Substitution
vs. Elimination Reactions
Unimolecular
vs. Bimolecular
Dr. Howard Black - Department of Chemistry - Eastern Illinois University
When you treat an alkyl halide with a nucleophile/base in a certain solvent, what's the likely reaction? The flow chart below is designed to bring it all together for you, conceptually. If you plan to jot it down (or, more likely, print it), scurry into a corner, and commit it to memory, please don't - it can't be done easily, and you'll just get very confused, demoralized, and thinking that a Leisure Studies major sounds pretty good about now.
The flow sheet below is meant to be used from left to right. That is, the first step is to classify the halide structure (are unimolecular or bimolecular reactions more likely?) Then, assess the nucleophilicity vs. basicity of the nucleophile (is substitution (more Nu:) or elimination (more basic) likely to predominate?) And so on....
Just
remember the following:
- Nucleophiles
are basic and bases are nucleophilic, but can be classified as more nucleophilic
than basic, or visa versa. [Hint: HO-, RO-, and NH2-
are strongly basic; the others aren't.]
- Solvents
can be classified as protic (having an OH group) or aprotic (not having
one).
* If the base is highly crowded (like t-butoxide), elimination occurs.
**
The alkene formed with a crowded base
is the one resulting from
abstraction of the sterically
most accessible proton
- and
this usually means the less-substituted,
less stable alkene.