title: Vinylidene-quinone methides, photochemical generation and β-silicon effect on reactivity.
abstract: Irradiation of 2-alkynylphenols resulted in the generation of vinylidene-quinone methides (QMs), which were detected by laser flash photolysis in organic solvents and aqueous acetonitrile. QMs' spectroscopic properties and electrophilicity were both significantly affected by β-silicon effect. The hydration of the alkynyl moiety (22 and 900 M(-1) s(-1)for QM-1 and QM-2, in aqueous acetonitrile) was an acid- and base-catalyzed process. The addition of amines was fast (9.2 × 10(3) M(-1) s(-1) < k(2) < 1.3 × 10(8) M(-1) s(-1)), yielding ketimines, with primary amines.
authors.affiliation: Dipartimento di Chimica, Università di Pavia, V.le Taramelli 10, 27100 Pavia, Italy.
authors.forename: Filippo
authors.initials: F
authors.lastname: Doria
authors.forename: Claudia
authors.initials: C
authors.lastname: Percivalle
authors.forename: Mauro
authors.initials: M
authors.lastname: Freccero