Deciding SN1/SN2/E1/E2 (3) – The Solvent

www.masterorganicchemistry.com /2012/12/04/deciding-sn1sn2e1e2-the-solvent/

James
The Quick N’ Dirty Guide To SN1/SN2/E1/E2 Reactions, Part 3

Let’s continue with our Quick N Dirty guide to SN1/SN2/E1/E2 – a quick walkthrough of thinking through this reaction decision.

After having examined the substrate and the base/nucleophile in an SN1/SN2/E1/E2 reaction, this post is about the next question to ask:

What’s The Solvent?

Recall that there are two important types of solvents to consider: polar protic solvents and polar aprotic solvents.

Let’s do a little review, looking at polar protic solvents first.

Polar protic solvents are capable of hydrogen bonding. Recall that hydrogen bonding occurs where we have a highly electronegative atom
such as O or N directly bonded to hydrogen:

Quick N’ Dirty Tip: Solvents with OH or NH groups are polar protic solvents

Hydrogen bonding is directly responsible for the high boiling points of solvents such as water and ethanol; the partial positive charges on
hydrogen are attracted to the partial negative charges on the electronegative atoms. This is also why water is such an excellent solvent for
charged species such as halide ions; hydrogen bonding solvents surround negatively charged ions like a jacket.

Beatlemania!

This “jacket” of solvent molecules – much like a protective crowd of bobbies – means that these anions do not have the freedom of action they
would normally have if they weren’t surrounded by clingy hordes of solvent molecules. That is, they’re less nucleophilic! The propensity to
form hydrogen bonds is highest for small, highly electronegative ions such as fluorine and decreases as ions get larger (and the charge is
more diffuse). This means that in polar protic solvents, the nucleophilicity of halide anions increases as we go down the periodic table.

Now let’s talk about polar aprotic solvents; polar aprotic solvents are polar enough to dissolve charged species (such as halide ions) but do not
donate hydrogen bonds. This means that in solvents such as DMSO, DMF, acetone, or acetonitrile, nucleophilicity correlates much better with
basicity – and therefore decreases as we go down the periodic table.

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So what’s the bottom line when it comes to SN1/SN2/E1/E2?

The bottom line is this:

Quick N’ Dirty Rule #5: Polar protic solvents tend to favor elimination (E2) over substitution (SN2). Polar aprotic solvents tend
to favor substitution (SN2) relative to elimination (E2)

Let’s go back to the examples we were looking at in the first two posts. Practically, you’ll only need to consider the solvent in an
SN1/SN2/E1/E2 decision when you’ve already analyzed the substrate and the nucleophile/base. This is usually the case when you have a
secondary alkyl halide with a strongly basic nucleophile such as NaOCH3 or NaOH.
That’s especially the case in example #2, where we really can’t make the call as to whether it’s SN2 or E2 until we’ve looked at the solvent. The
fact that we are using a polar protic solvent (EtOH) is the crucial piece of information that clinches the reaction as E2.

In the last post in this series we’ll look at the impact of temperature on these reactions.
Next Post: The Role Of Temperature
[Edit Dec 13]: What’s the weakness of the Quick N’ Dirty approach? Well, it doesn’t really capture the true situation in these reactions,
that is, that they don’t always give one product exclusively. So keep in mind that when the Quick N’ Dirty approach says that E2 is the
major product, you may also have a small amount of competing SN2 occurring as well, or if SN1 is favored, you might have small amounts of
other reaction products also. The key points of this exercise is to 1) remember the major factors that affect each type of reaction, and 2) once
you know the type of reaction, be able to apply it.

Related Posts:

Guest Post On SN1/SN2/E1/E2 (5) – The Solvent

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Guest Post on SN1/SN2/E1/E2 (4): The Electrophile
Guest Post on SN1/SN2/E1/E2 (2): Three And A Half Steps To Any Substitution Or Elimination Reaction
Wrapup: The Quick N’ Dirty Guide To SN1/SN2/E1/E2

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