Ministry of Higher Education and Scientific Research

University Of Thi-Qar
College Of Sciences
Department of Chemistry

Asst .prof. Dr. Athraa hameed mekky

MSC 2st attemp
2020-2021
L5

Nuclear magnetic resonance (NMR) spectroscopy,

Introduction to 1H-NMR Spectroscopy

which tells us about the carbon skeleton and the environments of the
hydrogens attached to it. NMR is concerned with change in the direction of spin
orientation as the result of the absorption of radiofrequency radiation.

Many kinds of nuclei behave as if they were spinning about an axis, much as
the earth spins daily. Because they’re positively charged, these spinning
nuclei act like tiny magnets and interact with an external magnetic field,
denoted B0. both the proton 1H and the 13C nucleus do have spins. The more
common 12C isotope, however, does not have nuclear spin. The words
proton and hydrogen are often used interchangeably, since a hydrogen
nucleus is just a proton.) Let’s see what the consequences of nuclear spin
are and how we can use the results.
Nuclear magnetic resonance spectroscopy depends on the absorption of
energy when the nucleus of an atom is excited from its lowest energy spin
state to the next higher one.

The nuclei of many elements can be studied by NMR, and the two elements
that are the most common in organic molecules (carbon and hydrogen) have
isotopes (1H and 13C) capable of giving NMR spectra that are rich in
structural information

A proton nuclear magnetic resonance (1H-NMR) spectrum tells us about the

environments of the various hydrogens in a molecule; a carbon-13 nuclear
magnetic resonance (13C NMR) spectrum does the same for the carbon atoms.
Separately and together 1H and 13C NMR take us a long way toward
determining a substance’s molecular structure.
The 13C- NMR discussion is shorter, not because it is less important than 1H-
NMR, but because many of the same .

Like an electron, a proton has two spin states with quantum numbers of +1/2
and -1/2 .There is no difference in energy between these two nuclear spin
states; a proton is just as likely to have a spin of +1/2 as −1/2 .
Absorption of electromagnetic radiation can occur only when the two spin
states have different energies. A way to make them different is to place the
sample in a magnetic field.

A spinning proton behaves like a tiny bar magnet and has a magnetic moment
associated with it (Figure 1). In the presence of an external magnetic field B0,
the spin state in which the magnetic moment of the nucleus is aligned with B0
is lower in energy than the one in which it opposes B0.
Figure 1 : In the absence of an external magnetic field, the nuclear spins of
the protons are randomly oriented. (b) In the presence of an external
magnetic field B0, the nuclear spins are oriented so that the resulting nuclear
magnetic moments are aligned either parallel or antiparallel to B0. The lower
energy orientation is the one parallel to B0, and more nuclei have this
orientation
As shown in Figure below , the energy difference between the two
states is directly proportional to the strength of the applied field. Net
absorption of electromagnetic radiation requires that the lower state be
more highly populated than the higher one, and quite strong magnetic
fields are required to achieve the separation necessary to give a
detectable signal.

From Planck’s equation ΔE = hν , this energy gap corresponds to

radiation having a frequency of 2 × 108 Hz (200 MHz), which lies in
the radio-frequency (r.f) region of the electromagnetic spectrum .
Figure 2: An external magnetic field causes the two nuclear spin states to have
different energies. The difference in energy ΔE is proportional to the strength of the
applied field.
Most of the NMR spectra in this text were recorded on a spectrometer having a field
strength of 7 T (300 MHz for 1H). The first generation of widely used NMR
spectrometers were 60-MHz instruments.

The essential features of an NMR spectrometer consist of a powerful magnet to align

the nuclear spins. a radio frequency (r.f) transmitter as a source of energy to
excite a nucleus from its lowest-energy state to the next higher one, and a way to
monitor the absorption of r.f radiation and display the spectrum.

