By James Ashenhurst

Introduction to Rearrangement Reactions

Last updated: January 12th, 2023 |

Introduction to Rearrangement Reactions

  • Reactions that involve a carbocation intermediate may be accompanied by rearrangements where a pair of electrons from a C-H or C-C bond migrates toward the carbocation, resulting in breakage and formation of a C-H or C-C bond, and formation of a new carbocation.
  • The new carbocation (generally more stable) then undergoes a second reaction to give the final product.
  • Rearrangements can accompany addition, substitution, and elimination reactions if they progress through a carbocation intermediate.

Rearrangement Reactions

Rearrangement reactions can accompany many of the reactions we’ve previously covered such as substitution, addition, and elimination reactions.

The point of this article is not to understand why just yet, but to be able to see from the diagrams what bonds are broken and formed.

You need to understand how to read line diagrams.  But other than that no further skills are required. The point here is to be able to follow the plot – to see what is happening.

example of rearrangement reactionof an alkyl bromide with hydride shift and substitution

Subsequent posts will go into more detail as to why things happen, but it takes time to build up that knowledge.

Nucleophilic Substitution Accompanied By Rearrangement

In fact, if you don’t look closely, sometimes you can miss the fact that a rearrangement reaction has occurred. Let’s look at a substitution reaction first.

typical substitution reaction versus substitution with hydride shift

On the top is a “typical” substitution reaction: we’re taking an alkyl halide and adding water. The C-Br bond is broken and a C-OH bond is formed. If you look at the table on the right you’ll see this follows the typical pattern of substitution reactions.

However if we change one thing about this alkyl halide – move the bromine to C-3 instead of C-2 – now when we run this reaction we see a different product emerge.

It is also a substitution reaction (we’re replacing Br with OH) but it’s on a different carbon. That’s because if you look closely, you can see there are actually 3 bonds broken and 3 bonds formed. The C2-H bond broke and the C3-H bond formed.

Very strange!

This represents a rearrangement reaction – when you see a group “move” from one carbon to another.

Alkene Addition Accompanied By Rearrangement

Let’s look at another example, but involving an addition reaction (the addition of HCl to alkenes).

typical alkene addition reaction versus alkene addition with hydride shift

Here we have an addition reaction. On top, nothing special – as with all additions, we break a C-C double bond (π bond )and form two new single bonds to the adjoining carbons (H and Cl). But look at the bottom example. If we use that alkene instead, we find that the Cl ends up on C3, not C-2.

Again, examining the bonds broken/formed, we see that there’s an extra pair of events: the C3-H bond was broken and the C-2H bond was formed. In other words, the hydrogen “migrated” from one carbon to another. Weird!

Elimination (E1) Accompanied By Rearrangement

Finally, let’s look at an elimination reaction. If you take an alcohol like the one below and add an acid (like H2SO4, pictured) and help the reaction along with some heat, you break the C1-OH and C2-H bonds, and form a new double bond between C1-C2. This is, in other words, a typical elimination reaction.

But if you take a slightly modified alcohol like the bottom example (with an extra methyl group on C1) and try the same reaction, something strange happens again. Analyzing the bonds broken and formed,  there’s an “extra” bond being broken and an “extra” bond being formed here. If you look closely you can see that one of the methyl groups on C1 (we’ll call it C8) moved over to C2.

typical elimination of alcohol with acid versus elimination of alcohol with alkyl shift

So what can we conclude about rearrangement reactions?

  • They can accompany many of the reactions we’re already familiar with, such as substitution, addition, and elimination reactions.
  • They involve the “movement” of an atom (H in the top two examples, C in the third) from one carbon to another.

three examples of rearrangement reactions in substitution alkene addition and elimination reactions

What other insight might we glean from these examples? Here’s two questions.

  • look up, if you don’t know already, what “primary, secondary and tertiary alcohols and alkyl halides are (See post: Primary, Secondary, Tertiary and Quaternary in Organic Chemistry)
  • In the substitution reactions and the elimination reactions, classify every alcohol (or alkyl halide) according to whether it is primary, secondary or tertiary. Notice any difference between the “normal” cases and the “rearrangement” cases?

For more detail on rearrangement reactions, start here:

Rearrangement Reactions (1) – Hydride Shifts



Comment section

15 thoughts on “Introduction to Rearrangement Reactions

  1. Just wanted to let you know that the bond formed in your example with Cyclohex-2-ylethen should be C1-H and not C2-H! The error is in the same row with the H-Cl bond broken.

    Thanks for your explanation!

  2. Really it’s an amazing website I really loved it. I’m regretting for not knowing about this website at the beginning of my organic chemistry course. Initially I used to hate organic chemistry but now I am not willing to leave it. It’s all because of this website
    Lucky to have known about this website

  3. thanks so much for the hammond postulate explanation. I was wondering which aspects of a reaction I should be looking at when i have a relatively hindered secondary alkyl halide and wondering if it goes into SN1 or E1. We keep on coming up to this conclusion. It seems to me the relative strength of the nucleophile and solvent seem to matter. For SN1 there seems to be a need for a polar solvent to stabilize the carbocation formed. In E1 it doesn’t seem to matter. Any words of perspective?

    1. For these types of problems I’d look at these variables in order of importance: 1. primary/sec/tert 2. nucleophile (strong/weak) 3. solvent 4. temp

      Hindered secondary alkyl halide. First thing I’d look at is strength of nucleophile. Is it a good base/nucleophile (read: does it bear a negative charge)? If so, E2 and SN2 are more likely (E2 probably more than SN2 if hindered). If the nucleophile is weak (e.g. water, alcohols – anything neutral) you’ll be comparing E1 vs. SN1.

      Next after strength of nucleophile I’d rank solvent. For determining SN2/E2 (strong nucleophile/base) polar protic solvent (e.g. ethanol) generally signifies elimination. Polar aprotic signifies substitution.

      For SN1/E1 (weak nucleophile/base) the solvent will generally be polar protic. Heat favors elimination over substitution.
      Hope this helps!

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.