NM R INTE RP RET ATION

1
H NMR data is reported in a specific format. Knowing what the numbers mean
can help you to determine the answer to some the most important questions in synthesis:
“Did I make my stuff?” and, if you didn’t: “What did I make?” This tutorial is designed
to help you to interpret 1H NMR data reported in the literature and to compare it to your
own spectra. For your final paper, you will write up an experimental from your synthesis,
fully characterize one compound, and hopefully appreciate the importance of accurate
NMR interpretation and reporting. NMR is very powerful, giving the most structural
information about a compound in a short period of time. Coupled with IR, mass
spectrometry, and occasionally crystal structures, chemists can definitively delineate the
structures of the compounds they have made.

The problems in this handout are real-life NMR problems. Each is an example
from my dissertation. The problems increase in difficulty, and they include guided
explanations. Refer to the pages of spectra at the back of the handout to interpret the data.
This is not a basic tutorial; you should look to your organic text and lecture notes for the
fundamentals. Read about the theory of NMR, and understand the concepts of equivalent
protons, multiplicity, coupling constants, shift, and shielding. Knowledge of these
concepts is critical to help you to understand this tutorial.

There is a sequence of numbers and letters that are used to describe the proton
NMR in an experimental. The meanings of these designations are as follows:

shift in ppm (multiplicity, J value if appropriate, number of protons),

For example: 2.00 (dd, J = 9.8, 2.2 Hz, 1 H), 1.89 (s, 9 H),…

Notes:
ppm value is reported to two decimal places
J is italicized
J value is reported to one decimal place
The larger coupling constant (J value) goes first
There is a space between the 1 and the H (also the 9 and the H)

Abbreviations:
s = singlet
d = doublet
t = triplet
q = quartet
app = apparent
m = multiplet (denotes complex pattern for a single proton)
comp = complex (a group of overlaid protons that is difficult to interpret)

For problem 1, I’ve made you a worksheet to organize your work. For problems 2 and 3,
you will need to make your own worksheet. My worksheet is only an example; organize
the table/data in a way that makes sense to you.

1
Worksheet for problem 1

11 10
Si
Br
4 3
7
O 2
1 O
5 Si 8
S
CH3
6 9

Proton Expected Integral Shift

Multiplicity Assignment
1
3
5
6
7
9
10
11

Carbon Shift Assignment

159.3
147.8
128.4
123.3
57.4
26.0
18.4
18.3
15.6
-4.4
-5.2

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PROBLEM 1: Understanding shielding effects

First, determine the expected multiplicity of all of the protons in compound 3.118.
I’ve included my full experimental as a guide for you to write your paper, so look over it.
For now, you can just skip down to the proton NMR data and spectrum once you’ve
written down the expected multiplicity for the protons on each numbered carbon.

Scheme 1
Me
n-BuLi, Et2O Si Me
then Br
O
OTBS Me Me O
Si Br OTBS
MeS Cl
79% MeS
3.121 3.118

Experimental 1

11 10
Si
Br
4 3
7
O 2
1 O
5 Si 8
S
CH3
6 9

3.118

(Bromomethyl)(4-((tert-butyldimethylsilyloxy)methyl)-5-(methylthio)furan-2-
yl)dimethylsilane (3.118). (KP5-186). A solution of n-BuLi in hexanes (2.23 M, 150
µL, 0.34 mmol) was added to furan 3.121 (80 mg, 0.31 mmol) in Et2O (3 mL) at rt and
the mixture was stirred for 2 h. Bromomethylchlorodimethylsilane (51 µL, 0.37 mmol)
was added dropwise, and the mixture was stirred for 12 h, whereupon a saturated solution
of NH4Cl (3 mL) was added. The layers were separated, and the aqueous layer was
extracted with Et2O (3 x 2 mL), dried (MgSO4), and concentrated under reduced pressure.
The residue was purified by flash chromatography eluting with PhCH3/hexanes (1:5) to
afford 101 mg (79%) of bromide 3.118 as a light oil: 1H NMR (600 MHz, CDCl3) δ 6.76
(s, 1 H), 4.56 (s, 2 H), 2.60 (s, 2 H), 2.35 (s, 3 H), 0.90 (s, 9 H), 0.39 (s, 6 H), 0.075 (s, 6
H); 13C NMR (125 MHz, CDCl3) δ 159.3, 147.8, 128.4, 123.3, 57.4, 26.0, 18.4, 18.3,
15.6, –4.4, –5.2; IR (neat) 1253, 1082, 1054 cm-1; mass spectrum (CI) m/z 409.0686
[C15H29BrO2SSi2 (M+1) requires 409.0688], 395, 329 (base).

