# High-yielding and scalable synthesis of furfural acetals using protonated κ-carrageenan as a biorenewable acid catalyst

## TL;DR

A new renewable acid catalyst from marine biomass efficiently produces furfural acetals with high yields and scalability.

## Contribution

A biorenewable acid catalyst, protonated κ-carrageenan, enables high-yield synthesis of furfural acetals with excellent scalability and reusability.

## Key findings

- Protonated κ-carrageenan (kCH) catalyzes acetalization of furfural derivatives with yields over 90%.
- The catalyst is reusable without significant loss of activity and works with various glycols and aldehydes.
- A 10 g scale synthesis of 2-(furan-2-yl)-1,3-dioxolane was successfully achieved.

## Abstract

The acetals of carbohydrate-derived furfurals have potential applications as fuel oxygenates and chemical intermediates. This work reports the use of protonated κ-carrageenan (kCH) as a marine biomass-derived renewable acid catalyst for the acetalization of furfural and 5-methylfurfural with ethylene glycol, 1,2-propanediol, and 1,3-propanediol. Since these glycols have promising catalytic production routes from biomass, the corresponding acetals are biorenewable to their entirety. Cyclohexane was used as the water removal agent by azeotropic distillation in a Dean–Stark apparatus. The isolated yields of the acetals were excellent (>90%), and the 2-(furan-2-yl)-1,3-dioxolane was conveniently prepared on a 10 g scale. The broad substrate scope of the catalyst was demonstrated by the successful preparation of acetals from benzaldehyde in excellent isolated yields. The kCH catalyst was conveniently recovered after the reaction and reused without catastrophic loss in catalytic activity. The effect of the extent of proton exchange on the activity, thermal stability, and recyclability of the kCH catalyst was also explored.

The acetals of carbohydrate-derived furfurals have potential applications as fuel oxygenates and chemical intermediates.