Substitution vs. Elimination Reactions
Unimolecular vs. Bimolecular

Dr. Howard Black - Department of Chemistry - Eastern Illinois University

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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.