Alkyne Halogenation: Bromination, Chlorination, and Iodination of Alkynes

Halogenation of Alkynes With Cl₂, Br₂, and I₂

Last time we discussed the similarities (and differences) between the carbocation pathway for alkenes and alkynes. In this post, we’ll do the same for the “3-membered ring pathway”.

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. Common examples are the “bromonium ion” and the “mercurinium ion”.  These intermediates then undergo backside attack by a nucleophile, giving products with trans stereochemistry.

So… we might also expect that alkynes, being so similar to alkenes, should also react in a similar fashion. [Of course, as someone who has studied organic chemistry for awhile could tell you, what we “expect” to happen is not always what does actually happen!].

Table of Contents

1. Reaction of Alkynes With Cl₂, Br₂ , and I₂
2. The Reaction Also Proceeds Through A Bridged-Ion Intermediate, Providing Trans Products
3. Comparing the “Three-Membered Ring” Pathway For Alkenes And Alkynes
4. Notes
5. (Advanced) References and Further Reading

1. Halogenation of Alkynes With Cl₂, Br₂, and I₂

Well, happily for us, the reaction of alkynes with electrophiles such as Cl₂, Br₂, and I₂ does give very similar results to what is observed with alkenes. For example, treatment of an alkyne with 1 equivalent of Cl₂ provides a dichlorinated alkene with the two chlorides opposite to each other. If a second equivalent of Cl₂ is added, the tetrachloro derivative will form. [Note 1]

So how might this reaction work? Here’s a proposal.

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

Just as with alkenes, a π bond from the alkyne can act as a nucleophile, attacking Cl₂ and giving rise to a bridged intermediate. In the next step, chloride ion attacks the carbon from the back face, leading to the trans product.

There is actually a very interesting observation to point out here, but I’ll leave that to the “Notes” section below as it isn’t absolutely essential for most readers’ purposes. Here’s the teaser, though: alkynes are considerably slower to react than alkenes are. [Note 2].

What’s next on this list? Well, for our purposes, halogenation of alkynes just about covers the important reactions for the 3-membered ring pathway of alkynes. Yes, oxymercuration of alkynes proceeds through the 3-membered ring pathway, but as discussed in this earlier post, this reaction is a bit of an anomaly:  treatment of alkynes with mercury (II) and water [and acid] actually provides us with a carbonyl species [ketones, generally] after keto-enol tautomerism of an enol intermediate.

3. Comparing the “Three-Membered Ring” Pathway For Halogenation of Alkenes And Alkynes

At this point it’s worth summarizing the key similarities and differences between the 3-membered ring pathway for alkynes and alkenes.

In the next post, we’ll compare the “Concerted” pathway for alkynes and alkenes.

Next Post: Alkynes – The “Concerted” Pathway

Notes

[Note 1]. It’s not a problem to isolate the dichlorinated alkene here: the two electron-withdrawing chlorines make it a poorer nucleophile than the starting alkyne. This means that it’s possible to add a different electrophile to the alkene, for instance. So if you wanted to chlorinate then brominate, that would be a feasible option here (still giving the tetrahalide product).

[Note 2]. Why might the reaction of alkynes be slower than that for alkenes? After all, shouldn’t the alkyne be more “exposed” than the alkene, less sterically hindered? Well, the 3-membered ring intermediate formed from alkynes and halogens has two properties which make it more unstable than the corresponding 3-membered ring intermediate formed from alkenes. First of all, 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. That is, there are 4 π electrons constrained in a conjugated ring, similar to the [never isolated] oxirene. Therefore this intermediate should be particularly high-energy and have a higher activation barrier to formation.

Note that there is some disagreement on the mechanism; it has been proposed that this reaction might proceed through nucleophilic attack on alkyne, at least for the first equivalent of Br₂ [according to my March 5th ed. – Sinn, H. et. al., Montash Chem 1965, 96, 1036 ]

[Note 3] What about formation of halohydrins with, say, Cl₂ and H₂O, like we did with alkenes? Well, that reaction also works, but just as with oxymercuration, it’s complicated: we make a halogenated enol intermediate, which again goes through keto-enol tautomerization and forms a carbonyl. Because tautomerization is usually a 2^nd semester topic, and most textbooks figure that it’s not worth going into this reaction in detail at this time , the topic is usually absent from the chapter on alkynes. For the super curious, here’s a proposal:

Next Post: Alkynes – The “Concerted” Pathway

(Advanced) References and Further Reading

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. Vergleichende Untersuchung der Bromaddition an symmetrisch substituierte Stilben- und Tolan-Derivate
   Sinn, H., Hopperdietzel, S. & Sauermann, D.
   Monatshefte für Chemie 1965, 96, 1036–1055
   DOI: 1007/BF00919180
   There is some disagreement on the mechanism of additions to alkynes, and this paper provides some evidence for nucleophilic attack of Br₂.
3. 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”.
4. 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 brumation of phenylacetylene.
5. Reactions of sulfenyl halides and their derivatives. 14. Effect of acetylene structure on the rates and products of addition of 4-chlorobenzenesulfenyl chloride
   George H. Schmid, Agnieszka Modro, Fred Lenz, Dennis G. Garratt, and Keith Yates
   The Journal of Organic Chemistry 1976, 41 (13), 2331-2336
   DOI: 1021/jo00875a025
   Where electrophilic addition involves bridged-ion intermediates, those arising from triple bonds are more strained than those arising from alkenes. This may be a reason why electrophilic additions by such electrophiles as Br, I, SR and so on, is slower for triple than for double bonds.
6. 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.