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In simple cases, the equilibrium lies well to the left. In certain cases, however, a larger amount of the enol form is present. There are three main types of the more stable enols: i. Molecules in which the enolic double bond is on conjugation with another double bond. For example, carboxylic esters have a much smaller enolic content than ketons. In molecules like acetoacetic ester, the enol is also stabilized by intramolecular hydrogen bonding.
ii.
Molecules that contain two or three bulky aryl groups. For example, in case of 2, 2-dimesitylethenol, the keto content at equilibrium is only 5%. In this case steric hindrance destabilizes the keto form.
iii.
Highly Fluorinated enols: The extent of enolization is greatly affected by solvant, concentratiom and temperature. Thus, acetoacetic ester has an enol content of 0.4% in water and 19.8% in toluene. In this case, water reduces the enol content by hydrogen bonding with the carbonyl, making this group less available for intramolecular bonding.
For most simple phenols, the equilibrium lies well to the side of the phenol, since only on that side is there aromaticity.
2.
Nitroso-Oxime Tautomerism
This equilibrium lies far to the right, and as a rule nitroso compounds arestable only when there is no hydrogen. 3. Nitro-acinitro Tautomerism Primary and secondary nitroalkanes containing -H undergo tautomerism.
4.
Imine-enamine Tautomerism
Enamines are normally stable only when there is no hydrogen on the nitrogen (such as R 2C = CR Otherwise, the imine from predominates.
NR2).
3.
Mesomeric Effect The permanent polarization of a group conjugated with a through the This is called mesomeric effect. + M effect possessing groups are : M effect possessing groups are : -bond or a set of alternate -bonds is transmitted -electrons of the system resulting in a different distribution of electrons in the unsaturated chain.
4.
Hyperconjugation The ability of the -bond electrons of an -C H bond to undergo conjugation with the adjacent -electrons is called hyperconjugation.
The ortho-and para-directing effect of methyl group in toluene is attributed to electron release by hyperconjugation.