1H NMR Spectroscopy

Nuclear Magnetic Resonance

CHEMICAL SHIFTS
AND
FACTORS INFLUENCING CHEMICAL SHIFTS

By,
Archana Vanjari
M. Pharmacy (Pharmacology)
BLDE college of Pharmacy, Vijaypura
 Chemical Shift

Chemical shift is a measure of

the degree to which a nucleus
in a molecule is shielded.

C H
Protons in different
environments are shielded to
greater or lesser degrees;
they have different chemical
shifts.
H0
 Shielding

An external magnetic field

affects the motion of the
electrons in a molecule,
inducing a magnetic field
within the molecule. C H
The direction of the induced
magnetic field is opposite to
that of the applied field.

H0
 Shielding

The induced field shields the

nuclei (in this case, C and H)
from the applied field.
A stronger external field is
needed in order for energy C H
difference between spin states
to match energy of rf radiation.

H0
 Downfield Upfield
Decreased shielding Increased shielding

(CH3)4Si (TMS)

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

Chemical shift (d, ppm)

measured relative to TMS
The electrons surrounding a nucleus affect the effective
magnetic field sensed by the nucleus
Chemical Shift: H3C

H3C Si CH
CH3 3

H3C

The common scale for chemical shifts = d (ppm)

Frequency of signal (Hz) - Frequency of a reference (Hz)
d= X 10
operating frequency of the spectrometer (MHz)
 Effects of Molecular Structure
on
1H Chemical Shifts

protons in different environments experience different

degrees of shielding and have different chemical
shifts
The chemical shift is independent of the operating
frequency of the spectrometer
 Chemical Shift

Example: The signal for the proton in chloroform

(HCCl3) appears 1456 Hz downfield from TMS at
a spectrometer frequency of 200 MHz.
position of signal - position of TMS peak
d = x 106
spectrometer frequency

1456 Hz - 0 Hz
d = x 106
200 x 106 mHz

d = 7.28
Effects of Inductive Effect
on
1H Chemical Shifts
 Inductive Effect
Electronegative atom likes Halogens,
Oxygen and Nitrogen deshield the
protons and therefore the absorption
occurs at downshield.
Example: Protons in Dimethyl ether
(CHOCH) show a signal more
downfield than the Protons of ethane
(CH-CH)
Electron withdrawal produces NMR signals downfield
at
higher frequency (at larger d values)
 To sum up an Electron withdrawing
group is able to reduce electron density
around the proton and deshields the proton.

On the other hand, an electron releasing

group (such as Alkyl group) increases the
electron density and gives rise to shielding.
 Electronegative substituents decrease
the shielding of methyl groups

CH3F d 4.3 ppm least shielded H

CH3OCH3 d 3.2 ppm
CH3N(CH3)2 d 2.2 ppm
CH3CH3 d 0.9 ppm
CH3Si(CH3)3 d 0.0 ppm most shielded H
Effects of Anisotropic Effect
on
1H Chemical Shifts
 Anisotropic Effect (Space Effect)

Anisotropic Effect Constitute shielding and

deshielding effect on the proton because of
induced magnetic fields in other parts of the
molecule which operate through space.
For Example: If a magnetic field is applied to
a molecule having electrons, these
electrons begin to circulate at right angles to
the direction of the applied field thereby
producing induced magnetic field.
 The effect of this field on the nearby
proton has been found to depend upon
the orientation of the proton with respect
to the bond producing the induced
field.
Effects of Hydrogen
Bonding
on
1H Chemical Shifts
 Hydrogen Bonding

If a hydrogen atom exhibits the property

of hydrogen bonding in a compound, it
will get deshielded due to strongly
electronegative atom attached to it.
As such absorption is shifted downfield.
 Chemical Shift Table

Type of proton Chemical shift (d), Type of proton Chemical shift (d),
ppm ppm

H R 0.9-1.8 H C C C 2.5
C

H C C C 1.6-2.6 H C Ar 2.3-2.8

O H
C C 4.5-6.5
H C C 2.1-2.5
 Chemical Shift Table

Type of proton Chemical shift (d), Type of proton Chemical shift (d),
ppm ppm

H Ar 6.5-8.5 H C Cl 3.1-4.1

H C 9-10 H C Br 2.7-4.1

H C O 3.3-3.7
H C NR 2.2-2.9
 Chemical Shift Table

Type of proton Chemical shift (d),

ppm

H NR 1-3

H OR 0.5-5

H OAr 6-8

HO C 10-13
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