TY - JOUR
T1 - A study of N-nitrosoamide-mediated Friedel-Crafts type benzylation of benzene-toluene and benzene-anisole
AU - Darbeau, Ron W.
AU - White, Emil H.
PY - 2000/2/25
Y1 - 2000/2/25
N2 - Nitrogen-separated carbocation-carboxylate ion pairs were employed as sources of carbocations in the alkylation of aromatic compounds. The N- nitrosoamide approach to these nitrogenous-molecule-separated ion pairs is an excellent alternative to the standard acid-catalyzed Friedel-Crafts approach for studies of the alkylation because of the following variables: high reactivity of the electrophile, stability of the products, strict kinetic control, homogeneity, lack of overalkylation, straightforward chemistry, and good product balance. In deaminative benzylations of benzene-toluene and anisole-benzene mixtures, the values of k(X)/k(B) and % meta isomer are significantly different from those observed in the standard benzylations in a manner that indicates the deaminative electrophiles are more reactive than those generated by the standard Friedel-Crafts approach. The reactions show a direct proportionality between inter- and intramolecular selectivities and thus follow the Brown selectivity relationship (BSR). The benzylation of 2,4,6-trideuteriotoluene provided no evidence for deuterium rearrangements (or coupled benzyl rearrangements) in the arenium ion intermediate. Kinetic isotope effects were not detected. The methyl substituent on toluene appears to affect intermolecular selectivity (k(T)/k(B)) and intramolecular selectivity (o, m, p distribution) to similar degrees. A mechanism is proposed in which both selectivities are determined by activation energy differences in the transition states leading to the σ-complex intermediates. The observation that most standard Friedel-Crafts benzylations do not follow the BSR is discussed in terms of possible systematic errors in those cases. Silver ion-assisted Friedel-Crafts benzylations were performed under dry, basic conditions to investigate whether the standard approach could lead to data that obey the BSR.
AB - Nitrogen-separated carbocation-carboxylate ion pairs were employed as sources of carbocations in the alkylation of aromatic compounds. The N- nitrosoamide approach to these nitrogenous-molecule-separated ion pairs is an excellent alternative to the standard acid-catalyzed Friedel-Crafts approach for studies of the alkylation because of the following variables: high reactivity of the electrophile, stability of the products, strict kinetic control, homogeneity, lack of overalkylation, straightforward chemistry, and good product balance. In deaminative benzylations of benzene-toluene and anisole-benzene mixtures, the values of k(X)/k(B) and % meta isomer are significantly different from those observed in the standard benzylations in a manner that indicates the deaminative electrophiles are more reactive than those generated by the standard Friedel-Crafts approach. The reactions show a direct proportionality between inter- and intramolecular selectivities and thus follow the Brown selectivity relationship (BSR). The benzylation of 2,4,6-trideuteriotoluene provided no evidence for deuterium rearrangements (or coupled benzyl rearrangements) in the arenium ion intermediate. Kinetic isotope effects were not detected. The methyl substituent on toluene appears to affect intermolecular selectivity (k(T)/k(B)) and intramolecular selectivity (o, m, p distribution) to similar degrees. A mechanism is proposed in which both selectivities are determined by activation energy differences in the transition states leading to the σ-complex intermediates. The observation that most standard Friedel-Crafts benzylations do not follow the BSR is discussed in terms of possible systematic errors in those cases. Silver ion-assisted Friedel-Crafts benzylations were performed under dry, basic conditions to investigate whether the standard approach could lead to data that obey the BSR.
UR - http://www.scopus.com/inward/record.url?scp=0034712226&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0034712226&partnerID=8YFLogxK
U2 - 10.1021/jo9916378
DO - 10.1021/jo9916378
M3 - Article
AN - SCOPUS:0034712226
SN - 0022-3263
VL - 65
SP - 1121
EP - 1131
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 4
ER -