The Use of NMR Spectroscopy

1- It is used to determine relative location of atoms within a molecule .
2- It is the most helpful spectroscopic technique in organic chemistry
3-It is related to Magnetic Resonance Imaging (MRI) in medicine
4- It maps carbon-hydrogen framework of molecules
5- It depends on very strong magnetic fields
magnetic nuclei include:
– all nuclei with an odd number of protons (1H, 2H, 14N, 19F, 31P,...)
– all nuclei with an odd number of neutrons (13C)
• Nonmagnetic nuclei include:
– nuclei with even numbers of protons and neutrons (12C , 16O,…)

Nuclear Spin
• A nucleus with an odd mass number and odd atomic number has a nuclear spin.
• The spinning charged nucleus generates a magnetic field.
The Nature of NMR Absorptions
All nuclei in molecules are surrounded by electrons. When an external
magnetic field is applied to a molecule, the electrons moving around nuclei
set up tiny local magnetic fields of their own. These local magnetic fields
act in opposition to the applied field so that the effective field actually
felt by the nucleus is a bit weaker than the applied field.

In describing this effect of local fields, we say that nuclei experience shielding
from the full effect of the applied field by the surrounding electrons. Because
each chemically distinct nucleus in a molecule is in a slightly different electronic
environment, each nucleus is shielded to a slightly different extent and the effective
magnetic field felt by each is slightly different.
These tiny differences in the effective magnetic fields experienced by different
nuclei can be detected, and we thus see a distinct NMR signal for each chemically
distinct 13C or 1H nucleus in a molecule.

Nuclear Shielding and 1H Chemical Shifts

Our discussion so far has concerned 1H nuclei in general without regard for
the environments of individual protons in a molecule. Protons in a molecule
are connected to other atoms carbon , oxygen, nitrogen, and so on by
covalent bonds. The electrons in these bonds, indeed all the electrons in a
molecule, affect the magnetic environment of the protons. Alone, a
proton would feel the full strength of the external field, but a proton in
an organic molecule responds to both the external field and any local
fields within the molecule.
An external magnetic field affects the motion of the electrons in a molecule,
inducing local fields characterized by lines of force that circulate in the opposite
direction from the applied field .Thus, the net field felt by a proton in a
molecule will always be less than the applied field, and the proton is said to be
shielded.

Figure 3: The induced magnetic field of the

electrons in the carbon–hydrogen bond opposes
the external magnetic field. The resulting magnetic
field experienced by the proton and the carbon is
slightly less than B0

All of the protons of a molecule are shielded from the applied field by the electrons,
but some are less shielded than others. The term deshielded is often used to describe
this decreased shielding of one proton relative to another.
The more shielded a proton is the greater must be the strength of
the applied field in order to achieve resonance and produce a
signal.

A more shielded proton absorbs rf radiation at higher field strength

(upfield) compared with one at lower field strength (downfield).

The dependence of the resonance position of a nucleus that results

from its molecular environment is called its chemical shift.
This is where the real power of NMR lies. The chemical shifts of
various protons in a molecule can be different and are characteristic of
particular structural features.
Fig 4 shows the 1H-NMR spectrum of chloroform (CHCl3) to illustrate how
the terminology just developed applies to a real spectrum.
Instead of measuring chemical shifts in absolute terms, we measure them

with respect to a standard Tetramethylsilane (CH3)4Si, abbreviated TMS.

The protons of TMS are more shielded than those of most organic

compounds, so all of the signals in a sample ordinarily appear at lower

field than those of the TMS reference. When measured using a 100-MHz

instrument, the signal for the proton in chloroform (CHCl3), for example,

appears 728 Hz downfield from the TMS signal. But because frequency is

proportional to magnetic field strength, the same signal would appear

2184 Hz downfield from TMS on a 300-MHz instrument.

We simplify the reporting of chemical shifts by converting them to parts

per million (ppm) downfield from TMS, which is assigned a value of 0.