Note: Include is a colon after the experimental procedure, and then begin listing
the shifts and peaks for the spectrum. The first information listed is about the power of
the instrument and the solvent system used. In this case the following is written: 1H NMR
(600 MHz, CDCl3) δ… This spectrum was taken on a 600 MHz NMR and the deuterated
chloroform was the NMR solvent. The symbol δ designates the numbers outside of the
parenthesis as chemical shifts, with the unit ppm. Now, back to those multiplicities…

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 All singlets! So now all we have to do is figure out where everything is on the
spectrum. To assign this proton NMR we do not need to use a 2D spectrum. Remember
the 2D spectrum called a COSY tells you which protons couple to which. This will not
help us here–they’re all singlets! There are a few important pieces of information that you
need to know to interpret this spectrum:

1. Silicon atoms are less electronegative than hydrogen atoms. The hydrogen
atoms on carbons attached to silicon will therefore be very shielded. They typically
appear below 1 ppm in the spectrum.

2. CHCl3 shows up at 7.24 and H2O shows up between 1.5–1.6.

3. Find the electronegativity of sulfur and compare it to carbon and hydrogen.

Predict a shift for the sulfur atom… Go on, just take a shot. Recall that aromatic stuff is
around 7–8 ppm and unsubstituted alkyl chains show up around 0.9–1.7 ppm.

The most important feature to help you assign this spectrum is shift. The furan
ring is aromatic, so first find the proton directly attached to the furan. Now check your
integral! It should be 1. If not, adjust all of your integral values by dividing by this
number. Assign the rest of the spectrum. Note the shifts and think about why some
protons are more deshielded than others. If you aren’t sure why, ask me.

BIG HINT: Use the integrals to help with your assignments!

Now we need to assign the carbon spectrum. A 2D spectrum called an HSQC is

included to help you. The 1H NMR is on the horizontal axis and the 13C NMR is on the
vertical axis. All you need to do is match up the spot that appears on the 2D spectrum
with the corresponding carbon. Note that the shifts on the carbon spectrum are similar to
the corresponding proton shifts in most cases. OK! Now check your assignments:

NMR Assignments: 1H NMR (600 MHz, CDCl3) δ 6.76 (s, 1 H, C3-H), 4.56 (s, 2
H, C5-H), 2.60 (s, 2 H, C11-H), 2.35 (s, 3 H, C6-H), 0.90 (s, 9 H, C9-H), 0.39 (s, 6 H,
C10-H), 0.075 (s, 6 H, C7-H); 13C NMR (150 MHz, CDCl3) δ 159.3 (C1), 147.8 (C2),
128.4 (C4), 123.3 (C3), 57.4 (C5), 26.0 (C9), 18.4 (C8 or C6), 18.3 (C8 or C6), 15.6
(C11), –4.4 (C10), –5.2 (C7).

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PROBLEM 2: Aromatic coupling

Another big lie: protons are only coupled to protons on the “neighbor” carbon
atom. Aromatic compounds are a good example of an exception to this rule, and coupling
constants can be seen for protons that are ortho, meta, and para! Ortho coupling is
large—in the range of 6–10 Hz (Figure). This is expected since it is the proton on the
neighboring carbon. Meta coupling is generally observed, and para coupling is very
small; often no coupling is seen at all.

Figure 1

ortho coupling meta coupling para coupling

H H H
R H R R R R

R R R H R R
R R H
J = 6–10 Hz J = 1–4 Hz J = 0–2 Hz

This is a good time to talk about doublets of doublets. When a proton is split by
two equivalent protons, a triplet is observed. However, when the proton is split by two
nonequivalent protons, the proton shows up as a doublet of doublets on the spectrum.
This is because each nonequivalent proton splits the proton with it’s own, unique J value.
Look at Figure 2 and consider the circled hydrogen atom.

