INVESTIGADORES
BONESI Sergio Mauricio
artículos
Título:
Effect of protic cosolvents on the photooxygenation of diethyl sulfide
Autor/es:
SERGIO M. BONESI, ANGELO ALBINI
Revista:
JOURNAL OF ORGANIC CHEMISTRY
Editorial:
ACS
Referencias:
Lugar: EEUU; Año: 2000 vol. 65 p. 4532 - 4536
ISSN:
0022-3263
Resumen:
The sluggish (kr < 10kq) photooxygenation of diethyl sulfide in both benzene and other aprotic
solvents such as acetone and acetonitrile is made efficient by addition of small amounts of alcohols
and, with a much more conspicuous increase, of phenols and carboxylic acids (,0.1% additive is
sufficient in this case). A kinetic analysis shows that the effect is accounted for by interaction of
the protic additives with the first formed intermediate, the persulfoxide, in competition with cleavage
to the components. The thus obtained rate constants kH linearly correlate with the acid strength
of the additives, and the effect is rationalized as a general acid catalysis. Hydrogen bonding of the
persulfoxide under this condition accounts in an economic way for the observed data, including
co-oxygenation of Ph2SO in mixed solvents.kr < 10kq) photooxygenation of diethyl sulfide in both benzene and other aprotic
solvents such as acetone and acetonitrile is made efficient by addition of small amounts of alcohols
and, with a much more conspicuous increase, of phenols and carboxylic acids (,0.1% additive is
sufficient in this case). A kinetic analysis shows that the effect is accounted for by interaction of
the protic additives with the first formed intermediate, the persulfoxide, in competition with cleavage
to the components. The thus obtained rate constants kH linearly correlate with the acid strength
of the additives, and the effect is rationalized as a general acid catalysis. Hydrogen bonding of the
persulfoxide under this condition accounts in an economic way for the observed data, including
co-oxygenation of Ph2SO in mixed solvents.,0.1% additive is
sufficient in this case). A kinetic analysis shows that the effect is accounted for by interaction of
the protic additives with the first formed intermediate, the persulfoxide, in competition with cleavage
to the components. The thus obtained rate constants kH linearly correlate with the acid strength
of the additives, and the effect is rationalized as a general acid catalysis. Hydrogen bonding of the
persulfoxide under this condition accounts in an economic way for the observed data, including
co-oxygenation of Ph2SO in mixed solvents.kH linearly correlate with the acid strength
of the additives, and the effect is rationalized as a general acid catalysis. Hydrogen bonding of the
persulfoxide under this condition accounts in an economic way for the observed data, including
co-oxygenation of Ph2SO in mixed solvents.2SO in mixed solvents.