ON THE REGIOSELECTIVITY OF 4-NITROANISOLE PHOTOSUBSTITUTION WITH PRIMARY AMINES - A MECHANISTIC AND THEORETICAL-STUDY

被引:33
作者
CANTOS, A [1 ]
MARQUET, J [1 ]
MORENOMANAS, M [1 ]
GONZALEZLAFONT, A [1 ]
LLUCH, JM [1 ]
BERTRAN, J [1 ]
机构
[1] UNIV AUTONOMA BARCELONA,DEPT CHEM,E-08193 BARCELONA,SPAIN
关键词
D O I
10.1021/jo00297a059
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
4-Nitroanisole photoreacts with n-hexylamine and ethyl glycinate, giving rise to regioselective methoxy and nitro group photosubstitution, respectively. Mechanistic evidence indicates that the latter is produced through a SN23Ar* reaction, whereas the former arises from a radical ion pair via electron transfer from the amine to a 4-nitroanisole triplet excited state. AM1 semiempirical calculations on the actually involved excited states and intermediates indicate that the change of regioselectivity between the ground-state and the triplet-state substitution can be justified on the basis of frontier orbital considerations. On the other hand, neither the frontier orbital nor the net charge can explain the regioselectivity when the reaction involves electron transfer. A discussion of the influence of other previously neglected factors such as the intermediate stabilities is advanced. © 1990, American Chemical Society. All rights reserved.
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页码:3303 / 3310
页数:8
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