Figure 2
J1

O
Ha
J2
H
Hb Cl

Hb splits the proton into a doublet. In this example, Hb splits the circled proton
into a doublet with a large coupling constant, J1. Ha splits each peak of the doublet into a
second doublet, with a small coupling constant, J2. Therefore we get four lines, but it is
not a quartet; the distances between the peaks are not all the same! Make yourself a
worksheet for problem 2, and predict the multiplicities of each hydrogen atom on
compound 3.143.

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 Scheme 2
OH OBn
Cl BnBr Cl
NaH
DMF
81%
OH OBn

3.142 3.143

Experimental 2
7
O Ph
1
Cl 2 6

3 5
4
O Ph
8

(2-Chloro-1,4-phenylene)bis(oxy)bis(methylene)dibenzene (3.143). (KP6-65).

NaH (1.23 g, 31.5 mmol, 60 % dispersion) was added in two portions to a solution of
chlorohydroquinone (3.142) (2.08 g, 12.9 mmol, 90%) and BnBr (3.7 mL, 30.1 mmol) in
DMF (100 mL). The mixture was stirred for 24 h, whereupon H2O (100 mL) and Et2O
(300 mL) were added. The layers were separated, and the organic layer was washed with
H2O (3 x 100 mL) and brine (2 x 100 mL), dried (MgSO4), and concentrated. The
residue was recrystallized from EtOH to provide 3.37 g (81%) of 3.143: 1H NMR (500
MHz, CDCl3) δ 7.45–7.29 (comp, 10 H), 7.04 (d, J = 2.9 Hz, 1 H), 6.87 (d, J = 9.0 Hz, 1
H), 6.77 (dd, J = 9.0, 2.9 Hz, 1 H), 5.07 (s, 2 H), 4.98 (s, 2 H); 13C NMR (150 MHz,
CDCl3) δ 153.4, 148.7, 136.8, 136.7, 128.6, 128.5, 128.1, 127.9, 124.2, 117.2, 115.9,
113.9, 71.9, 70.8; IR (neat) 1454, 1225, 1052, 1018, 736 cm-1; mass spectrum (CI) m/z
324.0917 [C20H17O2 (M+1) requires 324.0917] (base), 289, 181.

You’ll need to think about a few key things to assign this spectrum:

1. The phenyl rings on the benzyl protecting group are usually overlaid on the 1H
NMR spectrum. They also often exhibit second order coupling, which is difficult to
interpret. Much of the time, I group these protons in my assignment and label them as
“comp.”

2. In this case, things are coupled to each other. If we hypothesize that one proton
is coupled to another, we can verify this using the COSY 2D spectrum that correlates
coupled protons. Note that there are many spots on the diagonal. Each proton gives a spot
on the 2D spectrum that corresponds to itself. The spots on the diagonal are thus not
useful for assignment. Assign the carbon spectrum using the HSQC.

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 NMR Assignments: 1H NMR (500 MHz, CDCl3) δ 7.45–7.29 (comp, 10 H, PhC-
H), 7.04 (d, J = 2.9 Hz, 1 H, C6-H), 6.87 (d, J = 9.0 Hz, 1 H, C3-H), 6.77 (dd, J = 9.0, 2.9
Hz, 1 H, C5-H), 5.07 (s, 2 H, C7-H), 4.98 (s, 2 H, C8-H); 13C NMR (150 MHz, CDCl3) δ
153.4 (Ph C), 148.7 (Ph C), 136.8 (Ph C), 136.7 (Ph C), 128.6 (Ph C), 128.5 (Ph C),
128.1 (Ph C), 127.9 (Ph C), 124.2 (Ph C), 117.2 (C5) 115.9 (C3), 113.9 (C6), 71.9 (C7),
70.8 (C8).

Problem 3: How many ddds can there be?

This is a tricky one! In addition to doublets of doublets, there can be doublets of

triplets and doublets of quartets. Draw a splitting tree to show how these might arise
and get an idea of how they might look. We will learn to calculate the coupling constants
for the complex patterns of this compound in mini meeting.1 For now, try to predict the
multiplicities of compound 2.72. Hint: This compound sits in a chair conformation, so
axial and equatorial protons may not be equivalent! Draw out the chair to help you with
your predictions.

