1.

The Birch Reduction

When benzene is treated with metallic sodium (or lithium) in liquid ammonia as a solvent, in the
presence of a proton source (e.g. ethanol, methanol, or t-butanol) the result is the net reduction of
one of the double bonds of the benzene ring to give 1,4-cyclohexadiene. This reaction is known
as the Birch reduction. [Note 1]

(I say “net” because two C-C pi bonds are broken and one C-C pi bond is formed)

Ordinary alkenes are unaffected by Birch reduction conditions. Conjugated alkenes can be
reduced, however. Alkynes are partially reduced to give trans-alkenes under these
conditions (see Na/NH3 reduction of alkynes)

2. Mechanism Of The Birch Reduction

Ammonia (NH3) is a gas at room temperature, boiling at a balmy –33 °C. Gaseous ammonia can
be condensed to a liquid using a dry ice/acetone (–78°C) cold-finger, where it can serve as a
solvent for alkali metals (e.g. Li, Na, and K). Although these metals are only sparingly soluble in
liquid ammonia (about 1-5 g of Na per liter of NH3) the result is a spectacular blue color: once
made, never forgotten.
 Photo of a Birch reduction, from ChemTips by
Brandon Findlay.
The intense blue color is due to the presence of solvated electrons (e –) , swimming in the
ammonia solution. [Note 2]

Upon meeting benzene, an electron adds to the aromatic pi system, resulting in a radical
anion with seven pi electrons. [Note 3]

[Note that in the arrow-pushing mechanism, two C-C pi bonds are broken and one C-C pi bond
is formed, which is why we said that the reaction results in the net breakage of a C-C pi bond].

Being strongly basic, the radical anion is immediately protonated at carbon by the alcohol. [Note
4]
The resulting pentadienyl radical can then accept a second electron from the “electron soup”,
resulting in a new anion (a “pentadienyl anion”). (why pentadienyl and not hexadienyl? see Note
5)

It is at this stage where the presence of an alcohol (e.g. ethanol or t-butanol) becomes necessary,
since NH3 is not a strong enough acid to protonate this anion.

Protonation of this species, at the central carbon results in the 1,4-cyclohexadiene. Studies by 13-
C NMR indicate that the central carbon has the highest electron density.
So although we said that the reaction involves the net breakage of a single pi bond, actually we
break two pi bonds and form one.

3. Don’t Confuse Na/NH3 With NaNH2/NH3

Birch reduction conditions can easily be confused for conditions that form sodium amide
(NaNH2).

The key is to know the difference between sodium metal (neutral, easily gives up its single
electron) in NH3 (solvent) and NaNH2 (sodium amide, strong base) in NH3 (solvent, also
conjugate base)

For example this is not a Birch reduction – this is elimination of a chloride to

form benzyne followed by attack!

Another common mistake is to imagine that the role of Na / NH3 is to put an NH2 on the ring.
This is also incorrect.
4. Substituent Effects In The Birch Reduction
The next question to ask is, what happens when substituents are present on the ring? What kinds
of products are obtained?

Since the “nucleophile” here is essentially free electrons (e – ) , the reaction is faster on aromatic
rings with electron-withdrawing substituents (e.g. CO2H) and slower on aromatic rings with
electron-donating substituents (OCH3).

Electron-withdrawing substituents and electron-donating substituents also give different

products.

With electron withdrawing groups you get protonation adjacent to the electron-withdrawing
group.

With electron donating groups like OCH3 you get protonation on the carbon adjacent to the
carbon bearing the OCH3 (“ortho” to the -OCH3). Like this:
Why the difference?

When a substituent is present, the formation of the first C–H bond determines which product
will form. This, in turn, depends on the site where the most stable anion will form.

5. Aromatic Rings With Electron Withdrawing

Groups (EWGs) Are Protonated Adjacent To
The EWG
When an electron-withdrawing group like CO2CH3 is present, the anion can be delocalized
through resonance from carbon to oxygen (which being more electronegative, is much better at
stabilizing negative charge). Recall that this is an example of the CO2CH3 being a pi acceptor.

The protonation thus occurs on the carbon bearing the electron-withdrawing (i.e. pi-accepting)
substituent. [Note 6]
6. Aromatic Rings With Electron Donating
Groups (EDG’s) Are Protonated On The
Carbon “Ortho” To The EDG
When there’s a group that’s a strong pi donor (OCH3) then formation of an anion adjacent to that
group is actually disfavored. Electrons repel, after all!

In this case the product is determined by placing the negative charge as far away from the pi-
donating group as possible.

The resulting vinyl ethers can be hydrolyzed to ketones with aqueous acid. This process became
particularly important in the development of steroid hormones, which led to the development of
the birth control pill. For instance the synthesis of norethisterone from estradiol relied on a Birch
reduction, which we explored a little bit in this post.

As Carl Djerassi once said, “Que viva Don Arturo Birch! ”

7. Birch Reduction of Anthracene

Another interesting dissolving metal reduction is that of the polyaromatic hydrocarbon
anthracene.

Anthracene contains three aromatic rings and has a total resonance energy (i.e. the stabilization
due to aromaticity) of 83 kcal/mol, or about 27.7 kcal/mol per ring (compare to 36 kcal/mol for
benzene). [Ref]

Anthracene undergoes Birch reduction such that the central aromatic ring is reduced and a total
of two hydrogens are added to the molecule. [Note 8]. The resulting hydrocarbon has two
aromatic rings for a total resonance energy of about 72 kcal/mol. [Procedure here]