Methylation of Chitosan with Iodomethane: Effect of Reaction Conditions on Chemoselectivity and Degree of Substitution

Authors

  • Elisabete Curti,

    1. Universidade de São Paulo, Instituto de Química de São Carlos, Avenida Trabalhador são-carlense, 400, Caixa Postal: 480, 13560-970 São Carlos/SP, Brasil
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  • Douglas de Britto,

    1. Universidade de São Paulo, Instituto de Química de São Carlos, Avenida Trabalhador são-carlense, 400, Caixa Postal: 480, 13560-970 São Carlos/SP, Brasil
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  • Sérgio Paulo Campana-Filho

    Corresponding author
    1. Universidade de São Paulo, Instituto de Química de São Carlos, Avenida Trabalhador são-carlense, 400, Caixa Postal: 480, 13560-970 São Carlos/SP, Brasil
    • Universidade de São Paulo, Instituto de Química de São Carlos, Avenida Trabalhador são-carlense, 400, Caixa Postal: 480, 13560-970 São Carlos/SP, Brasil. Fax: 55 16 273-9952
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Abstract

N,N,N-trimethylchitosan (TMC) was prepared by reacting purified chitosan with iodomethane, in the presence of sodium hydroxide, water and sodium iodide, at room temperature. The reaction medium was N-methyl-2-pyrrolidone. Different samples of TMC were obtained by adding to the reaction medium a fixed volume (5.5 mL) of aqueous NaOH solutions at different concentrations (15, 20, 30 and 40 wt.-%) and carrying out the reactions for 9 or 24 h. The features observed in the 1H and 13C NMR spectra of these chitosan derivatives, in respect of the chemical shift, number and relative intensity of the signals, depended strongly on the excess of NaOH and H3CI added to the reaction medium, but when the lowest excess was employed, the characteristics of the derivative were not affected by the reaction time to the same extent. The average degree of quaternization of these N-methylated derivatives of chitosan ranged from 10.5% to 44.8%, according to the reaction conditions. Increasing the excess of NaOH, in reactions carried out for 9 h, resulted in TMC samples with progressively higher content of trimethylated sites however, the reaction yields were correspondingly lower and O-alkylation was favored in these cases.

original image

1H NMR spectrum of sample [AX]24h dissolved in D2O (Cp = 10 g/L).

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