The investigation into the intramolecular nucleophilic attack in carbanion [RCH 鈭?/sup>NCHC6H4Y] in the gas phase has been carried out by mass spectrometry and density functional theory (DFT). The main results of the present work are as follows: the regioselectivity of the intramolecular attack depends on the substituent on the para-position of the benzene ring. NO2 favors C3-attack to form spiro-蟽-adduct and it also contributes to the loss of HCN, while other substituents (H, OMe, NMe2 and Cl) favor C4-attack to yield bicyclo-蟽-adduct and in this condition, HCN cannot be lost. In the meantime, DFT calculations also demonstrate that the loss of HCN from the spiro-蟽-adduct is both thermodynamically and kinetically beneficial, while that from the bicyclo-蟽-adduct is disadvantageous either in kinetics or thermodynamics.
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