NMR SPECTROSCOPY

.
NMR
Nuclear magnetic resonance spectroscopy is a powerful
analytical technique used to characterize organic
molecules by identifying its structure frameworks
.within molecules
THER ARE two abundant types of NMR spectroscopy
are used to characterize organic structure: 1H NMR is
used to determine the type and number of H atoms in a
molecule; 13C NMR is used to determine the type of
carbon atoms in the molecule
Principles
All nuclei have charge because they contain protons and
some of them also behave as a tiny magnet
if they possess a spin. A spinning charge generates a
magnetic dipole and is associated with a
small magnetic field H Such nuclear magnetic dipoles
are characterised
by nuclear magnetic spin quantum numbers which are designated
by the letter I and
....can take up values equal to 0, l/2,1,3/2,2 etc
 I Atomic number Mass number

5/2, 3/2 , ½ Odd odd

0 even even

3 , 2 , 1 odd even
Here we have three types of nuclei

Type 1

Nuclei with I = O
These nuclei do not interact with the applied magnetic
field and are not NMR chromophores. Nuclei with I = 0
have an even number of protons and even number of
.neutrons and have no net spin as 12C and Br 160

:Type 2
'Nuclei with I >1/2
These nuclei have both a magnetic moment and an
electric quadrupole. This group includes some common isotopes (1H
and 14N) but they are more difficult to observe and spectra are generally

.very broad
= 1Type3: Nuclei with I|2

These nuclei have a non-zero magnetic moment and

are NMR visible and have no nuclear electric quadrupole (Q). The two
most important nuclei for NMR spectroscopy belong to this category:
1H
and l3C (a non-radioactive isotope of carbon )ordinary hydrogen(
occurring to the extent of 1.06% at natural abundance). Also, two other
' commonly observed nuclei 19F and 31p have 1 = I/2
The most important consequence of nuclear
spin is that
in a uniform magnetic field, a
nucleus of spin 1 may assume 2 I+1 orientations. For nuclei with I = 1/2'
there are
just 2 permissible orientations (since 2 * 1/2 1 = 2). These two orientations
will be
of unequal energy (by analogy with the parallel and antiparallel orientations
of a bar
magnet in a magnetic field) and it is possible to induce a spectroscopic
transition
by the absorption of a quantum of electromagnetic energy (∆E) of )spin-flip(
the
:appropriate frequency (v)
 In the case of NMR, the energy required to induce the
nuclear spin flip also depends
on the strength of the applied field, H
' o

where K is a constant characteristic of the nucleus observed. Equation

s known
as the Larmor equation and is the fundamental relationship in NMR
spectroscopy
Unlike other forms of spectroscopy, in NMR the
frequency of the absorbed
electromagnetic radiation is not an absolute value for
any particular transition, but has
a different value depending on the strength of the
applied magnetic field. For every
value of Ho' there is a matching value of v corresponding
to the condition of
resonance according to the larmor equation, and this is
the origin of the term Resonance in
.Nuclear Magnetic Resonance Spectroscopy
The source of energy in NMR is radio waves which have
.long wavelengths, and thus low energy and frequency
When low-energy radio waves interact with a molecule,
they can change the nuclear spins of some elements,
.including 1H and 13C
Any absorption signal observed in a spectroscopic
experiment must originate from
excess of the population in the lower energy state, the so
,called Boltzmann excess
which is equal to Nβ-N where Nβand N are the
α, α

populations in the lower (β) and

.upper (α) energy states
For molar quantities, the general Boltzmann relation
Quntaum mechanics description of
NMR
When we applied magnetic field with intensity H the
angular momentum vector can take an orientation or
energy levels at angles  relative to the applied
magnetic field
We can recognized this energy levels according to the
quantum number Ml
where Ml equals 2L+1
IF WE PUT A NUCLUES HAVE AMAGNETIC FIELD
n in a magnetic field
H the potential energy for this nucleus is
E=n H
And for proton is n=ɣ h/2π mj=gnβn mj
Where mj is the angular spin
Quantum numbers and Bn nuclear magneton which
Is equals(eh/4πmp)and its value 5.058*10-27 J .T gn the
nuclear separation factor equals 5.585 for proton
The energy for one levels is
E=gn βn ml H
THE IN ENERGY BETWEEN TWO LEVELS IS
PROPORTIONAL TO THE INTENSITY OF APPLIED FIELD
The selection rules here is ∆mj=+-1
Finally the larmor frequancy is
V=∆E/h=gn BnH/h=Ɣh/2π

