NUCLEAR MAGNETIC RESONANCE

SPECTROSCOPY

1
 KEY POINTS
 B/c of its charge & spin, a nucleus can behave like a
magnet.

 NMR operates by applying B0 & then measuring the

amount of energy necessary to put various nuclei in
resonance.

 Nuclei in d/t electronic env’ts (shielded/deshielded)

require d/t amounts of energy to bring them into
resonance.

 An NMR spectrum provides a signal/peak

representing 2
the energy necessary to bring each nuclei into
resonance.
 NMR

 All nuclei carry a +ve charge b/c they contain protons.

 But only some have a charge spin w/c causes a

magnetic dipole, therefore, possess an
angular momentum.

 The angular momentum of spinning charge is

described in spin quantum number, & then nuclei
behave like magnetic bars.
 The spinning charged nucleus generates a magnetic field. 3
 NMR
 All nuclei with unpaired protons or neutrons are
magnetically active.

 They have a magnetic field arising from the unpaired

nuclear particle.

 However, inactive nuclei have an even # No of protons

& neutrons that pair up with antiparallel spins giving I
= 0 (no net spin).
 i.e no angular momentum/magnetic mov’t 4

 NB: unpaired electrons, protons & neutrons each has a spin of 1/2
 The spectra obtained from NMR answer many questions such as:
1. What is it?

2. Where is it located in the molecule?

3. How many of they are there?

4. What and where are its neighbors?

5. How is it related to its neighbors?

 In absence of an applied B0, nuclear spins are
randomly oriented.

 However, when a sample is placed in an applied B0,

nuclei twist & turn to align themselves with or against
the field of the stronger magnet.
 More energy is needed for a proton to align against field
than with it.
 More nuclei are in the a-spin state than in the b-spin
state.
6
7
RANDOMLY ORIENTED NUCLEAR SPINS

8
 Aligned nuclei with or against B0

B0
9
TWO ENERGY STATES

A photon with the right amount of energy can be

absorbed and cause the spinning proton to flip.
 Application of RF energy – Flipping

B0 In this context, “resonance” refers to the flipping back

and forth of nuclei between the a and b-spin states in 11
response to the RF radiation.
 NMR INSTRUMENT
4 components:

1. NMR powerful magnet

2. NMR probe

3. NMR console
 Radio-frequency generator
 Radio-frequency detector
 Signal amplifier

4. Computer workstation & control software (data 12

processing)
 13
NMR Spectroscopy
Schematic operation of a basic NMR spectrometer
A radio transmitter coil that produces a short
powerful pulse of radio waves.

A powerful magnet that produces strong magnetic

fields

 The sample is placed in a glass tube that spins so the

test material is subject to uniform magnetic field.
 The sample is dissolved in deuterated solvents (CDCl3
/D2O) to eliminate 1H signals from the solvent.

A radio receiver coil that detects radio frequencies

15
emitted as nuclei relax to a lower energy level
 1 H NMR
 The number of signals shows how many different kinds of
protons are present.
 The location of the signals shows how shielded or
deshielded the proton is.
 The intensity of the signal shows the number of protons of
that type.
 Signal splitting shows the number of protons on adjacent
atoms.
16
CHEMICAL SHIFT

 Measured in parts per million.

 Ratio of shift downfield from TMS (Hz) to total

spectrometer frequency (Hz).

 Same value for 60, 100, or 300 MHz machine.

 Called the delta scale.

=>

17
• An NMR spectrum is a plot of the intensity of a peak against its chemical
shift, measured in parts per million (ppm).

18
 NMR absorptions generally appear as sharp peaks.

 Most protons absorb b/n 0-10 ppm.

 The terms “upfield” & “downfield” describe the relative

location of peaks.
 Upfield means to the right.
 Downfield means to the left.

 NMR absorptions are measured relative to the position

of a reference peak at 0 ppm on the  scale due to
(TMS).
19
 from
TMS typical NMRinert
is a volatile absorptions.
cpd that gives a single peak upfield
 CH3
Chemical Shift (δ) CH3 Si

CH3 (TMS)
Tetramethylsilane
C
 Signals are measured relative to the signalHof
3 TMS.

 For a 1H-NMR spectrum, signals are reported by their shift

from the 12 H signal in TMS.

 For a 13C-NMR spectrum, signals are reported by their shift

from the 4 C signal in TMS.

 Chemical shift (): The shift in ppm of an NMR signal

from the signal of TMS.

• Called the delta scale.

Chemical Shift (δ)…

 The advantage of the  scale is that the chemical shift of

a given nucleus is independent of the operating frequency of the
NMR spectrometer.

21
Chemical Shift (δ)…

Reference cpd: TMS, (CH3)4Si

Only one peak on NMR spectrum

High electronic density of H in TMS.

 Almost all the H peaks of organic compounds appear on the left of

the TMS peak.

It gives a single intense peak  easily recognized

22
Chemical Shift (δ)…

 Factors Influencing Chemical Shift

 Electronegativity

 Hydrogen bonding

 Hybridization

23
Chemical Shift (δ)…

Molecules having hydrogen bonding have higher

chemical shift & absorb radiation at low field.

That is due to the decrease of electronic density around

the nucleus
FUNCTIONAL GROUP CHEMICAL SHIFT

RCOOH 10.5 – 12.0 ppm

ArOH 4.5 – 7.0 ppm

ROH 0.5 – 5.0 ppm

RNH2 0.5 – 5.0

24
ppm

RCONH2 5.0 – 8.0 ppm

Chemical Shift (δ)…

Chemical shift increases with increasing electronegativity

of X in methyl halides.

