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REACTION OF THE DAY_18
Chemistry
The Pinacol Rearrangement
When the 1, 2-diol ‘pinacol’ is treated with acid, a rearrangement takes place.
Mechanism of Pinacol Rearrangement :
Step 1 : Protonation of a hydroxyl group.
Step 2 : Loss of water gives a carbocation.
Step 3 : Methyl migration forms a resonanace-stabilized carbocation.
Step 4 : Deprotonation gives the product.
(1)
Important point:
You can view the pinacol as a rearrangement with a ‘push’ and a ‘pull’. The carbocation left by the depar-
ture of water ‘pull’s the migrating group across at the same time as the oxygen’s lone pair ‘pushes’ it.
Try Yourself
1. Complete the following reaction
OH H
+
H
Ph – C – C – OH P
*
Ph Ph
The major product P is
Ph O Ph O
(1) Ph – C*– C – H (2) Ph – C – C – H
*
Ph Ph
H O H O
(3) Ph – C*– C – H (4) Ph – C – C – H
*
Ph Ph
Ph
OH H+
Major Product (P)
2.
OH
Ph
Product P is
Ph
Ph
Ph
(1) O (2)
Ph
O
(2)
Ph Ph
Ph
(3) O (4)
O
Ph
3.
Sum of locants of methyl groups in major product is ___
(1) 8 (2) 2
(3) 4 (4) 3
4. In how many of the following reactions alkyl or phenyl migration is observed?
(I) Pinacol-Pinacolone rearrangement
(II) Preparation of alcohol from cumene hydroperoxide
(III) Baeyer villiger oxidation
(IV) Beckmann rearrangement
(V) Diazonium ion formation from aniline
(VI) Hofmann bromide degradation
(1) 5 (2) 7
(3) 4 (4) 6
5. What is the major product of given reaction?
(i) MgBr2
H5C6 C6H5 (ii) H O
major product
O
2
(Given order of migratory aptitude is aryl > alkyl > hydrogen)
O
(1) C6H5–C–CH2–C6H5
O
(2) H–C–CH–C6H5
C6H5
O
(3) C6H5–C–CHO
O
(4) C6H5–C–H
(3)
Answer of Question Based on Etard Reaction
1. Answer (2)
2. Answer (1)
3. Answer (3)
4. Answer (1)
5. Answer (2)
(4)