The energy transferred from the elecromagnetic radiation to

the nucleus
When the frequancy of the electromagnetic radiation is
equals to the larmor of the nucleus
So this conditions called resonance where the electron
transferred from lower energy to the higer energy state at
this moment we get signals
 Relaxation processes
When the nuclear absorb the energy from the electromagnetic
radiation it will be excited to the high spin levels and its
continuous because there was an excesses in the number of the
nucleus at the ground state level, at the detect time the
number of the nuclear at the two levels will be equal this case
called the saturation , where the absorption process will be
stopped . for the absorption process continuous and keeping
the poltizman distribution ratio that must be the nucleus at
the excited state must loss their excess energy to absorb
. energy this process is called relaxation processes

The time that required before return to the equilibrium state

called relaxation time.
 There are two types of relaxation
spin –lattice relaxation-1
spin – spin relaxation-2
Spin – lattice relaxation in this type of relaxation the spin
nucleus loss its energy by combination with lattice
environment . ( the molecules system the sample and solvent ,
liquid, gas and solid)which have precession nucleus . the
relaxation occurs because the combination between the spin
nucleus with position fields it's found in the nucleus
environment this fields is product from the vibration ,rotation
and transition movement of the system molecules and have
magnetic properties can induced the nucleus magnetic to
transition from the high state to the ground state
in this relaxation the total energy of system remain
.constant

∆ναT1\1
Where T1 is the time of spin –lattice relaxation

-:The factors that effect on the relaxation time

effect of viscosity 1
The increasing in the viscosity cause decreasing in the value
of T1
 paramagnetic substance effect -2
The presence of the paramagnetic substance ( substance
which have one or more single electron ) can contribute in
the relaxation processes of nucleus . for this reason the
nucleus which have a single electron have position
magnetic field about 103-105 G can decease the relaxation
time through the combination with nucleus spin but the
changes in the position fields its will be greatest where the
lines of absorbance will be more wide for this reason the
absorption in the NMR spectroscopy will be applied only on
the diamagnetic , weak paramagnetic substance
quaternary effect : the nucleus which I> 1/2 -3
have quaternary dipole is produce from the
distance the charge of nucleus from the
symmetric spherical and it's have position
electrostatic field the energy of this nucleus
transfer to the lattice environment ,the time of
relaxation is decrease ,the spectrum of these
nucleus is broad the nitrogen nucleus is the
. famous example
Spin – spin relaxation:- the time of relaxation
symbol T2 the lossing of excess energy through
the conjugated combination between the
neighbored nucleus spins without losing energy to
.the environment
CHEMICAL SHIFT IN 1H NMR
SPECTROSCOPY
It is clear that NMR spectroscopy could be used to detect certain nuclei (e.g.
,IH, l3C
19F, 31P) and, also to estimate them quantitatively. The real usefulness of
NMR
spectroscopy in chemistry is based on secondary phenomena, the chemical shift
and
spin-spin coupling and, to a lesser extent, on effects related to the time-scale of the

NMR experiment. Both the chemical shift and spin-spin coupling reflect the
chemical environment of the nuclear spins whose spin-flips are observed in
the
NMR experiment and these can be considered as chemical effects in NMR
.spectroscopy
H NMR—The Spectrum
1

• An NMR spectrum is a plot of the intensity of a peak against its

chemical shift, measured in parts per million (ppm).
+ .NMR absorptions generally appear as sharp peaks
Increasing chemical shift is plotted from right to
left
.Most protons absorb between 0-10 ppm
The terms “upfield” and “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 d
scale due to tetramethylsilane (TMS). TMS is a
volatile inert compound that gives a single peak
.upfield from typical NMR absorptions
The chemical shift of the x axis gives the position of an NMR
signal, measured in ppm, according to the following equation
:Information from 1H-nmr spectra

