ARNDT - EISTERT REACTION

* A carboxylic acid can be converted to a higher homologue with one additional carbon
atom by employing Arndt-Eistert reaction.
SOCl2 CH2N2 Ag+
R-
-------------> R-COCl --------------> R-COCHN2 ----------------------> R-CH2CONu
COOH
ether, Et3N Nucleophile (Nu)

* The steps involved in this reaction are:

1) Conversion of carboxylic acid to an active compound like acid chloride or an anhydride.

R-COOH + SOCl2 --------> R-COCl + SO2 + HCl

2) Conversion of acid chloride to a diazoketone. A base like Et3N is employed to neutralize

HCl liberated in this step.

R-COCl + CH2N2 --------> R-COCHN2 + HCl

3) Wolff rearrangement of diazoketone into a ketene and subsequent conversion of it to a
higher carboxylic acid or its derivative by using a nucleophile.
Ag2O, Δ or hν, -N2 Nucleophile (Nu)
-------------------------------- R- ---------------------------
R-COCHN2 R-CH2CONu
-----> CH=C=O ----->
higher
diazoketone Wolff rearrangement ketene
homologue

* Nucleophile (Nu) = water or alcohol or amines

MECHANISM

1) Initially the diazomethane is acylated by the acid chloride to give a diazoketone.

* The HCl liberated in the first step must be neutralized by a suitable base to avoid the
formation of chloromethyl ketone.

2) Thus formed diazoketone is rearranged to a ketene. This is called Wolff-rearrangement.

* Silver salts like PhCO2Ag, Ag2O along with heat or light catalyze the Wolff
rearrangement.

* The configuration of 'R' group during Wolff rearrangement is retained.

 3) The ketene is immediately attacked by an appropriate nucleophile in the solution.

ILLUSTRATIONS

1)

* Nitro group is not affected in the above reaction.

2)

* The carboxylic group is first converted to an anhydride using ethyl chloroformate,

ClCO2Et.

* Also note that the configuration at stereogenic carbon is retained.

BIRCH REDUCTION - EXERCISES

I) Suggest the products likely to be formed during the birch reduction of the
following compounds.
II) Write the products formed in the following reactions.