Multiple bond migration with participation of a protophilic agent 3. Double bond migration in 1-methoxy-2-propene molecule with participation of hydroxide ion
Nm. Vitkovskaya et al., Multiple bond migration with participation of a protophilic agent 3. Double bond migration in 1-methoxy-2-propene molecule with participation of hydroxide ion, RUSS CHEM B, 48(4), 1999, pp. 653-658
The pathways of migration of the double bond in the 1-methoxy-2-propene mol
ecule with participation of a hydroxide ion were investigated by the ab ini
tio RHF/6-31+G* and MP2/6-31+G* methods. Stationary points corresponding to
complexes between the molecule under study and the hydroxide ion and betwe
en the corresponding carbanion and a water molecule were found on the poten
tial energy surfaces of the proton transfer reactions. As in the propene mo
lecule, migration of the double bond in the 1-methoxy-2-propene molecule ca
n occur in the gas phase by the mechanism of intramolecular proton transfer
involving the proton of the hydroxide ion. Conformational isomerism of the
initial molecule and reaction products was considered. The proposed mechan
ism of 1,3-hydrogen shift involving the proton-containing base suggests the
formation of both E- and Z-products with predominance of the latter irresp
ective of the nature of the substituent. In this case the direction of mult
iple bond migration will be completely determined by the energy difference
between the initial reagents and final products.