High-yield regioselective synthesis of imines and oxazolidines derivatives of 2-amino-1,3-propandiol (serinol) was achieved by performing the reaction with aldehydes and ketones, in the absence of solvents and catalysts. Only imines were obtained when the carbonyl compound was aromatic and/or sterically hindered and when conjugated double bonds were formed. 1,3-Oxazolidines were specifically obtained with either aldehydes or ketones with limited steric hindrance. The “green” reaction conditions here adopted for the synthesis of these classes of derivatives are not due to the structural and functional peculiarity of the serinol as a reactant and can also be extended to lipophilic amines with the same good results in terms of yield and selectivity. A revision of the mechanism typically accepted in the presence of solvent and catalysis is proposed, and the quantum mechanics calculations applied to some derivatives are in good agreement with the proposed rationalizations of the selectivity observed. Serinol itself and the imine and oxazolidine derivatives were used, in place of guanidine, as accelerators in compounds based on diene rubbers and silica, suitable for application in tire treads with low environmental impact. Efficient sulfur-based cross-linking and composites with a low dissipation of energy were obtained. The oxazolidine and imine appear to act as protective groups of the serinol primary amine. This work paves the way for the selective synthesis of biosourced families of chemicals, which could be used for large-scale applications, such as the one in rubber compounds, replacing toxic oil-based chemicals.

Environmentally Friendly and Regioselective One-Pot Synthesis of Imines and Oxazolidines Serinol Derivatives and Their Use for Rubber Cross-Linking

Barbera, Vincenzina;Leonardi, Gabriella;Valerio, Antonio Marco;Rubino, Lucia;Sun, Shuquan;Famulari, Antonino;Galimberti, Maurizio;Citterio, Attilio;Sebastiano, Roberto
2020-01-01

Abstract

High-yield regioselective synthesis of imines and oxazolidines derivatives of 2-amino-1,3-propandiol (serinol) was achieved by performing the reaction with aldehydes and ketones, in the absence of solvents and catalysts. Only imines were obtained when the carbonyl compound was aromatic and/or sterically hindered and when conjugated double bonds were formed. 1,3-Oxazolidines were specifically obtained with either aldehydes or ketones with limited steric hindrance. The “green” reaction conditions here adopted for the synthesis of these classes of derivatives are not due to the structural and functional peculiarity of the serinol as a reactant and can also be extended to lipophilic amines with the same good results in terms of yield and selectivity. A revision of the mechanism typically accepted in the presence of solvent and catalysis is proposed, and the quantum mechanics calculations applied to some derivatives are in good agreement with the proposed rationalizations of the selectivity observed. Serinol itself and the imine and oxazolidine derivatives were used, in place of guanidine, as accelerators in compounds based on diene rubbers and silica, suitable for application in tire treads with low environmental impact. Efficient sulfur-based cross-linking and composites with a low dissipation of energy were obtained. The oxazolidine and imine appear to act as protective groups of the serinol primary amine. This work paves the way for the selective synthesis of biosourced families of chemicals, which could be used for large-scale applications, such as the one in rubber compounds, replacing toxic oil-based chemicals.
Serinol derivatives, Imines, 1,3-oxazolidines, isomers, Replacement of guanidines, rubber compounds, sulfur based cross-linking, accelerators
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11311/1141920
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