The Rearrangement of

Benzil to Benzilic Acid

REACTION: Representative of 1,2 Rearrangment
 Usually 1,2 Rearrangment involve migrating
carbocations, but in today’s reaction a migrating
carboanion is involved. Mechanism complex.

O O
C C O
1) H2O, EtOH
+ KOH C C OH
2) HCl, ice
OH
Benzil Benzilic acid

 Can you predict what the initial step would be in

the mechanism for this reaction?
[hint: look at reagents in step 1]

REACTION: Representative of 1,2 Rearrangment
 Usually 1,2 Rearrangment involve migrating
carbocations, but in today’s reaction a migrating
carboanion is involved.

O O
C C O
1) H2O, EtOH
+ KOH C C OH
2) HCl, ice
OH
Benzil Benzilic acid

 Can you predict what the initial step would be in the

mechanism for this reaction?
 The -OH will attack the C of one of the carbonyl groups

REACTION: Representative of 1,2 Rearrangment
 Usually 1,2 Rearrangment involve migrating
carbocations, but in today’s reaction a migrating
carboanion is involved.

O O
C C O
1) H2O, EtOH
+ KOH C C OH
2) HCl, ice
OH
Benzil Benzilic acid

 Can you predict what the initial step would be in the

mechanism for this reaction?

Which carbonyl group will be attacked first?

Why?
REACTION: Representative of 1,2 Rearrangment
 Usually 1,2 Rearrangment involve migrating
carbocations, but in today’s reaction a migrating
carboanion is involved.

O O
C C O
1) H2O, EtOH
+ KOH C C OH
2) HCl, ice
OH
Benzil Benzilic acid

Which carbonyl group will be attacked first?

Why?

Either carbonyl will be attacked – the molecule

Is symmetric.
PRECAUTIONS

 Be careful with the potassium hydroxide

solution.
 Be careful with concentrated hydrochloric
acid.
• Avoid spills handle carefully.
THINGS TO REMEMBER
• Heat and stir, with magnetic stir bar, the
chemicals to mild reflux for a short time…
15 minutes. No boiling stones.
• Reflux means that the solution is heated
into a gas and condenses to a liquid on
cold reflux condenser and drips into the
RBF.
• To remove the color and polymer
charcoal and water is added. Vacuum
filtration should result in almost clear
colorless solution.
THINGS TO REMEMBER
•Benzylic acid in the form of the potassium salt
is soluble in the water layer. SAVE THE
FILTRATE.
•Add ice and HCl to the filtrate and stir. Check
pH should be acidic.
•The solid should precipitate.
• Vacuum filter the mixture.
•Recrystallize in 250 mL beaker with a
minimum amount of water. Use between 90-
150 mL of water.
 TLC
• Be sure to run a TLC using starting
material Benzil and your product benzylic
acid. Run a silica gel TLC plate. Be sure
to make very small spots. Determine if
your product has any starting benzil.
Dilute your samples with acetone in a
small test tube. Determine Rf and put your
results in your notebook.
Solvent for TLC hexane ethyl acetate 50/50.
 Next Week

• Bring in data sheet.