Alkyne Reactions

By James Ashenhurst

Alkyne Halogenation: Bromination and Chlorination of Alkynes

Last updated: July 10th, 2025 |

Halogenation of Alkynes With Br2 and Cl2

  • Like alkenes, alkynes can undergo halogenation with Cl2, and Br
  • When 1 equivalent of the halogen is used, the products of these reactions are trans-dihaloalkenes.
  • Like halogenation of alkenes, the reaction is believed to proceed through a bridged intermediate
  • Alkynes react more slowly than alkenes towards Br2 and Cl by 3-5 orders of magnitude
  • Addition of a second equivalent of a halogen gives tetrahaloalkanes.

-summary-halogenation of alkynes with halogens cl2 br2 gives mostly trans dihaloalkenes

Table of Contents

    1. Halogenation of Alkynes With Cl2 and Br2
    2. Halogenation of Alkynes Also Proceeds Through a Bridged Ion INtermediate, Providing trans Products
    3. Addition Of A Second Equivalent of Halogen Gives Tetrahalogenated Products
    4. Notes
    5. Quiz Yourself!
    6. (Advanced) References and Further Reading

1. Halogenation of Alkynes With Cl2 and Br2

If you’ll recall from the series of posts on alkenes, alkenes react with certain electrophiles (such as halogens, among others) to give positively charged bridged intermediates. (See article – Bromination of Alkenes).  Common examples are the “bromonium ion” and the “mercurinium ion”.  These intermediates then undergo backside attack by a nucleophile, resulting in overall anti addition across the double bond (See article – Syn and Anti) .

How do the addition of Br2 and Cl2 across alkynes compare to their reactions with  alkenes with these reagents?

We might expect that alkynes, being so similar to alkenes, should also react in a similar fashion. Then again, this is organic chemistry, and sometimes changing one seemingly small variable can give an extremely different result (should you have any doubt on this, see Hydroboration of Alkynes

Happily for us, the reaction of alkynes with electrophiles such as Cl2 and Br2 does give very similar results to what is observed with alkenes.

For example, treatment of an alkyne with 1 equivalent of Br2 provides a dibrominated alkene with the two bromides opposite to each other, to give us trans-dihalides. [For slightly more detail, see Note 1.]

Bromination of alkynes with br2 gives trans dibromoalkenes with best selectivity for aliphatic alkynes

The story is similar with Cl2. Products of trans addition dominate. Although for more detail, see Note 2.

chlorination of alkynes with cl2 gives mostly trans dichloroalkenes but diminished selectivity and lower yields

2. Halogenation of Alkynes Also Proceeds Through A Bridged-Ion Intermediate, Providing Trans Products

So how does this reaction work?

Given that the reaction predominantly gives trans dihalides, the prevailing view of the mechanism is that it passes through a bridged halonium ion intermediate similar to that observed for alkenes.

In the first step, a pi-bond from the alkyne acts as a nucleophile, attacking Br2 and giving rise to a bridged-ion intermediate.

In the next step, a halide ion attacks the carbon from the back face, leading to the trans product.

mechanism for bromination of alkynes involves formation of cyclic bromonium ion followed by attack to give trans dibromoalkenes

There is actually a very interesting observation to point out here, but I’ll leave that to the “Notes” section below as it is not absolutely essential for most readers’ purposes. Here’s the teaser, though: alkynes are considerably slower to react than alkenes are. [Note 3].

3. Addition of a Second Equivalent of Halogen Results in Tetrasubstituted Products

Once the dihalogenated alkene is formed, it’s possible to subject that alkene to a second halogenation, leading to the formation of a tetrahalogenated alkane.

addition of a second equivalent of halogen to the dihaloalkene gives tetrahaloalkanes

This can either be the same halogen (Br2) or a different one (Cl2) depending on your needs.


Notes

Note 1. This falls firmly into the “You Don’t Need To Know This For Org 1 / Org 2” category, so here goes. While aliphatic alkynes (i.e. alkynes attached to alkyl groups) tend to give only trans dibromides, with aryl alkynes there is considerably less selectivity for the trans product. For instance, in the example above, we saw that phenylacetylene only gave a 82:18 ratio of trans: cis whereas there were no cis products observed at all for 3-hexyne.

This loss of stereoselectivity likely reflects a slightly different mechanism may be in play. One mechanism that has been proposed is the intermediacy of a vinyl cation, which could undergo attack from either face.

mechanism of bromination of phenylacetylene through vinyl cation intermediate gives reduced selectivity for trans dibromides

Note 2. Also falls into “You Don’t Really Need To Know This”, but chlorination is a considerably worse reaction than bromination (less selective).
For the reaction of Cl2 with 3-hexyne and 2-butyne, Yates and Go note, “these reactions are not clean, and many products were found”.  For the chlorination of 3-hexyne shown in the scheme above, the actual yield of trans-dichlroalkene was 19% and the yield of cis-dichloroalkene was 7%. The major product (51%) incorporated acetic acid into the final product via trans addition. This shows that a cyclic bridged ion intermediate is likely still present. ( Interestingly, the reactions of terminal alkynes (1-hexyne and 1-pentyne) cleanly gives only syn addition products, which the authors speculate proceeds via a vinyl cation followed by quick trapping of the proximal chloride ion.

chlorination of alkyl acetylenes has poor yields of trans dichloroalkenes and lots of incorporation of acetic acid

Note 3.  Since the reaction goes through essentially the same pathway for alkenes as for alkynes, it presents us with an opportunity for an interesting experiment.

