INVESTIGADORES
SCHMIDT Luciana Carina
artículos
Título:
Nature of the Chain Propagation in the Photostimulated Reaction of
Autor/es:
LUCIANA C. SCHMIDT,; JUAN E. ARGÜELLO; ALICIA B. PEÑÉÑORY
Revista:
JOURNAL OF ORGANIC CHEMISTRY
Editorial:
American Chemical Society
Referencias:
Año: 2007 vol. 72 p. 2936 - 2944
ISSN:
0022-3263
Resumen:
The reactivity of -SC(NH)NH2 (1), MeCOS- (2), and PhCOS- (3) toward 1-naphthyl radicals was studied
in DMSO. The photostimulated reaction of anions 1, 2, and 3 with 1-bromonaphthalene (4) after quenching
with MeI renders 1-(methylthio)naphthalene (6) as a main product together with bis(1-naphthyl) sulfide
(7) and naphthalene (5). The thioacetate ion (2) and thiobenzoate ion (3) were unreactive toward 4 as
electron-donor under photostimulation; however, in the presence of potassium tert-butoxide anion
(entrainment conditions), they gave the mentioned products 5, 6, and 7, after the addition of MeI. Quenching
of the triplet state of 4 was assigned as the photoinduced initiation step, with a rate constant value of (4.6-SC(NH)NH2 (1), MeCOS- (2), and PhCOS- (3) toward 1-naphthyl radicals was studied
in DMSO. The photostimulated reaction of anions 1, 2, and 3 with 1-bromonaphthalene (4) after quenching
with MeI renders 1-(methylthio)naphthalene (6) as a main product together with bis(1-naphthyl) sulfide
(7) and naphthalene (5). The thioacetate ion (2) and thiobenzoate ion (3) were unreactive toward 4 as
electron-donor under photostimulation; however, in the presence of potassium tert-butoxide anion
(entrainment conditions), they gave the mentioned products 5, 6, and 7, after the addition of MeI. Quenching
of the triplet state of 4 was assigned as the photoinduced initiation step, with a rate constant value of (4.61, 2, and 3 with 1-bromonaphthalene (4) after quenching
with MeI renders 1-(methylthio)naphthalene (6) as a main product together with bis(1-naphthyl) sulfide
(7) and naphthalene (5). The thioacetate ion (2) and thiobenzoate ion (3) were unreactive toward 4 as
electron-donor under photostimulation; however, in the presence of potassium tert-butoxide anion
(entrainment conditions), they gave the mentioned products 5, 6, and 7, after the addition of MeI. Quenching
of the triplet state of 4 was assigned as the photoinduced initiation step, with a rate constant value of (4.66) as a main product together with bis(1-naphthyl) sulfide
(7) and naphthalene (5). The thioacetate ion (2) and thiobenzoate ion (3) were unreactive toward 4 as
electron-donor under photostimulation; however, in the presence of potassium tert-butoxide anion
(entrainment conditions), they gave the mentioned products 5, 6, and 7, after the addition of MeI. Quenching
of the triplet state of 4 was assigned as the photoinduced initiation step, with a rate constant value of (4.67) and naphthalene (5). The thioacetate ion (2) and thiobenzoate ion (3) were unreactive toward 4 as
electron-donor under photostimulation; however, in the presence of potassium tert-butoxide anion
(entrainment conditions), they gave the mentioned products 5, 6, and 7, after the addition of MeI. Quenching
of the triplet state of 4 was assigned as the photoinduced initiation step, with a rate constant value of (4.6tert-butoxide anion
(entrainment conditions), they gave the mentioned products 5, 6, and 7, after the addition of MeI. Quenching
of the triplet state of 4 was assigned as the photoinduced initiation step, with a rate constant value of (4.65, 6, and 7, after the addition of MeI. Quenching
of the triplet state of 4 was assigned as the photoinduced initiation step, with a rate constant value of (4.64 was assigned as the photoinduced initiation step, with a rate constant value of (4.6
( 0.5) 108 M-1 s-1 for tert-butoxide anion and a rough estimated value of (8 ( 7) 107 M-1 s-1 for
