
TY  - JOUR
A1  - Freeman, DJ 
A1  - Newcombe, PJ 
A1  - Norris, RK 
T1  - An ionic chain mechanism for the substitution of an acetate group by the 2-Nitropropan-2-ide ion in benzylidene diacetates
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1976
VL  - 29
IS  - 2
SP  - 327
EP  - 337
KW  - 
UR  - https://doi.org/10.1071/CH9760327 
N2  - The reaction of 16 arylmethylene diacetates [benzylidene diacetates; ArCH(OAc)2] with lithium 2-nitropropan-2-ide in dimethyl sulphoxide has been studied. With the exception of aryl rings bearing strongly electron-donating substituents a ready reaction takes place giving l-aryl-2-methyl-2-nitropropyl acetates in good yield. The mechanism of this reaction, in which an acetate group is formally substituted by a (CH3)2C(N02) group, has been shown to be an ionic chain mechanisminvolving nucleophilic cleavage of the diacetate to catalytic quantities of the corresponding arene carbaldehyde (ArCHO) which subsequently undergoes a Henry condensation followed by a transacetylation reaction. In some cases (nitro heteroaromatic derivatives) a subsequent elimination reaction gives enol-acetates [ArC(OAc)=C(CH3)2]. 
ER  -