What reacts faster, alkenes or alkynes?

Researchers addressed this question by treating alkenes and alkynes with very similar structures (e.g. trans-3-hexene vs. 3-hexyne) and measuring the rate constants.

It was found that alkenes react with Cl2 and Br2  considerably faster than alkynes of similar structure, by factors of 1000 up to 100,000.

Another way of saying this is that the pi-bonds of alkenes are better nucleophiles than alkynes.

Remember that sp-hybridized carbons are better at stabilizing negative charge since the orbitals are closer to the nucleus? Well, that same effect means that these carbons are poorer at stabilizing positive charge (i.e. a lack of electron density) since, in effect, you are bringing an electron-deficient orbital closer to the nucleus.

You can think of alkynes as holding on to their electrons slightly more tightly than do alkenes.

acetylenes are not as reactive as alkenes with halogenation - rates of bromination are several orders of magnitude faster with alkenes olefins

Furthermore, the additional double bond leads to considerably more ring strain; sp2 hybridized carbons [ideal angle 120°] constrained into a triangle [internal angle 60°] is more unstable than an sp3 hybridized carbon [ideal angle 109°] would be.

There’s a second point which doesn’t become apparent for most students until second-semester organic chemistry. The 3-membered ring intermediate formed has antiaromatic character. (See post: Antiaromaticity)

 


Quiz Yourself!

[Quizzes]


(Advanced) References and Further Reading

Good reviews are to be found in Carey and Sundberg A.  Chapter 6 (Polar Addition and Elimination Reactions) p. 374 in the 4th ed. Also, Patai’s Chemistry of Triple Bonded Functional Groups part 1, p. 539 has a good discussion of the mechanism (vinyl cations with phenyl substituents, bridged intermediates with alkyl acetylenes).

  1. Untersuchungen über Alloisomerie. II
    Arthur Michael
    J. Prakt. Chem. 1892, 46 (1), 209-210
    DOI:
    10.1002/prac.18920460115
    An early paper on the bromination of alkynes. This paper mentions that bromination of dicarboxyacetylene gave 70% of the trans isomer!
  2. Kinetics and mechanism of electrophilic bromination of acetylenes
    James A. Pincock, Keith Yates
    Canadian Journal of Chemistry, 1970, 48 (21): 3332-3348
    DOI:
    1139/v70-561
    Stereoselective anti addition was found in the bromination of 3-hexyne, but both cis and trans products were obtained in the bromination of phenylacetylene. Notably, the reaction was found to be about 105 faster for 3-hexene than for 3-hexyne in acetic acid.
  3. Vinyl cation intermediates in electrophilic additions to triple bonds. 2. Chlorination of alkylacetylenes
    Keith Yates and T. Andrew Go
    The Journal of Organic Chemistry 1980 45 (12), 2385-2391
    DOI: 10.1021/jo01300a024
    Electrophilic chlorination of alkyl acetylenes is less stereospecific than for bromination. Yields are lower, and there is more incorporation of solvent.
  4. The Stereochemistry of Electrophilic Additions to Olefins and Acetylenes
    Robert C. Fahey
    Topics in Stereochemistry 1968, 3, 237-342
    DOI:
    1002/9780470147122.ch4
    This review is more weighted towards alkene reactions, but does contain sections on the addition of Cl2 and Br2 to acetylenes. On pg. 291, the author states, “[…] bromine additions to acetylenes […] in acetic acid follow kinetics similar to those found for olefins, but that acetylenes are 100- to 50,000-fold less reactive than the corresponding olefins”.
  5. Electron transmission study of the splitting of the p* molecular orbitals of angle-strained cyclic acetylenes: implications for the electrophilicity of alkynes
    Lily Ng, Kenneth D. Jordan, Adolf Krebs, and Wolfgang Rueger
    Journal of the American Chemical Society 1982, 104 (26), 7414-7416
    DOI:
    1021/ja00390a005
    Another possible explanation for the lower reactivity of alkynes relative to alkenes has to do with the availability of the unfilled orbital in the alkyne. It has been shown that a p* orbital of bent alkynes (e.g. cyclooctyne) has a lower energy than the p* orbital of alkenes, and it has been suggested that linear alkynes can achieve a bent structure in their transition states when reacting with an electrophile.

Comments

Comment section

13 thoughts on “Alkyne Halogenation: Bromination and Chlorination of Alkynes

  1. Hi ,

    Why in Note 2 you mentioned that the antiaromatic character of cyclic brominium ion of alkyne halogenation?
    Is the 1 pie bond makes it aromatic ??
    Kindly explain me sir

  2. I have seen somewhere that you even get a cis product,through what other mechanism can you get a it

  3. “The 3-membered ring intermediate formed has antiaromatic character. That is, there are 4 π electrons constrained in a conjugated ring,” does this mean that one of the two lone pairs of Cl is part of the antiaromatic system?

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