If the substrate is primary, can we rule out SN1 and E1 entirely?

1 Answer
Oct 31, 2015

No. You should assume that E1E1 and S_N1SN1 may still happen to some extent, because they usually still do.

Many factors contribute to that occurring; for primary alkyl halides in particular, they may include:

  • nucleophile strength
  • nucleophile steric hindrance and bulkiness
  • solvent steric hindrance and bulkiness
  • solvent interactions (nonpolar, polar protic, polar aprotic)
  • reaction temperature
  • etc.

Let us take some examples that I'm pulling from one of my 2013 worksheets:

(The given product ratios were on the worksheet as-is.)

You can tell that the substrate each time is a primary alkyl halide, but clearly there are exceptions that allow for elimination to occur, even at normal temperatures.

In the first one, the phase-transferable (organic/aqueous solubility) tetrabutylammonium chloride (t-BuNCl) nucleophile is extremely strong and is not hindered by the organic polar aprotic solvent, promoting substitution. This has no E1E1 or E2E2, but has an unknown mixture of S_N1SN1 and S_N2SN2.

In the second one, the nucleophile is pretty strong but not extremely so, and interacting with an organic polar protic solvent via H-bonding decreases the nucleophilicity, decreasing the amount of substitution by a bit. This has S_N2SN2, some E2E2, and little S_N1SN1 and E1E1, but still some.

In the third one, the steric hindrance of the nucleophile promotes elimination, particularly E2E2 and E1E1, but also allows for some S_N1SN1. Likely no S_N2SN2 because the bulkiness on the nucleophile prevents it from finding the substrate quickly.