Organic Reagents

By James Ashenhurst

Reagent Friday: Sodium (Na)

Last updated: January 29th, 2020 |

Sodium Metal (Na) As A Reagent In Organic Chemistry

In a blatant plug for the Reagent Guide and the Reagents App for iPhone, each Friday  I profile a different reagent that is commonly encountered in Org 1/ Org 2. 


Today’s topic, sodium metal is a pretty notorious reagent. You might know it from Youtube as “That solid that you drop in water and blows things up, a property it shares with potassium and other alkali metals.

Sodium has lots of uses in organic chemistry. Sodium metal has but a lone electron in its valence shell, and gives it up quite easily to any molecule that will accept. That includes water: what’s happening when you drop sodium metal into water is that H2O is being reduced to hydrogen gas, forming sodium hydroxide in the process. Sodium can also be used to reduce many types of organic compounds such as alkynes and aromatic compounds among many others not discussed here.

What it’s used for: a strong reducing agent, will reduce alkynes to trans-alkenes. Will also form hydrogen gas when added to alcohols, resulting in alkoxides. Will also reduce aromatic groups to alkenes (the Birch reduction). Sodium metal will generally not reduce alkenes.

Sodium Metal In NH3 –  Reduction Of Alkynes To Give trans-Alkenes

Let’s look at the first example:  reduction of alkynes to trans-alkenes. Sodium will dissolve in liquid ammonia (boiling point –33  °C) producing a beautiful deep blue color. When alkynes are present, they will be reduced to the trans (i.e. E) alkene. This makes Na/NH3 a useful companion to the Lindlar reduction of alkynes, which gives cis-alkenes.


Formation Of Alkoxides From Alcohols

As mentioned previously, sodium metal will also convert alcohols to alkoxides (remember: alkoxides are the conjugate bases of alcohols). In the process this liberates hydrogen gas, so it must be done with great caution and advisably under an oxygen-free atmosphere. This is a useful way to make the conjugate base of an alcohol without worrying about the conjugate acid hanging around in solution, since the only byproduct is hydrogen gas.


Sodium Metal In Ammonia: The Birch Reduction

Finally, sodium metal in ammonia (NH3) containing several equivalents of t-butanol will reduce aromatic compounds to (non-conjugated) dienes. This useful reaction is called the Birch reduction. Note that the pattern depends on whether the substituent on the aromatic group is electron donating (such as OCH3) or electron withdrawing (CO2Me).


Sodium In NH3 For Reduction Of Alkynes: The Mechanism

How it works – we’ll just discuss the alkyne reduction here for now, but reduction of the alkyne by sodium results in breakage of the C-C double bond and formation of an anion adjacent to a radical. The radical that is formed can interconvert between its cis and trans form, but the trans is generally more stable due to steric factors. The anion is then protonated by NH3 (the only acid present in solution) to give the vinyl radical, which is then reduced by a second equivalent of Na to give a second anion. This is then (you guessed it) then converted to the alkene by protonation with a second equivalent of NH3. So the net process gives a trans-alkene and two equivalents of NaNH2.


Real life tips. Since sodium metal is a solid, many of its reactions are surface-area dependent. That means that it is most effective as a reagent when cut up into fine strips or wires rather than chunks. As you can imagine, a reagent that reacts violently with water is potentially very hazardous.  Sodium is notoriously dangerous when used to remove traces of water from solvents in distillation setups: chunks can be passivated with a surface layer of NaOH, and scratching the surface of the material during quench will then expose reactive sodium metal, which can then react rapidly with the quenching agent, leading to explosions and fires. Potassium is even worse for this. Do a Google search for “solvent still fire” and you will get the idea.

P.S. You can read about the chemistry of Na and more than 80 other reagents in undergraduate organic chemistry in the “Organic Chemistry Reagent Guide”, available here as a downloadable PDF. The Reagents App is also available for iPhone, click on the icon below!


