NMR

DR Md Ashraful Alam
 NMR Solvents
• Most NMR spectra are recorded for compounds dissolved in a solvent.
Therefore, signals will be observed for the solvent and this must be accounted
for in solving spectral problems.

To avoid spectra dominated by the solvent signal, most 1H NMR spectra are
recorded in a deuterated solvent. However, deuteration is not "100%", so
signals for the residual protons are observed. In chloroform solvent (CDCl 3),
this corresponds to CHCl3, so a singlet signal is observed at 7.26 ppm. For
methanol solvent, this corresponds to CHD 2OD, so a 1:2:3:2:1 pentet signal is
observed at 3.31 ppm.
• (Recall that deuterium has a spin quantum number (I) of 1, so n deuterium
atoms will split a proton signal into 2In+1 lines.) The same solvents are used
for 13C NMR spectra, so the same rules about splitting patterns apply here also.

It used to be common practice to add Me 4Si, or related compounds, as an

internal reference standard for 1H and 13C NMR spectra with the proton signal
occurring at 0.0 ppm and the carbon signal occurring at 0.0 ppm in the 13C NMR
spectrum. However, modern spectrometers can "lock" on solvent signals, so
addition of internal reference standards is not usually required.
 The chemical shifts (d) of solvent signals observed for 1H NMR and 13C NMR spectra
are listed in the following table. The multiplicity is shown in parentheses as 1 for singlet,
2 for doublet, 3 for triplet, etc.

Solvent 1
H NMR Chemical Shift 13
C NMR Chemical Shift
Acetic Acid 11.65 (1) , 2.04 (5) 179.0 (1) , 20.0 (7)
Acetone 2.05 (5) 206.7 (13) , 29.9 (7)
Acetonitrile 1.94 (5) 118.7 (1) , 1.39 (7)
Benzene 7.16 (1) 128.4 (3)
Chloroform 7.26 (1) 77.2 (3)
Dimethyl Sulfoxide 2.50 (5) 39.5 (7)
Methanol 4.87 (1) , 3.31 (5) 49.1 (7)
Methylene Chloride 5.32 (3) 54.00 (5)
150.3 (1) , 135.9 (3) , 123.9
Pyridine 8.74 (1) , 7.58 (1) , 7.22 (1)
(5)
Water (D2O) 4.8
Peak area and Proton counting
 Integration

• It is a process by which relative areas under

spectral peaks are measured . These areas are
proportional to the number of equivalent
protons giving the signal.
• Benzyle acetate-
• It is found that,
three set of proton gives
Three signals in the
integral ratio
52:21:32 or 5:2:3
 INTEGRATION

• the area under a signal is proportional to the number of hydrogen atoms present
• an integration device scans the area under the peaks
• the ratio of relative areas is displayed on the spectrum
• historically, lines on the spectrum showed the relative abundance of each H type

By measuring the distances between the integration lines one can

work out the simple ratio between the various types of hydrogen.

before integration after integration

NOTICE THAT THE O-H SIGNAL IS ONLY A SINGLET

(see later for an explanation of this)
 INTEGRATION – HISTORICAL PRESENTATION

Measure the
distance between
the top and
bottom lines.

Compare the
heights from
each signal and
make them into a
simple ratio.

Computers now
do the integration
automatically

HOW TO WORK OUT THE SIMPLE RATIOS

• Measure how much each integration line rises as it goes of a set of signals
• Compare the relative values and work out the simple ratio between them
• In the above spectrum the rises are in the ratio... 1:2:3

IMPORTANT: It doesn’t provide the actual number of H’s in each environment, just the ratio
 LOW RESOLUTION - HIGH RESOLUTION
• low resolution nmr gives 1 peak for each environmentally different group of protons
• high resolution gives more complex signals - doublets, triplets, quartets, multiplets
• the signal produced indicates the number of protons on adjacent carbon atoms

LOW RESOLUTION SPECTRUM OF 1-BROMOPROPANE

 LOW RESOLUTION - HIGH RESOLUTION
• low resolution nmr gives 1 peak for each environmentally different group of protons
• high resolution gives more complex signals - doublets, triplets, quartets, multiplets
• the signal produced indicates the number of protons on adjacent carbon atoms

HIGH RESOLUTION SPECTRUM OF 1-BROMOPROPANE

The broad
peaks are split
into sharper
signals

The splitting pattern depends on the number of hydrogen atoms on adjacent atoms
 MULTIPLICITY (Spin-spin splitting)
• low resolution nmr gives 1 peak for each environmentally different group of protons
• high resolution gives more complex signals - doublets, triplets, quartets, multiplets
• the signal produced indicates the number of protons on adjacent carbon atoms