The TMS need not actually be present in the sample, nor even appear in

the spectrum in order to serve as a reference. When chemical shifts are

reported this way, they are identified by the symbol δ and are

independent of the magnetic field strength.

At 300 MHz the chemical shift for the proton in chloroform is:
Schematic operation of a basic NMR spectrometer. A thin glass tube
containing the sample solution is placed between the poles of a strong
magnet and irradiated with rf energy.
NMR spectra are usually run in solution and, although chloroform is a good
solvent for most organic compounds, it’s rarely used because its own signal at δ
7.28 would be so intense that it would obscure signals in the sample. Because the
magnetic properties of deuterium (D = 2H) are different from those of 1H, CDCl3
gives no signals at all in a 1H NMR spectrum and is the most commonly used
solvent in 1H NMR spectroscopy. Likewise, D2O is used instead of H2O for water-
soluble substances such as carbohydrates.

The Chemical Shift

NMR spectra are displayed on charts that show the applied field strength increasing from
left to right (Figure ). Thus, the left part of the chart is the low-field, or downfield, side, and
the right part is the high-field, or up field, side. Nuclei that absorb on the downfield side of
the chart require a lower field strength for resonance, implying that they have less
shielding. Nuclei that absorb on the up field side require a higher field strength for
resonance, implying that they have more shielding
The NMR chart. The downfield, DE shielded side is on the left, and the up field, shielded side is on the
right. The tetramethylsilane (TMS) absorption is used as reference point

To define the position of an absorption, the NMR chart is calibrated and a reference
point is used

Effects of Molecular Structure on 1H Chemical Shifts

Nuclear magnetic resonance spectroscopy is such a powerful tool for structure
determination because protons in different environments experience different
degrees of shielding and have different chemical shifts. In compounds of the
type CH3X, for example, the shielding of the methyl protons increases as X
becomes less electronegative.
In as much as the shielding is due to the electrons, it isn’t surprising to find that the
chemical shift depends on the degree to which X draws electrons away from the
methyl group.
A similar trend is seen in the methyl halides, in which the protons in CH3F are the
least shielded (δ 4.3) and those of CH3I (δ 2.2) are the most
The decreased shielding caused by electronegative substituents is primarily an inductive
effect and, like other inductive effects, falls off rapidly as the number of bonds between the
substituent and the proton increases. Compare the chemical shifts of the protons in propane
and 1-nitropropane.
The strongly electron-withdrawing nitro group Deshields the protons on C-1 by 3.4
ppm (δ 4.3 − 0.9). The effect is smaller on the protons at C-2 (0.7 ppm), and almost
completely absent at C-3. The DE shielding effects of electronegative substituents are
cumulative, as the chemical shifts for various chlorinated derivatives of methane
indicate.
Figure 6 collects chemical-shift information for protons of various types .
The major portion of the table concerns protons bonded to carbon. Within each type, methyl
(CH3) protons are more shielded than methylene (CH2), and methylene protons are
more shielded than methine (CH).

Given that the chemical shift of methane is δ 0.2, we attribute the decreased
shielding of the protons of RCH3, R2CH2, and R3CH to the number of carbons
attached to primary, secondary, and tertiary carbons, respectively. Carbon is
more electronegative than hydrogen, so replacing the hydrogens of CH4 by one,
then two, then three carbons decreases the shielding of the remaining protons .
Likewise, the generalization that sp2-hybridized carbon is more electronegative than
sp3-hybridized carbon is consistent with the decreased shielding of allylic and
benzylic protons.
Hydrogens that are directly attached to double bonds (vinylic protons) or to aromatic
rings (aryl protons) are especially deshielded .

The main contributor to the deshielding of vinylic and aryl protons is the
induced magnetic field associated with π electrons. The local field resulting from
electrons in a C-H σ bond opposes the applied field and shields a molecule’s protons.
The hydrogens of ethylene and benzene, however, lie in a region of the molecule
where the induced magnetic field of the π electrons reinforces the applied field,
deshielding the protons (Figure ).
In the case of benzene, this is described as a ring current effect that originates in the
circulating π electrons. It has interesting consequences, some of which are described
in the boxed essay Ring Currents: Aromatic and Antiaromatic in this chapter.

