Abstract
The reaction between an alkoxide ion R1O and a dialkyl carbonate (R2O)2CO produces the product ions R1OCO2 and R2OCO2 . The former ion is produced by nucleophilic attack of R1O at the carbonyl centre of the dialkyl carbonate, whereas the latter ion is produced by attack of alkoxide ions at both the carbonyl centre and at an alkyl group R2. The results obtained from 2H- and 18O-labelling studies suggest that the decomposing species formed during nucleophilic addition to the carbonyl centre has a tretrahedral structure. No stable species corresponding to [R1O+(R2O)2CO] is observed. The extent of nucleophilic attack at the carbonyl centre (compared with that at the alkyl group R2) decreases with elaboration of the alkyl groups R1 or R2.

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