Scheme 3

O OBn O OBn
NaH, MeI, DMF

MeO 97% MeO

NHBoc NMeBoc
2.71 2.72

Experimental 3
6
O O Ph
4 1
7 5
3 2
O
N O
8
O

2.72

(2S,3R,4S,6R)-(6-Benzyloxy-3-methoxy-2-methyltetrahydropyran-4-yl)-
methylcarbamic acid tert-butyl ester (2.72). (KP2-167). A mixture of carbamate 2.71
(398 mg, 1.13 mmol), MeI (84 µL, 1.36 mmol) and NaH (68 mg, 1.70 mmol, 60%
dispersion in mineral oil) in anhydrous DMF (15 mL) was stirred at room temperature for
30 min, whereupon MeOH (5 mL), H2O (30 mL), and Et2O (50 mL) were added. The
layers were separated, and the organic layer was washed with H2O (2 x 30 mL) and brine
(1 x 30 mL). The combined organic layers were dried (Na2SO4), and concentrated under
reduced pressure. The residue was purified by flash chromatography, eluting with
1
For those of you that are very interested in learning more about complex splitting patterns in 1H NMR,
read the following paper: Hoye, T. R.; Hanson, P. R.; Vyvyan, J. R. J. Org. Chem.1994, 59, 4096-4103.

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Et2O/hexanes (1:1) to afford 400 mg (97%) of 2.72 as a clear oil: 1H NMR (500 MHz,
CDCl3) δ 7.36–7.26 (comp, 5 H), 4.91 (d, J = 3.5 Hz, 1 H), 4.61 (d, J = 12.1 Hz, 1 H),
4.46 (d, J = 12.1 Hz, 1 H), 4.25-4.20 (m, 1 H), 3.64 (dq, J = 9.3, 6.3 Hz, 1 H), 3.33 (s, 3
H), 3.08 (app t, J = 9.3 Hz, 1 H), 2.74 (s, 3 H), 1.97 (td, J = 12.9, 3.5 Hz, 1 H), 1.73 (dd, J
= 12.9, 4.7 Hz, 1 H), 1.41 (s, 9H), 1.19 (d, J = 6.3 Hz, 3 H); 13C NMR (125 MHz, CDCl3)
δ 154.5, 137.7, 127.6, 126.9, 126.8, 95.3, 80.2, 78.1, 67.6, 67.1, 57.4, 52.8, 32.8, 27.6,
17.5; IR (neat) 1693, 1365, 1151, 1127 cm-1; mass spectrum (CI) m/z 366.2284
[C20H32NO5 (M+1) requires 366.2202], 258, 202 (base).

If = your multiplicities were incorrect, try to figure out why. If you can’t, come
ask me. Now it is time to assign the 1H NMR spectrum.

HINT: Try to find the proton that corresponds to carbon 1 on the 2D COSY spectrum
first.

HINT: Use your integrals.

HINT: Sometimes there can be slow rotation. If a bond is not rotating rapidly, you may
see splitting from protons that you expected to be equivalent. BIG HINT: This is
observed in this compound.

NMR Assignments: 1H NMR (500 MHz, CDCl3) δ 7.36–7.26 (comp, 5 H, PhC-H), 4.91
(d, J = 3.5 Hz, 1 H, C1-H), 4.61 (d, J = 12.1 Hz, 1 H, C12-H), 4.46 (d, J = 12.1 Hz, 1 H,
C12-H), 4.25–4.20 (m, 1 H, C3-H), 3.64 (dq, J = 9.3, 6.3 Hz, 1 H, C5-H), 3.33 (s, 3 H,
C7-H), 3.08 (app t, J = 9.3 Hz, 1 H, C4-H), 2.74 (s, 3 H, C8-H), 1.97 (td, J = 12.9, 3.5
Hz, 1 H, C2-H), 1.73 (dd, J = 12.9, 4.7 Hz, 1 H, C2-H), 1.41 (s, 9H, C11-H) 1.19 (d, J =
6.3 Hz, 3 H, C6-H); 13C NMR (125 MHz, CDCl3) δ 154.5 (C9), 137.7 (PhC), 127.6
(PhC), 126.9 (PhC), 126.8 (PhC), 95.3 (C1), 80.2 (C4), 78.1 (C10), 67.6 (C12), 67.1
(C5), 57.4 (C7), 52.8 (C3), 32.8 (C2), 27.6 (C11), 17.5 (C6).