anion 1. By using hydrogen abstraction from DMSO as the competitive reaction, the absolute rate constants
for the addition of anions 1, 2, and 3 to 1-naphthyl radicals have been determined to be 1.0 109, 1.20.5) 108 M-1 s-1 for tert-butoxide anion and a rough estimated value of (8 ( 7) 107 M-1 s-1 for
anion 1. By using hydrogen abstraction from DMSO as the competitive reaction, the absolute rate constants
for the addition of anions 1, 2, and 3 to 1-naphthyl radicals have been determined to be 1.0 109, 1.21. By using hydrogen abstraction from DMSO as the competitive reaction, the absolute rate constants
for the addition of anions 1, 2, and 3 to 1-naphthyl radicals have been determined to be 1.0 109, 1.21, 2, and 3 to 1-naphthyl radicals have been determined to be 1.0 109, 1.2
109, and 3.5 109 M-1 s-1, respectively. This reactivity order is in agreement with the stability of the
resulting radical anions (ArNu)¥- (10-12)¥-. The inhibition experiments of the photoinduced substitution
reaction in the presence of radical scavengers and the global quantum yield higher than the unity are
evidence of a radical chain mechanism for these substitution reactions by anions 1 and 2. Anion 3 adds
to the 1-naphthyl radical, but is neither able to initiate nor to keep the propagation cycle. Evaluation of
the electron-transfer driving forces for the reaction between (ArNu)¥- and 4 together with the absence of
a chain reaction for the anion 3 indicate that the propagation in the proposed mechanism is given by an
acid-base reaction between the radical âC(O)Me or âC(NH)NH2 (13) and a base.109, and 3.5 109 M-1 s-1, respectively. This reactivity order is in agreement with the stability of the
resulting radical anions (ArNu)¥- (10-12)¥-. The inhibition experiments of the photoinduced substitution
reaction in the presence of radical scavengers and the global quantum yield higher than the unity are
evidence of a radical chain mechanism for these substitution reactions by anions 1 and 2. Anion 3 adds
to the 1-naphthyl radical, but is neither able to initiate nor to keep the propagation cycle. Evaluation of
the electron-transfer driving forces for the reaction between (ArNu)¥- and 4 together with the absence of
a chain reaction for the anion 3 indicate that the propagation in the proposed mechanism is given by an
acid-base reaction between the radical âC(O)Me or âC(NH)NH2 (13) and a base.¥- (10-12)¥-. The inhibition experiments of the photoinduced substitution
reaction in the presence of radical scavengers and the global quantum yield higher than the unity are
evidence of a radical chain mechanism for these substitution reactions by anions 1 and 2. Anion 3 adds
to the 1-naphthyl radical, but is neither able to initiate nor to keep the propagation cycle. Evaluation of
the electron-transfer driving forces for the reaction between (ArNu)¥- and 4 together with the absence of
a chain reaction for the anion 3 indicate that the propagation in the proposed mechanism is given by an
acid-base reaction between the radical âC(O)Me or âC(NH)NH2 (13) and a base.1 and 2. Anion 3 adds
to the 1-naphthyl radical, but is neither able to initiate nor to keep the propagation cycle. Evaluation of
the electron-transfer driving forces for the reaction between (ArNu)¥- and 4 together with the absence of
a chain reaction for the anion 3 indicate that the propagation in the proposed mechanism is given by an
acid-base reaction between the radical âC(O)Me or âC(NH)NH2 (13) and a base.¥- and 4 together with the absence of
a chain reaction for the anion 3 indicate that the propagation in the proposed mechanism is given by an
acid-base reaction between the radical âC(O)Me or âC(NH)NH2 (13) and a base.3 indicate that the propagation in the proposed mechanism is given by an
acid-base reaction between the radical âC(O)Me or âC(NH)NH2 (13) and a base.-base reaction between the radical âC(O)Me or âC(NH)NH2 (13) and a base.