CHAIN PROPAGATION IN THE PHOTOSTIMULATED REACTION OF 1-
BROMONAPHTHALENE WITH SULFUR CENTERED NUCLEOPHILES IN
DMSO
Luciana C. Schmidt, Juan E. Argüello, Valentina Rey and Alicia B. Peñéñory
Instituto de Investigaciones en Físico Química de Córdoba (INFIQC), Departamento de
Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba,
Córdoba (5000), Argentina.
E-mail: penenory@dqo.fcq.unc.edu.ar
penenory@dqo.fcq.unc.edu.arPalabras clave: photoinduced electron transfer, aromatic substitution, reactivity
The reactivity of -SCNH(NH2) (1), CH3COS- (2) and PhCOS- (3) in photoinduced
substitution reactions with 1-bromonaphthalene (4) was studied in DMSO. The
photostimulated reaction of ion 1 with 4 renders after quenching with MeI 1-
(methylthio)naphthalene (50%), bis (1-naphthyl) sulfide (22%) and naphthalene (9%). This reaction does not occur in the dark and is inhibited in the presence of DTBN. The thioacetate ion (2) was unreactive towards 4 as electron donor under
photostimulation, but in the presence of potassium ter-butoxide or the enolate anion of
cyclohexenone under irradiation (entrainment conditions), it gave 1-(methylthio) naphthalene (40%), bis (1-naphthyl) sulfide (14%) and naphthalene (6%), after quenching with MeI. Similar results were obtained with the ion 3. The lack of reaction
in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 cyclohexenone under irradiation (entrainment conditions), it gave 1-(methylthio) naphthalene (40%), bis (1-naphthyl) sulfide (14%) and naphthalene (6%), after quenching with MeI. Similar results were obtained with the ion 3. The lack of reaction
in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 photostimulation, but in the presence of potassium ter-butoxide or the enolate anion of
cyclohexenone under irradiation (entrainment conditions), it gave 1-(methylthio) naphthalene (40%), bis (1-naphthyl) sulfide (14%) and naphthalene (6%), after quenching with MeI. Similar results were obtained with the ion 3. The lack of reaction
in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 cyclohexenone under irradiation (entrainment conditions), it gave 1-(methylthio) naphthalene (40%), bis (1-naphthyl) sulfide (14%) and naphthalene (6%), after quenching with MeI. Similar results were obtained with the ion 3. The lack of reaction
in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (methylthio)naphthalene (50%), bis (1-naphthyl) sulfide (22%) and naphthalene (9%). This reaction does not occur in the dark and is inhibited in the presence of DTBN. The thioacetate ion (2) was unreactive towards 4 as electron donor under
photostimulation, but in the presence of potassium ter-butoxide or the enolate anion of
cyclohexenone under irradiation (entrainment conditions), it gave 1-(methylthio) naphthalene (40%), bis (1-naphthyl) sulfide (14%) and naphthalene (6%), after quenching with MeI. Similar results were obtained with the ion 3. The lack of reaction
in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 cyclohexenone under irradiation (entrainment conditions), it gave 1-(methylthio) naphthalene (40%), bis (1-naphthyl) sulfide (14%) and naphthalene (6%), after quenching with MeI. Similar results were obtained with the ion 3. The lack of reaction
in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 photostimulation, but in the presence of potassium ter-butoxide or the enolate anion of
cyclohexenone under irradiation (entrainment conditions), it gave 1-(methylthio) naphthalene (40%), bis (1-naphthyl) sulfide (14%) and naphthalene (6%), after quenching with MeI. Similar results were obtained with the ion 3. The lack of reaction
in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 cyclohexenone under irradiation (entrainment conditions), it gave 1-(methylthio) naphthalene (40%), bis (1-naphthyl) sulfide (14%) and naphthalene (6%), after quenching with MeI. Similar results were obtained with the ion 3. The lack of reaction
in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 photostimulated reaction of ion 1 with 4 renders after quenching with MeI 1-
(methylthio)naphthalene (50%), bis (1-naphthyl) sulfide (22%) and naphthalene (9%). This reaction does not occur in the dark and is inhibited in the presence of DTBN. The thioacetate ion (2) was unreactive towards 4 as electron donor under
photostimulation, but in the presence of potassium ter-butoxide or the enolate anion of
cyclohexenone under irradiation (entrainment conditions), it gave 1-(methylthio) naphthalene (40%), bis (1-naphthyl) sulfide (14%) and naphthalene (6%), after quenching with MeI. Similar results were obtained with the ion 3. The lack of reaction
in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 cyclohexenone under irradiation (entrainment conditions), it gave 1-(methylthio) naphthalene (40%), bis (1-naphthyl) sulfide (14%) and naphthalene (6%), after quenching with MeI. Similar results were obtained with the ion 3. The lack of reaction
in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 photostimulation, but in the presence of potassium ter-butoxide or the enolate anion of
cyclohexenone under irradiation (entrainment conditions), it gave 1-(methylthio) naphthalene (40%), bis (1-naphthyl) sulfide (14%) and naphthalene (6%), after quenching with MeI. Similar results were obtained with the ion 3. The lack of reaction
in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 cyclohexenone under irradiation (entrainment conditions), it gave 1-(methylthio) naphthalene (40%), bis (1-naphthyl) sulfide (14%) and naphthalene (6%), after quenching with MeI. Similar results were obtained with the ion 3. The lack of reaction
in the dark and the inhibition of the photoinduced one by the presence of di-tertbutylnitroxide
(DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 (DTBN) and p-dinitrobenzene (p-DNB) are evidence of a radical chain
mechanism for these substitution reactions. To account for the chain reaction, a radical anion intermediate 9 is possible from deprotonation of 7 which by electron transfer to 4 mechanism for these substitution reactions. To account for the c
