Insight into the hydrophobic functionalization of cellulose microfibrils using the Passerini three-component reaction

The aqueous catalyst-free one-pot Passerini 3-component reaction (P-3CR) was employed for the functionalization of dialdehyde cellulose (DAC) derived from the periodate oxidation of microfibrillated cellulose (MFC) with insights provided by ¹³C and ¹⁵N CP-MAS NMR and FTIR analyses. The kinetics of the P-3CR revealed rapid progress within the initial 2 h, reaching a plateau between 6 and 18 h. The reaction achieved a maximum degree of substitution (DS) with only 1 equivalent of carboxylic acid and isocyanide with respect to the number of aldehydes, therefore demonstrating the atom economy character of the P-3CR performed on MFC. Variable DS values (0.08 to 0.37) were achieved by altering the degree of oxidation of DAC (ranging from 0.48 to 1.1) when reacted with heptanoic acid and tert-butyl isocyanide. Additionally, aliphatic chain lengths of carboxylic acids from C4 to C11 were successfully used for the functionalization of DAC with distinct hydrophobic chains. Furthermore, while cosolvents negatively affected the DS when using heptanoic acid, a significant increase was observed in the case of undecanoic acid due to an improved solubility of the reagent. The aqueous medium P-3CR can thus be considered a versatile tool to tailor the functionalization of MFC and provide it with hydrophobicity.