The origin of the quartet in Problem 29 (dibenzyl sulfoxide) Set Two of Spectral

Problems ACT Workshop Two, in the final week of semester

We discussed how to solve this question in the last lecture. You were provided with all of the
information to arrive at a single structure the only correct one.
That is all that is required as an answer. What follows below is a detailed explanation as to
the origin of the quartet. You should be able to follow the arguments, but do not worry if
you cannot at this point.
The quartet is not actually a quartet, but two separate doublets, that happen to have a similar
chemical shift to one another.
Carefully read through the figure on the following page. If you are to follow the discussion,
you need to make sure that you understand how to draw Sawhorse Projections and their
meaning, how they can be converted into Newman Projections (and their meanings and
value, particularly in providing insight into this question). These are things that were taught
is CBMS103, and are probably at the front of your text book.
So, all of the above work is meant to provide you with a compelling and convincing rationale
that the two protons on a given benzylic carbon are NOT equivalent to one another they
never can be (see part (iv) above. From this, HA and HB are predicted to be separate signals,
and as they each have one inequivalent neighbour, they should appear as two geminally
(geminal means they are on the same carbon) coupled doublets.

Now to our mysterious quartet actually two doublets with a similar chemical shift. This
explanation is usually part of CBMS303.
The scenarios (possible situations that one can imagine) discussed below refer to the
interaction between two protons, H1 and H2 (you could re-label as HA and HB in reference to
the diagrams above).
J12 refers to the coupling constant (the degree of splitting in the signal) between H1 and H2.
1 is the chemical shift (measured in Hz not so important for this discussion, but to convert
ppm the usual x-axis in HMR, to Hz, we multiply by spectrometer frequency, so 4 ppm =
1600 Hz for a 400 MHz spectrometer) of the signal from H1, and 2 is the chemical shift of
H2. 12 is the chemical shift difference (in Hz) between the two signals.

The point of all this is as follows: as the chemical shift difference between the two coupled
signals gets smaller and smaller (they become closer together), the doublets look less like
classical doublets two lines of equal intensity. In the top of the four illustrations above, we
see the two outside lines already dropping away in intensity in comparison with the
inside ones. In the illustration second from the top, above, we are close to seeing our
quartet in Problem 29. The outside lines have dropped away in their intensity and it is
looking like a quartet. Note, the intensity of the four lines from the two signals are not in a
1:3:3:1 ratio of a true quartet (as predicted by Pascals triangle), but one can imagine as the
two signals become closer together (smaller chemical shift difference, transitioning from
illustration second from top to the one second from the bottom), the ratio of the intensity of
the four lines will continue to change, and there will be a spot at which it will coincidently
look a lot like a quartet!!
This happens to be the case for the benzylic protons of dibenzyl sulfoxide. The appearance
of the signal as a quartet is the result of a perfect storm of trickery. The chemical shift
difference of our two different geminal benzylic protons was just enough for the outside line
to drop down to the extent that the four lines of the two doublets appear to be in the intensity
of 1:3:3:1.

You are welcome to discuss this further if you wish leave it until after the exam.

Andrew