p-Menthane-3,8-diol
(PMD) is gradually
dethroning
the synthetic golden standard mosquito repellent, N,N-diethyl-m-toluamide (DEET),
as PMD is natural and considered safer while displaying an excellent
repellent activity. In this study, we revisited the synthetic route
of PMD from citronellal in greener conditions, while maintaining the
highest yield, and developed a sustainable post-reaction process.
Biosourced ammonium salts were tested to catalyze the carbonyl-ene
reaction-hydration transforming citronellal and essential oils rich
in citronellal into PMD. Ammonium salts led to excellent conversions
and selectivities toward PMD, better than previously reported, even
at low catalytic loading and rapidly. Catalytic solution of ammonium
salts could be directly reused, up to six times without any loss of
activity. The sustainability of the methodology was evaluated using
a holistic approach which gave excellent green metrics, such as the
PMI (6), TON (708), TOF (17), and E-factor (0.68)
in comparison to other processes. The repellent activities of PMD
synthesized from citronellal and from essential oils were evaluated
against Aedes albopictus, the most
invasive mosquito in the world, and were as much or even more repellent
than pure PMD.