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Organic Reagents

By James Ashenhurst

Reagent Friday: Aluminum Chloride (AlCl3)

Last updated: January 29th, 2020 |

Aluminum Chloride (AlCl3) – A Lewis Acid Reagent For Aromatic Halogenation And The Friedel-Crafts Reactions

In a blatant plug for the Reagent Guide, each Friday  I profile a different reagent that is commonly encountered in Org 1/ Org 2. 
Note: there’s going to be an exciting announcement within the next little while on a new development regarding the Reagent Guide…more details to come soon!

Aluminum Chloride (AlCl3)


Also known as: aluminum trichloride

What it’s used for: Aluminum chloride is a strong Lewis acid. It’s most commonly used as a catalyst for the halogenation (especially chlorination) of aromatic groups, as well as in the Friedel Crafts alkylation and acylation reactions. It’s also used in the Meerwein-Ponndorf-Verley reduction

Similar or equivalent to: Iron chloride (FeCl3) is another reagent which performs many of the same reactions as AlCl3. In addition AlCl3 has essentially the same mode of action as AlBr3 and FeBr3.

Example 1: As A Lewis-Acid Catalyst For Electrophilic Chlorination


AlCl3 promotes the chlorination of aromatic molecules such as benzene, when chlorine (Cl2) is added. The AlCl3 is regenerated, and HCl is a byproduct.

Example 2: As A Reagent For The Friedel-Crafts Acylation Reaction


The Friedel-Crafts reaction is also promoted by AlCl3. In Friedel-Crafts acylation, the product is an aromatic ketone, and the byproduct is HCl. (Note:  since AlCl3 tends to coordinate to the ketone product of these reactions, it’s typically used in stoichiometric amounts and therefore is not technically a “catalyst” in this case.)

Example 3: In the Friedel-Crafts Alkylation Reaction


The Friedel-Crafts alkylation reaction is also promoted by AlCl3. Since AlCl3 will lead to the formation of a carbocation, one thing to watch out for in these cases is the possibility for rearrangement to more substituted carbocations.

Example 4: In the Meerwein-Ponndorf-Verley reduction


Finally, AlCl3 will react with alcohols to make aluminum alkoxides. The aluminum alkoxides, once formed, will catalyze the Meerwein-Ponndorf-Verley reduction of ketones to give alcohols. Interestingly, the reductant in this case is not the aluminum, but the alcohol from the aluminum alkoxide.  In the process, this alcohol is oxidized.

AlCl As A Lewis Acid Catalyst: How it works

AlCl3 (and other Lewis acids like it) will coordinate to halogens, and facilitate the breaking of these bonds.  In doing so, it increases the electrophilicity of its binding partner, making it much more reactive.

The aromatic group then attacks the resulting strong electrophile, leading to what is often called the Wheland intermediate.  (or “arenium ion”). Finally, this loses a proton to regenerate the aromatic.


The process for the Friedel-Crafts reaction is very similar (note: only the Friedel-Crafts acylation is shown here… for examples of the Friedel Crafts alkylation, see here.)


You might get some deja vu looking at the reactions of AlCl3, FeCl3, AlBr3, and FeBr3. They all behave essentially identically in these types of reactions. One final question: why do you think AlCl3 or FeCl3 might be preferred for chlorination reactions and AlBr3 or FeBr3 for bromination reactions? Why not use AlCl3 for bromination reactions?

P.S. You can read about the chemistry of AlCl3 and more than 80 other reagents in undergraduate organic chemistry in the “Organic Chemistry Reagent Guide”, available here as a downloadable PDF.

(Advanced) References and Further Reading

  1. The kinetics of aromatic halogen substitution. Part IV. The 1-halogenonaphthalenes and related compounds
    P. B. D. de la Mare and P. W. Robertson
    J. Chem. Soc., 1948, 100-106
    A paper studying the kinetics of electrophilic aromatic halogenation.A lot of chemists, including some influential figures such as Profs. H. C. Brown and G. A. Olah, put in a significant amount of work into studying the electrophilic aromatic chlorination reaction. This is important since chlorinated aromatics are useful end products and intermediates for synthesis. The following papers are a highlight of all the work that has been done in the last century.
  2. The kinetics of aromatic halogen substitution. Part IX. Relative reactivities of monosubstituted benzenes
    P. W. Robertson, P. B. D. de la Mare and B. E. Swedlund
    J. Chem. Soc., 1953, 782-788
  3. Rates of Chlorination of Benzene, Toluene and the Xylenes. Partial Rate Factors for the Chlorination Reaction
    Herbert C. Brown and Leon M. Stock
    Journal of the American Chemical Society 1957, 79 (19), 5175-5179
  4. Rates and Isomer Distributions in the Chlorination of Benzene, Toluene and t-Butylbenzene in Aqueous Acetic Acid Solvents. The Influence of Solvent on the Reaction and the Baker-Nathan Effect
    Leon M. Stock and Albert Himoe
    Journal of the American Chemical Society 1961, 83 (8), 1937-1944
  5. Aromatic Substitution. XVII. Ferric Chloride and Aluminum Chloride Catalyzed Chlorination of Benzene, Alkylbenzenes, and Halobenzenes
    George A. Olah, Stephen J. Kuhn, and Barbara A. Hardie
    Journal of the American Chemical Society 1964, 86 (6), 1055-1060
    DOI: 10.1021/ja01060a017
    C. Nonhebel
    Org. Synth. 1963, 43, 15
    DOI: 10.15227/orgsyn.043.0015
    Since anthracene is significantly more electron-rich than benzene, it is more reactive in electrophilic reactions and therefore reacts with much milder conditions – in this case chlorination is effected simply with CuCl2 rather than with the harsher combination of Cl2+FeCl3. Additionally, this procedure can be used as a convenient synthesis of CuCl, which is prone to oxidation in air.
  7. Production of hexachlorobenzene
    Inventor: Bernard H Nicolaisen, Olin Mathieson Chemical Corporation
    US Patent US2777003A
    Granted: 1957-01-08
    This patent details an industrial process for the synthesis of hexachlorobenzene from benzene and Cl2. FeCl3 can be used as the catalyst.
  8. N-Halosuccinimide/BF3−H2O, Efficient Electrophilic Halogenating Systems for Aromatics
    K. Surya Prakash, Thomas Mathew, Dushyanthi Hoole, Pierre M. Esteves, Qi Wang, Golam Rasul, and George A. Olah
    Journal of the American Chemical Society 2004, 126 (48), 15770-15776
    DOI: 10.1021/ja0465247
    A modern approach to electrophilic aromatic substitution using N-halosuccinimides, which are easier to handle than the elemental halogens. This uses BF3-H2O as the acid, which was developed by Hans Meerwein in the early 20th century.


