Using 1 H NMR Spectroscopy

for Structure Determination

 Example #1
Deduce the structure of a compound with the
formula C3H7Br that has the following 1 H NMR
spectrum: 3.1 ppm (triplet; integral = 1), 1.7
ppm (sextet; integral = 1), and 1.0 ppm (triplet;
integral = 1.5).
To Start: calculate the number of double bond
equivalents.
1 H-NMR Analysis
Step 1: summarize the 1 H-NMR data in a table.
Step 2: The total of the integrals is 1 + 1 + 1.5 =
3.5. Because there are seven hydrogens, we
conclude that each unit of the integral
corresponds to two hydrogens.
Step 3: For each 1 H-NMR signal, use the
number of hydrogens to decide if each signal
corresponds to a CH3 , CH2 , CH, OH, NH, etc.
For example, a three hydrogen signal might arise
from a CH 3 , 3 x CH, or 3 x OH. OH is possible
only when there is enough oxygen in the
formula, if the IR does not rule it out, and if the
1 H-NMR signal is not split.
Step 4: Use the n+1 rule and the observed splitting
patterns to determine all the possibilities that would
give the observed 1 H-NMR signals. Example: The
2H triplet at 3.1 ppm could be due to a CH2 , or 2 CH
groups. The CH2 or 2 x CH groups must have two
neighbors, as the observed splitting pattern is a
triplet. Keeping things simple, it would appear that
the CH2 group has another CH2 group next to it; this
accounts for the triplet.
The sextet at 1.7 ppm must arise from a total of five
neighboring hydrogens. Since a single carbon cant
have five hydrogens, there must be two different
sets of hydrogens that sum to five; lets use a CH3
and a CH 2 group. We make record of this in the
table. (In this table the underlined hydrogens
correspond to the given chemical shift.) The triplet
at 1.0 ppm is determined accordingly.
Step 5: We now sum up the atoms that are
underlined. We do this as a check to make sure
we have used all the hydrogens and to look for
atoms that do not show up in the 1 H-NMR
spectrum, such a COO portion of an ester.
Step 6: Atom Check. Look for unused atoms.
Given formula - atoms from 1 H-NMR or other
sources such as IR = unused atoms. For this
example: C3H7 Br C3H7 = Br. Therefore
1 H-NMR data accounts for all of the atoms in
the formula except the bromine. This bromine
atom must be included when assembling the
pieces.
Step 7: DBE Check. Look for unused DBEs. DBEs
calculated from formula DBE accounted
for (by 1 H-NMR, etc.) = unused DBEs. In this
example the formula has no DBEs and the
1 H- NMR data does not require any DBEs, so
there are no left over DBEs to consider when
assembling the pieces.
Step 8: List and assemble the pieces. At this
point youve done 90% of the work. Now we
assemble the pieces to come up with the final
structure. The pieces suggested by the 1 H-NMR
data are:
Also include pieces suggested by other means such
as IR data.
There is often many ways to go about assembling
the pieces in solving NMR spectroscopy
problems. Use the clues provided by the spectra,
such as coupling patterns. Sometimes trial and
error is all that works. In this case, the middle
fragment uses all three of the available carbons
and fits with the other fragments as shown below.
The fragments have been reduced to CH3 CH2
CH2 and Br, which can only be assembled one
way:
Step 9: Check to make sure the proposed
structure is consistent with the original data, i.e.,
chemical shift (use table), splitting, and
integration. In this case, examine CH2 next Br:
is the chemical shift consistent with what we
expect?
This process might seem long and unnecessarily
complicated for such a simple molecule, but
can be very useful in organizing your
thoughts for more complex examples.
The process becomes much faster
with practice and a little bit of experience.
 Example #2:
Deduce the structure of a compound with the
formula C9H12 that has the following
1 H NMR spectrum:
7.40 7.02 ppm (multiplet, integral = 2.5); 2.57
ppm (triplet, integral = 1); 1.64 ppm (sextet,
integral = 1) and 0.94 ppm (triplet, integral =
1.5).
 Example #3:
Deduce the structure of a compound with the
formula C4H8O2 that has the following
1 H NMR spectrum:
3.67 ppm (singlet, integral = 1.5); 2.32 ppm
(quartet, integral = 1); 1.15 ppm (triplet, integral
= 1.5).