Number of signals: How many different-1

.types of hydrogens in the molecule
Position of signals (chemical shift): What-2
types of hydrogens.2
Relative areas under signals (integration): -3
.How many hydrogens of each type
Splitting pattern: How many neighboring-4
.hydrogens
 CHEMICAL SHIFT
The frequency difference between the resonance of a
nucleus and the
resonance of the reference compound
.Each IH nucleus is shielded or by the electrons that surround it
Consequently each nucleus feels the influence of the main magnetic field to a
different extent, depending on the efficiency with which it is screened. Each IH
nucleus with a different chemical environment has a slightly different shielding and
hence a different chemical shift in the IH NMR spectrum
For IH NMR, the intensity of the signal (which may be measured
by electronically
measuring the area under individual resonance signals) is directly
proportional to the
number of nuclei undergoing a spin-flip and proton NMR
I


spectroscopy is a
.quantitative method
Nuclei tend to be deshielded by groups which withdraw electron density.
Deshielded
nuclei resonate at higher 8 values (away from TMS). Conversely shielded nuclei
.resonate at lower 8 values (towards TMS)
Electron withdrawing substituents (-OH, -OCOR, -OR, -
N0 halogen) attached to an
2,

aliphatic carbon chain cause a downfield shift of 2-4

ppm when present at and
.have less than half of this effect when present at C13
When sp2 hybridised carbon atoms (carbonyl groups,
olefinic fragments, aromatic
rings) are present in an aliphatic carbon chain they
cause a downfield shift of 1-2 ppm
The electron density surrounding a given nucleus
depends on the electronegativity of the attached
.atoms
The more electronegative the attached atoms, the
less the electron density around the nucleus in
.question
We say that that nucleus is less shielded, or is
.deshielded by the electronegative atoms
Deshielding effects are generally additive. That is,
two highly electronegative atoms (2 Cl atoms, for
example) would cause more deshielding than only
.1 Cl atom
1
H Chemical Shifts
C H
C C
O
C
CH3 CH3
X
O O C CH2
C H
C C
OH H Aromatic H O H CH
C C Ar CH3
TMS
H C C H

12 11 10 9 8 7 6 5 4 3 2 1 0
1H Chemical shift ( )

downfield upfield
Aromatic ring effect anisotropic

In an
aromatic ring, the "circulation" of electrons effectively forms a current loop which
gives rise to an induced magnetic field. This is called the ring current effect and the
induced field opposes the applied magnetic field of the spectrometer (Bo) inside the
loop and enhances the field outside the loop. The resonance of a nucleus which is
located close to the face of an aromatic ring will be shifted to high field (towards
TMS) because it experiences the effect of both the main spectrometer magnetic field
.but also the magnetic field from the ring current effect of the aromatic ring
Conversely a proton which is in the plane of an aromatic ring is deshielded by the
ring
.current effect
The ring current effect is the main reason that protons attached to aromatic rings
typically appear at the low field end of the IH NMR spectrum since they are in the
deshielded zone of the aromatic ring
Π.bond effect
• In a magnetic field, the loosely held  electrons of the
double bond create a magnetic field that reinforces
the applied field in the vicinity of the protons.
• The protons now feel a stronger magnetic field, and
require a higher frequency for resonance. Thus the
protons are deshielded and the absorption is
downfield
In a magnetic field, the  electrons of a carbon-
carbon triple bond are induced to circulate, but in
this case the induced magnetic field opposes the
.applied magnetic field (B0)
Thus, the proton feels a weaker magnetic field, so a
lower frequency is needed for resonance. The
nucleus is shielded and the absorption is upfield
NMR—Intensity of Signals
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. Note that this gives a ratio, and not the
absolute number, of absorbing protons
H NMR—Intensity of Signals
1

40
41
H NMR—Spin-Spin Splitting
1
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…..)
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
:If Ha and Hb are not equivalent, splitting is observed when

Splitting is not generally observed between protons separated by

.more than three  bonds

45
 The Origin of 1H NMR—Spin-Spin Splitting
Spin-spin splitting occurs only between nonequivalent protons on the
.same carbon or adjacent carbons
:Let us see how the doublet due to the CH2 group on BrCH2CHBr2 occurs