Comment section

53 thoughts on “Reagent Friday: Aluminum Chloride (AlCl3)

  1. AlCl3 is one of my favorite Lewis acids. The MPV reduction is a really interesting reaction—it’s fallen by the wayside because it’s thermodynamically controlled and poor yields are common, but you see hydride shifts like the key step of the MPV reaction coming back in a big way these days!

    1. I love that reaction too! Just love the fact that alcohols can act as reductants, and aldehydes/ketones can act as oxidants. Hydride transfers are a pet interest of mine.

  2. Actually, the yields in the MPV reaction aren’t always too bad, and you can force it towards product just by using a lot of isopropanol, which is nice and cheap. It’s also great on a large scale for that reason – R. B. Woodward used it as the second step in his famous reserpine synthesis (; no yields unfortunately) on – if I recall correctly – 300g batches. As an aside, they also do that Diels-Alder in the first step on 2kg scale, in something like 3 gallons of benzene (the volume is given in gallons, but I forget the exact number). Those were the days.

  3. I understand that AlCl3/FeCl3 acts as a halogen carrier during chlorination of an arene.
    But why is it that the AlCl3/FeCl3 has to be ANHYDROUS? What happens if it is not anhydrous?

    1. AlCl3 reacts with water to give aluminium hydroxide and HCl. The Lewis acidity of AlCl3 and FeCl3 is greatly attenuated if water is present.

  4. Why is iron(III) chloride attractive as an alternative to the traditional AlCl3 as a catalyst for Friedel Crafts reactions?

    1. Well, even though AlCl3 is typically a stronger Lewis acid than it’s Iron equivalent, it is sometimes preferred precisely because of it’s milder acidity, and can actually generate higher yields because of this. I am not completely sure as to why that is, but it may have something to do with the fact that Aluminium trichloride is so strong that it is less selective with what it complexes with, or, on the other hand, maybe it has something to do with the fact that often stoichiometric quantities are essential for AlCl3, precisely because it complexes so strongly that it is not recycled as in the true definition of a catalyst, it is more of a “sacrificial” catalyst, and is used up during the reaction.

  5. 1) Is FeCl3 a suitable catalyst for electrophilic substitution with iodine monochloride?
    2) Can FeBr3 be used as well?
    3) Which one of these is a stronger Lewis acid?

    I have a few arguments to prove my point that FeCl3 can be used as a catalyst for the reaction of ICl with benzene. But I am unable to confirm them experimentally

  6. I read somewhere that the substrate does not undergo rearrangement in the presence of FeCl3.
    Is this true? (If it is, why does this happen?)

  7. I read that Phenols and Aniline do not undergo friedel craft acytylation as aniline forms salt with lewis acid and in phenol the acytylation occurs at O. Does this happen in case of friedel craft alkylation too? (for phenol)

    1. Phenol is a very reactive aromatic. The trick is to get it to stop at doing a single alkylation. Often, the way to do it is to protect the alcohol as an ester, do the FC alkylation, and then cleave the ester to give you back the alcohol.

  8. The picture displaying the scheme for the FC acylation is an alkylation. It looks like you had some pictures disappear from this post? The older must have been overwritten with the alkylation scheme.

    1. AlCl3 is a Lewis acid, attaches to the epoxide, makes it more likely to attack. Although I wouldn’t be surprised if LiAlH4 reacts with AlCl3 directly to make some derivative of Alane (AlCl3)

    1. They’re not the same type of compound. Neutral sodium is a reducing agent. Neutral aluminium generally has a surface oxide layer rendering it unreactive. In this post we’re talking about AlCl3, which is an Al(3+) species and a strong Lewis acid.

  9. During the Friedel-Crafts alkylation reaction, the aluminum chloride was not reacting. what are some things that could have been wrong with my aluminum chloride?
    Thank you

  10. Hi I think u have added the same example for Friedel craft acylation and alkylation as there is no ketone forming in the first one.

  11. Could you add 1-chloro-2-propanol to benzene using AlCl3? Or, is it that when you do a Friedel Crafts alkylation, it has to be a chloroalkane with no other functional groups? Any help would be appreciated

    1. It is best for it to be a simple haloalkane. The OH group will bind to the aluminum even better than the chlorine. I’m not sure what you’d get as a product, but it would likely be a complex mixture. If you must mix functional groups, it’s best to use a hydroxy protected as an ether of some kind.

  12. I think that “anhydrous ” word is missing here in the catalyst section…and according to me, it does changes the products!

  13. I am a student studying the Friedel-Craft reaction.

    I used to AlCl3 in CHCl3, polystyrene

    At the end of Friedel-Craft reaction, What should I remove with AlCl3?

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