Electroneg-
CH 3 -X ativity of X  of H

C H 3F 4.0 4.26
C H 3 OH 3.5 3.47
C H 3 Cl 3.1 3.05
C H 3 Br 2.8 2.68
C H 3I 2.5 2.16
(CH 3 )4 C 2.1 0.86
25
(C H 3 ) 4 Si 1.8 0.00 (by definition
Chemical Shift (δ)…

 Hybridization of adjacent atoms.

Type of Hydrogen Name of Chem ical

(R = alkyl) Hydrogen Shift
()
RCH3 , R2 CH2 , R3 CH Alkyl 0.8 - 1.7
R2 C= C(R)CHR2 Allylic 1.6 - 2.6
RC CH Acetylen ic 2.0 - 3.0
R2 C= CHR, R2 C= Vinylic 4.6 - 5.7
CH2 RCHO Aldehydic 9.5-10.1
A. 1H NMR—Number of Signals

The number of NMR signals equals the number of

different types of protons in a compound.
Protons in different environments give different NMR signals.
Equivalent protons give the same NMR signal.

27
1H NMR—Number of Signals…

 In comparing two H atoms on a ring

or double bond, two protons are equivalent only if they are cis
(or trans) to the same groups.

28
B. 1H NMR—Position of Signals

In the vicinity of the nucleus, the magnetic field (Bi)

generated by the circulating electron decreases the
external magnetic field (B0) that the proton “feels”.
The effective field at nucleus: B = B0 - Bi

29
SHEILDING & DESHEILDING EFFECTS
Higher Chemical Shift Lower Chemical
Shift
 The nucleus is more  The nucleus is more
desheilded sheilded
 Downfeild  Upfeild

 Paramagnetic shift  Diamagnetic shift

 Large δ value  Small δ value

30
THE RELATIVE POSITIONS OF 1H NMR SIGNALS
 A nucleus in the vicinity of an electronegative atom
experiences reduced electron density & a nucleus
is therefore deshielded.
 More electronegative atoms deshield more and give larger
shift values.
 Additional electronegative atoms cause increase in
chemical shift.

31
32
33
34
An 1H NMR spectrum can be divided into six regions. Rather than memorizing
chemical shift values, if you remember the kinds of protons that are in each
region, you will be able to tell what kinds of protons a molecule has from a quick
look at its NMR spectrum.

35
Without referring to the Table of chemical shifts, label the protons in the
following compounds.
(Note that) The proton that gives the signal at the lowest frequency should be
labeled a, the next b, ….. etc.
 C. 1H NMR—Intensity of Signals/integration

• The area under an NMR signal is proportional to the number of absorbing

protons.

• An NMR spectrometer automatically integrates the area under the peaks, and
prints out a stepped curve (integral) on the spectrum.

• The height of each step is proportional to the area under the peak, which in
turn is proportional to the number of absorbing protons.

• Modern NMR spectrometers automatically calculate and plot the value of

each integral in arbitrary units.

• The ratio of integrals to one another gives the ratio of absorbing protons in a
spectrum. 37
38

=>
H NMR—Intensity of Signals…
1

The integration tells us the relative number of protons that give

rise to each signal, not the absolute number.

For example, integration could not distinguish between 1,1-

dichloroethane and 1,2-dichloro-2-methylpropane because both
compounds would show an integral ratio of 1:3.
 Nuclear Magnetic Resonance Spectroscopy
H NMR—Spin-Spin Splitting
1

• Consider the spectrum below:

40
 SPIN-SPIN SPLITTING IN 1H NMR SPECTRA
 Peaks are often split into multiple peaks due to magnetic interactions between nonequivalent
protons on adjacent carbons, the process is called spin-spin splitting

 The splitting is into one more peak than the number of H’s on the adjacent carbon(s), This is
the “n+1 rule”

 The relative intensities are in proportion of a binomial distribution given by Pascal’s Triangle

 The set of peaks is a multiplet (2 = doublet, 3 = triplet, 4 = quartet, 5=pentet, 6=hextet,

7=heptet…..)

41
SPIN-SPIN SPLITTING…
Rules for Spin-Spin Splitting
 Equivalent protons do not split each other

 Protons that are farther than two carbon atoms apart do not split each other

42
 Spin-Spin Splitting…

Splitting is not generally observed between protons separated by

more than three  bonds.

43

43
Splitting pattern: how many neighboring hydrogens.

In general, n-equivalent neighboring hydrogens will split a 1H signal into

an ( n + 1 ) Pascal pattern.

“neighboring” – no more than three bonds away

n n+1 Pascal pattern:
0 1 1 singlet
1 2 1 1 doublet
2 3 1 2 1 triplet
3 4 1 3 3 1 quartet
4 5 1 4 6 4 1 quintet
45
46
47
 Rules Governing the Interpretation

The following rules govern the

appearance of spectra.
1. Equivalent nuclei do not interact with
one another to give multiple absorption
peaks.
2. Couplingconstants decrease
significantly withat distances
seldom observed separationgreater
of groups,
than
fourand
bondcoupling
lengths. is
3. The multiplicity of a band is determined by
the number n of magnetically equivalent
protons on the neighboring atoms and is
given by the quantity n + 1.
 Rules Governing the Interpretation…

4. If the protons on B are affected

atom
protons on atoms A by an
C
nonequivalent, the multiplicity of B is equal to
that
(nA+1)(nC+1), where nA & nC are the are of
number
equivalent protons on A & C, respectively.
5. The approximate relative areas of a multiplet
are symmetric around the midpoint of the
band.
6. The coupling constant is independent of the
applied field.
50
51
ALKANES, CYCLOALKANES

52
ALKENES, CYCLOALKENES

53
ALKYNES

54
AROMATIC HYDROCARBONS

55
HETEROAROMATIC COMPOUNDS

56