Number of peaks = number of chemically different H’s on adjacent atoms + 1

1 neighbouring H 2 peaks “doublet” 1:1

2 neighbouring H’s 3 peaks “triplet” 1:2:1

3 neighbouring H’s 4 peaks “quartet” 1:3:3:1

4 neighbouring H’s 5 peaks “quintet” 1:4:6:4:1

Signals for the H in an O-H bond are unaffected by hydrogens on adjacent atoms - get a singlet
Fig . Pascal's triangle
• Chemists quantify the spin-spin coupling effect
using something called the coupling constant,
which is abbreviated with the capital letter J. The
coupling constant is simply the difference,
expressed in Hz, between two adjacent sub-peaks
in a split signal.
• For our doublet in the 1,1,2-trichloroethane
spectrum, for example, the two subpeaks are
separated by 6.1 Hz, and thus we write 3Ja-b = 6.1
Hz.
Geminal proton-proton coupling (2JHH)
Germinal coupling generates through two bonds (Fig). Two proton having geminal
coupling are not chemically equivalent. This coupling ranges from -20 to 40
Hz. 2JHHdepends on hybridization of carbon atom and the bond angle and the substituent
such as electronegative atoms. When S-character is increased, Geminal coupling constant
is increased : 2Jsp1>2Jsp2>2Jsp3 The bond angle(HCH) gives rise to change 2JHH value and
depend on the strain of the ring in the cyclic systems. Geminal coupling constant
determines ring size. When bond angle is decreased, ring size is decreased so that
geminal coupling constant is more positive. If a atom is replace to an electronegative
atom, Geminal coupling constant move to positive value.

Fig . Geminal coupling

• A few characteristics of geminal coupling constant-
• 1- The value of coupling constant increases with the
increase in bond angle (increase in s character).
J is -12.4cps for methane, whereas, it is +2.5 cps for ethylene.
• 2. The increase of electonegativity of the atom or group,
which withdraws sigma electrons, increases the value of
coupling constant.
e.g. CC of Methyl chloride is -10.8 cps, whereas, it is -9.4 cps
for methyl fluoride.
• 3. The value of J decreases if an electronagative substituent
withdraw electrons from the pi bonds.
e.g Jgem is +2.3 for ethane whereas, -3.3 cps for vinyle
fluoride.
Vicinal proton-proton coupling (3JHH)
Vicinal coupling occurs though three bonds (Fig 7.). The Vicinal coupling is the most useful
information of dihedral angle, leading to stereochemistry and conformation of molecules. Vicinal
coupling constant always has the positive value and is affected by the dihedral angle (?;HCCH),
the valence angle (?; HCC), the bond length of carbon-carbon, and the effects of electronegative
atoms. Vicinal coupling constant depending on the dihedral angle (Fig 8) is given by the Karplus
equation.

When ? is the 90o, vicinal coupling constant is zero. In addition, vicinal

coupling constant ranges from 8 to 10 Hz at the and ?=180o, where ?
=0o and ?=180omeans that the coupled protons have cis and trans
configuration, respectively.
 Fig 7. Vicinal coupling

The valence angle(?;Fig 8) also causes change of 3JHH value. Valence

angle is related with ring size. Typically, when the valence angle
decreases, the coupling constant reduces. The distance between the
carbons atoms gives influences to vicinal coupling constant.

Fig8. a) Dihedral angle and b) valence angle

The coupling constant increases with the decrease of bond length. Electronegative atoms
affect vicinal coupling constants so that electronegative atoms decrease the vicinal
coupling constants.
 Long-range Coupling
• Proton-proton couplings over more than three bonds are
usually too small to detect easily (< 1 Hz). However, there are a
number of important environments where such couplings are
present, and can provide useful structural information.
• Coupling across π-systems are the most frequently
encountered 4J couplings: the meta-coupling in aromatic
compounds, and the 4-bond allylic, propargylic and allenic
couplings.
• 4-Bond couplings across saturated carbons (sp 3) or heteroatoms
are rarer, and are usually seen only in cyclic compounds when
there is a favorable geometric alignment along the H-C-C-C-H
chain ("W-Coupling"). Longer range couplings (5J and higher) are
also observed, particularly in acetylenes and allenes
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