The spontaneous decarboxylation of 6-nitrobenzisoxazole-3-carboxylate ion is strongly catalysed by micelles of zwitterionic surfactants, viz., sulfobetaines [C14H29N+R2(CH2)3SO- ,R = Me, Pr and C16H33N+Me2(CH2)3S03-] and amine oxides (C14H29N+R2O-, R = Me, Pr), with rates enhanced by factors of up to 1800. These micelles and those of the corresponding carboxybetaines are more effective catalysts than those of the corresponding cationic surfactants. In all cases a change from Me to Pr at the head group speeds reaction by factors of ca. 5-8 for the sulfobetaines and amine oxides and ca. 14 for the cationic surfactants. Cyclizations of the o-3-halopropyloxyphenoxide ions (halogen = Br, I), which are intramolecular SN2 reactions, are modestly micellar catalysed, but structural effects on the micellar catalysis by cationic and betaine surfactants are in the same sequence, as for decarboxylation.

Cyclisation and decarboxylation in zwitterionic micelles. Effects of head group structure

SPRETI, Nicoletta;
1996

Abstract

The spontaneous decarboxylation of 6-nitrobenzisoxazole-3-carboxylate ion is strongly catalysed by micelles of zwitterionic surfactants, viz., sulfobetaines [C14H29N+R2(CH2)3SO- ,R = Me, Pr and C16H33N+Me2(CH2)3S03-] and amine oxides (C14H29N+R2O-, R = Me, Pr), with rates enhanced by factors of up to 1800. These micelles and those of the corresponding carboxybetaines are more effective catalysts than those of the corresponding cationic surfactants. In all cases a change from Me to Pr at the head group speeds reaction by factors of ca. 5-8 for the sulfobetaines and amine oxides and ca. 14 for the cationic surfactants. Cyclizations of the o-3-halopropyloxyphenoxide ions (halogen = Br, I), which are intramolecular SN2 reactions, are modestly micellar catalysed, but structural effects on the micellar catalysis by cationic and betaine surfactants are in the same sequence, as for decarboxylation.
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11697/14447
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus ND
  • ???jsp.display-item.citation.isi??? ND
social impact