Reaction of free [3H]phenylium ion, generated from nuclear decay of p-3H2C6H4 (I) in the presence of gaseous MeX (X = F, Cl, Br) at 30-760 Torr partial pressures, yields the corresponding labeled halobenzenes (F, 32-65%; Cl, 80-90%; Br, 84-91%), together with minor amts. of PhMe, MeC6H4X, PhCH2X, and fragmentation products. The resulting tritiated halobenzenes are characterized by significant 3H scrambling over the ring (ortho < meta < para), whose extent increased appreciably when the reaction is carried out at low MeX pressures. These results are consistent with previous expts. involving I decay in MeOH(g), and are interpreted in terms of a general mechanism involving a relatively fast (k ≃ 107 s-1) automerization sequence in the [3H]phenylium ion via consecutive 1,2-H shifts. An alternative interpretation of the MeOH data was excluded.

Automerization of gaseous phenylium ions. Direct evidence from the phenylation of methyl halides / Speranza, Maurizio; Y., Keheyan; Angelini, Giancarlo. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - STAMPA. - 105:(1983), pp. 6377-6380.

Automerization of gaseous phenylium ions. Direct evidence from the phenylation of methyl halides

SPERANZA, Maurizio;ANGELINI, Giancarlo
1983

Abstract

Reaction of free [3H]phenylium ion, generated from nuclear decay of p-3H2C6H4 (I) in the presence of gaseous MeX (X = F, Cl, Br) at 30-760 Torr partial pressures, yields the corresponding labeled halobenzenes (F, 32-65%; Cl, 80-90%; Br, 84-91%), together with minor amts. of PhMe, MeC6H4X, PhCH2X, and fragmentation products. The resulting tritiated halobenzenes are characterized by significant 3H scrambling over the ring (ortho < meta < para), whose extent increased appreciably when the reaction is carried out at low MeX pressures. These results are consistent with previous expts. involving I decay in MeOH(g), and are interpreted in terms of a general mechanism involving a relatively fast (k ≃ 107 s-1) automerization sequence in the [3H]phenylium ion via consecutive 1,2-H shifts. An alternative interpretation of the MeOH data was excluded.
1983
01 Pubblicazione su rivista::01a Articolo in rivista
Automerization of gaseous phenylium ions. Direct evidence from the phenylation of methyl halides / Speranza, Maurizio; Y., Keheyan; Angelini, Giancarlo. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - STAMPA. - 105:(1983), pp. 6377-6380.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/466342
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