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Dehydration of a secondary alcohol proceeds readily in the presence of strong acid such as
sulfuric or phosphoric acid, and proceeds via an E1 mechanism whose intermediates, but not
arrows, are shown in Scheme 1. In step 1, protonation of the hydroxyl group of the alcohol with
the acid catalyst converts the poor leaving group -OH to a much better leaving group, H2O. The
loss of a water molecule from the oxonium ion intermediate results in a carbocation intermediate
that undergoes E1 elimination to form an alkene. If the elimination occurs with either one of the
protons from the terminal methyl (CH3) group, the resulting product is the terminal alkene – 1-
butene. Elimination from the protons on the methylene (CH2) group leads to an internal alkene.
Depending on which hydrogen is deprotonated, either the cis- or trans-alkene can be formed. The
least substituted alkene product is also known as the Hoffman product, and the more-substituted,
alkenes are known as the Saytzeff products. Of the two possible Saytzeff products, the trans-
alkene is the most stable. Since the E1 reaction is under thermodynamic control, the relative
stability of the resulting alkenes should determine the product distribution ratio. This is also known
as Saytzeff’s rule.
Scheme 1:
H3C
CH3 CH3
H2SO4
CH3 H3C CH2
H3C
O
H H3C H3C +
HO H ∆ H
H H H3C CH3
Hoffman
product
Saytzeff
products
1
A part of this procedure is adopted from an article published by H.M. Gilow in the Journal of Chemical Education,
Scheme 2:
H
H2SO4
H
H3C OH
∆
H3C O
H
X H3C H H3C
H
the use of a very bulky base H H3C
H H3C
can change the outcome of H3C
Br
H
Hoffman H H
product
the reaction. When there
Br
are steric problems
approaching one of the
H
beta-hydrogens, the base H3C
Base H
will preferentially H
CH3
H3C CH3
deprotonate the hydrogen H CH3 H CH3
Br
that is least sterically Br
Base
H
H CH3
H CH3
H
Br
Before running a reaction, chemists apply concepts from similar reactions to try and predict
the results. Oftentimes, this works and the outcome is predicted correctly. Sometimes, this does
not work and it is left to the scientist (you) to come up with a rationale for the results observed.
Bear in mind that an unexpected outcome is not necessarily because the concepts you applied were
wrong, but perhaps because something else is at work.
One or more reactions in this set of experiments might give unexpected results. Your job is
to identify which reactions gave the expected results, which give unexpected results, and explain
the unexpected results.