table 4). The release of the volatiles was found to be efficient for fragrances with high vapor pressures and low H2O solubility. Furthermore, a special long-lasting effect was obtained for the release of ketones. The simplicity of generating dynamic mixtures combined with the high efficiency for the release of volatiles makes these systems particularly interesting for practical applications and will certainly influence the development of delivery systems in other areas such as the pharmaceutical or agrochemical industry.