(Advanced) References and Further Reading

  1. Reduction of Organic Compounds by Lithium in Low Molecular Weight Amines. 11. Stereochemistry. Chemical Reduction of an Isolated Nonterminal Double Bond
    J. Am. Chem. Soc. 1955, 77, 12, 3378-3379
    DOI: 10.1002/ja01617a066
    Lithium and low-molecular weight amines (methylamine, ethylamine, isopropylamine) can also be used for dissolving metal reduction of alkynes. The advantage is that these reagents are easier to handle over sodium/ammonia.
  2. Reactions involving electron transfer. V. Reduction on nonconjugated acetylenes
    Herbert O. House and Edith F. Kinloch
    The Journal of Organic Chemistry 1974 39 (6), 747-755
    Study of the product distribution of metal reduction of internal and terminal alkynes using Na in HMPA-THF.
  3. Dissolving Metal Reduction of Acetylenes:  A Computational Study
    Robert Damrauer
    The Journal of Organic Chemistry 2006 71 (24), 9165-9171
    This is a computational investigation using DFT (density functional theory) which studies the stability of proposed intermediates in the dissolving metal reduction of acetylene, both in the gas phase and with explicit ammonia solvation.


Comment section

20 thoughts on “Reagent Friday: Sodium (Na)

    1. Well, that is an excellent question. The prevailing opinion is that the blue color of sodium dissolved in liquid ammonia is due to solvated electrons, and it is the electrons that perform the reduction. One could (and it is has been done) alternatively use electrochemical means to perform these reactions. See:
      In those cases, it appears that reduction is not due to free electrons, but occurs at the surface of the electrode.

    1. I also found this to be a very useful and informative post. It leaves me with a question that I think you probably already sort of answered but here it is: Sodium is an efficient reduction agent for reducing halides. Your post mentions that Na/NH3 reductions will reduce alkynes to alkenes but generally not reduce the substrate further to an alkene. So is this an appropriate approach to reduce a substrate with both a bromo group and an alkene where the desired product is the reduction of the bromo group but not that of the alkene?

      Thank you in advance.


      1. I don’t understand why an alkene won’t be able to be reduced further.

        Even though the carbanion intermediate that would be formed then wouldn’t be that stable as sp3 bond is lesser electronegative than sp2, the high reactivity of Na radicals should overcome that, right?

        It would be a great help to me if you could please answer that.

        1. The resulting (sp3) carbanion would be many orders ( >10) of magnitude less stable than the (sp2) carbanion, and sodium doesn’t have the reduction potential to make that possible. One exception is alkenes adjacent to an electron withdrawing group (such as an ester) which can stabilize the negative charge. It turns out the pKa of the resulting anion is a pretty good guide to what species can be reduced.

      2. Best approach if you are looking to reduce off a bromo group is just to employ lithium halogen exchange with n-butyllithium or t-butyllithium depending on whether it’s sp2 or sp3. Very clean and fast reaction.

  1. “Your post mentions that Na/NH3 reductions will reduce alkynes to alkenes but generally not reduce the substrate further to an alkene.”

    Alkane was what I meant but I am sure you gathered that was a typographical error.

    1. A very low temperature is required because the boiling point of ammonia is –33 °C. Ammonia is a gas at room temperature, which makes it unsuitable.
      In order to obtain liquid ammonia, ammonia gas is passed through a flask attached to a coldfinger apparatus (usually dry ice / acetone).

  2. How shall i come to know that there will be Claisen Condensation or Bouveault-Blanc reduction of ester upon treatment with molten sodium in alcohol under refluxing condition. Because there will be sodium alkoxide formed, which will initiate Claisen Condensation.

  3. What happens if I react sodium with chiral carboned alcohol does it’s chirality or configuration retained

Leave a Reply

Your email address will not be published. Required fields are marked *

This site uses Akismet to reduce spam. Learn how your comment data is processed.