When placed in an applied field, (B0), the adjacent proton (CHBr2)

can be aligned with () or against () B0. The likelihood of
.either case is about 50% (i.e., 1,000,006 vs 1,000,000)
Thus, the absorbing CH2 protons feel two slightly different
magnetic fields—one slightly larger than B0, and one slightly
.smaller than B0
Since the absorbing protons feel two different magnetic fields,
they absorb at two different frequencies in the NMR spectrum,
thus splitting a single absorption into a doublet, where the two
46
.peaks of the doublet have equal intensity
The frequency difference, measured in Hz, between two peaks of the
.doublet is called the coupling constant, J

47
Now to see how a triplet arises

When placing in an applied magnetic field (B0), the adjacent protons Ha

and Hb can each be aligned with () or against () B0.
Thus, the absorbing proton feels three slightly different magnetic
fields—one slightly larger than B0(ab). one slightly smaller than
B0(ab) and one the same strength as B0 (ab).

48
Because the absorbing proton feels three different magnetic fields, it absorbs
at three different frequencies in the NMR spectrum, thus splitting a single
absorption into a triplet.
Because there are two different ways to align one proton with B 0, and one
proton against B0—that is, ab and ab—the middle peak of the triplet is
twice as intense as the two outer peaks, making the ratio of the areas
under the three peaks 1:2:1.
Two adjacent protons split an NMR signal into a triplet. When two protons
split each other, they are said to be coupled. The spacing between peaks
in a split NMR signal, measured by the J value, is equal for coupled protons
50
52
Theory of chemical shift
There is many factors that take place in shielding effect
on chemical shift
δ=δ dia+δ para+δs
δ dia equal the diamagnetic shielding
Which have a relation with electron rotation around the
nucleus &this rotation generates magnetic field which
apposite the applied magnetic field so its cause shielding
of nucleus from the magnetic field so its required higher
frequency its result in shifting the NMR signal to higher
frequency so its positive
While the δs
Is the solvent effect we can remove this factor from the
equation by measuring the chemical shift for the solute
in range of concentration and drawing this value against
concentration
Then extended the concentration to zero
δpara the para magnetic shielding result from rotation of
electrons by chemical bonding ,and it have a relation with
electronic configuration
so the magnetic field is in the direction of the applied
magnetic field so it gives desheilding & it has negative
value
Factors that effecting the coupling constant
Geminal protons-1
The electro negativity of the-2
substituent's
Angles-3
Distribution of pi electron-4
Vicinul protons-5
The numbers of bonds-6
 Rules for Proton coupling
Nuclei with the same chemical shift (isochronous) do not couple with each ).1
.other: the protons must be nonequivalent in order to couple
Vicinal protons (protons separated by 3 bonds) can ).2
couple with each other. Protons that are more than 3
bonds away cannot because the signal they feel from
their neighbor is too small to affect their spin. There is
also geminal coupling—coupling through 2 bonds) and
allylic coupling —coupling through1 4 bonds, if one is
16

a pi bond. Pi bonds do not follow the 3 bond rule because the electron density
around a pi bond is higher then in a single bond; hence, pi bonds can be
counted as a free spacer. All hydrogens on the benzene ring couple with each
other and the ring itself can be counted as a free spacer; however, H’s on the
benzene ring
Hydrogens onlytocouple
bonded with or
a Nitrogen each other and
Oxygen not do
usually with
notH’s attached
couple withtoother
other).3
protons
atomsand appear
even asare
if they singlets
withinonthe
the3 NMR spectra
bond max limit
Some examples of NMR spectra

CH3CHCH2CH3 Cl-CH2CH2CH2-Cl
Br

four two

CH3
CH2Cl

three
 CH3
H3C C CH3 CH3CH2-Br
Br
two
one

CH3CH2CH2-Br CH3CHCH3
Cl
three
two
?number of signals

H3C CH3
C
C
H3C CH3
one
one

CH3

CH3
one
two
 dimethyl-2-butene-2,3

H3C CH3
C C a singlet 12H
H3C CH3
 benzene

a singlet 6H
 tert-butyl bromide

CH3 a singlet 9H
H3C C CH3
Br
 ethyl bromide

a b
CH3CH2-Br

a triplet 3H
b quartet 2H
isopropyl chloride

a b a
CH3CHCH3
Cl

a doublet 6H
b septet 1H