The induced magnetic field of the π electrons of (a) ethylene and (b)
benzene reinforces the applied field in the regions near vinyl and aryl
protons and deshields them.
Acetylenic hydrogens are unusual in that they are more shielded than we
would expect for protons bonded to sp -hybridized carbon. This is because
the π electrons circulate around the triple bond, not along it (Figure )
Therefore, the induced magnetic field is parallel to the long axis of the triple bond
and shields the acetylenic proton (Figure ). Acetylenic protons typically have
chemical shifts in the range δ 1.8–3.1.

The induced field of a carbonyl group (C=O) deshields protons in much the same
way that C=C does, and its oxygen makes it even more electron withdrawing.

Thus, protons attached to C=O in aldehydes are the least shielded of any protons bonded to
carbon. They have chemical shifts in the range δ 9–10.
Protons on carbons adjacent to a carbonyl group are deshielded slightly more than allylic
hydrogens.
The chemical shifts of O-H and N -H protons vary much more than those of protons
bonded to carbon. This is because O-H and N-H groups can be involved in intermolecular
hydrogen bonding, the extent of which depends on molecular structure, temperature,
concentration, and solvent. Generally, an increase in hydrogen bonding decreases the
shielding.
This is especially evident in carboxylic acids. With δ values in the 10–12 ppm range,
O-H protons of carboxylic acids are the least shielded of all of the protons
Hydrogen bonding in carboxylic acids is stronger than in most other classes of compounds that
contain O-H groups.
Protons in specific compounds may appear outside of the cited range depending on
the shielding or deshielding effect of substituents. The chemical shifts of O-H and
N-H protons depend on the conditions (solvent, temperature, concentration) under
which the spectrum is recorded.

We have mentioned that the protons in benzene appear at relatively low field
because of deshielding by the magnetic field associated with the circulating π
electrons. The amount of deshielding is sufficiently large on the order of 2
ppm more than the corresponding effect in alkenes that its presence is
generally accepted as evidence for aromaticity

We speak of this deshielding as resulting from an aromatic ring current .

Something interesting happens when we go beyond benzene to apply the aromatic c ring
current test to annulenes.
The signals in the 1H NMR spectrum. The outside protons have a
chemical shift δ of 9.3 ppm, which makes them even less shielded than
those of benzene. The six inside protons, on the other hand, have a negative
chemical shift (δ −3.0), meaning that the signal for these protons appears at
higher field (to the light) of the TMS peak. The inside protons of [18]
annulene are more than 12 ppm more shielded than the outside protons
.
As shown in Figure , both the shielding of the inside protons and the deshielding of
the outside ones result from the same aromatic ring current. When the molecule is
placed in an external magnetic field B0, its circulating π electrons produce their own
magnetic field.

This induced field opposes the applied field B0 in the center of the molecule ,
shielding the inside protons. Because the induced magnetic field closes on itself, the
outside protons lie in a region where the induced field reinforces B0.

The aromatic ring current in [18]annulene shields the 6 inside protons and
deshields the 12 outside ones

Exactly the opposite happens in [16] annulene (Figure 14.11b). Now it is the
outside protons (δ 5.3) that are more shielded
The inside protons (δ 10.6) are less shielded than the outside ones and less
shielded than the protons of both benzene and [18]annulene .
This reversal of the shielding and deshielding regions in going from [18] to
[16] annulene can only mean that the directions of their induced magnetic
fields are reversed. Thus [16] annulene , which has 4n π electrons and is
antiaromatic , not only lacks an aromatic ring current, its π electrons produce
exactly the opposite effect when placed in a magnetic field. Score one for
Hückel .