Final

Proton NMR and Its Applications in Structural Determination
CHAPTER – 1
Introduction
Department of Chemistry Page 1

Introduction:
Nuclear Magnetic Resonance (NMR) Spectroscopy as is implied in the name
involves the change of spin state of a nuclear magnetic moment when the nucleus absorbs
electromagnetic radiation in a strong magnetic field. This phenomenon was first
enunciated by American physicist Felix Bloch and Edward parcel in 1946 for which they
shared research Noble Prize in 1952. The NMR spectroscopy depends upon the fact that
most isotopes of the elements possess gyro magnetic properties, meaning there by that
they behave like tiny spinning bar magnets.
Nuclear magnetic resonance spectroscopy is based on measurement of absorption

radiation in the radio frequency range of roughly about 4-900MHz it is one of the most
powerful tools available to the chemist for elucidating the structure of chemical species.
The technique is also useful for the quantitative determination of absorbing species.
Studying a molecule by NMR spectroscopy enables us to record differences in the
magnetic properties of the various magnetic nuclei present and to reduce in large measure
what the positions of there nuclei are with in the molecule and how many different kinds
of environments are in the molecule and also which atoms are present in neighboring
groups usually we can also measure how many atoms are present in each of these
environments.
The most appropriate starting point-for the study of NMR is proton it is the
13
simplest nucleus and another important NMR is c (Carbon-13) NMR. Both the types of
NMR spectroscopy in common use today and also equal importance.

Principal of NMR Spectroscopy
The nucleus of hydrogen atom behaves as a spinning bar magnet because it

possess both electric and magnetic spin. The nucleus of H atom generates a magnetic
field. NMR involves the interaction between an oscillating magnetic field of
electromagnetic radiation and magnetic energy of Hydrogen nucleus and when nucleus is
placed in an external static magnetic field. The sample absorb the electromagnetic
radiation in radio wave region at different frequencies since absorption depends upon the
different type of the proton or certain nuclei contained in sample.
Consider the spinning top it performs slower waltz like motion in which spinning
axis of the top moves slowly around the vertical axis. This is precessional motion and the
top is said to be precessing around the vertical axis of the gravitational field. This
precession arises from the interaction of the spin with earth’s gravity acting vertically
downwards it is known as Gyroscopic motion.

Ho.(applied magnetic field)
The energy difference between (ΔE) the two spin states depend on the strength of
the applied magnetic field (Ho). The greater the strength of the magnetic field , greater
the difference in energy.
This can be expressed by the equation-
ΔE = hν = (hγ/2π) Ho.
Where, h = Plank’s constant
γ = Gyromagnetic ratio.
Ho. = Applied magnetic field
Fundamental NMR equation which correlates electromagnetic frequencies with

the magnetic field strength.
ν = (γ / 2π) Ho.
Where, Ho. = Applied magnetic field

γ = Gyromagnetic ratio is a fundamental nuclear constant it is the proportionality

constant between moment v and spin number I.
v= Frequency of electromagnetic radiation
The value of frequency v is inserted is called precessional frequency

which may defined as number of revolutions per second made by the magnetic
moment vector of the nucleus around the external field Ho.
Some characteristic properties of selected nuclei are given in the following table.
Natural % Magnetic Magnetogyric

Isotope Spin (I)
Abundance Moment (μ)* Ratio (γ)†
1
H 99.9844 1/2 2.7927 26.753
2
H 0.0156 1 0.8574 4,107
11
B 81.17 3/2 2.6880 --
13
C 1.108 1/2 0.7022 6,728
17
O 0.037 5/2 -1.8930 -3,628
19
F 100.0 1/2 2.6273 25,179
29
Si 4.700 1/2 -0.5555 -5,319
31
P 100.0 1/2 1.1305 10,840

CHAPTER – 2
Proton NMR and Chemical Shift

PROTON NMR
Proton NMR is the application of nuclear magnetic resonance in NMR

spectroscopy with respect to Hydrogen-1 nuclei with in the molecules of a substance in
order to determine the structure of its molecules. In this spectra of most of organic
compounds and are characterized chemical shifts (δ) in the range 0 to 15 ppm and by
spin-spin coupling between protons. By studying a compound by 1H NMR spectroscopy
one can obtain in principle three kinds of information.
 The relation between the number of signals (or peaks) in the spectrum and the
number of different kinds of hydrogen atoms in the molecule. Thus, one can know
the different kinds of environments of the Hydrogen atoms in the molecule.
 The areas underneath each signal are in the same ratio as the number of hydrogen
atoms causing each signal.
For example: consider the 1H NMR spectra of C2H60 isomers, diethyl ether and
ethyl alcohol. The six hydrogen atoms in dimethylether (CH3-O-CH3) experience
identical average environments and therefore show one sharp resonance signal. The
hydrogen atoms of ethyl alcohol are found three different locations and consequently
three absorption peaks are observed and its ratio of the three peak areas is 1:2:3 and they
are assigned to OH, CH2 and CH3 respectively.
 The principal signal may get split in to smaller peaks that is spin-spin splitting
may be observed. The type of splitting pattern observed (doublet, triplet, Quartet
and so on) depends on number of neighboring non equivalent protons Spin-spin
splitting thus helps in deducing molecular structure.
 The spacing between the peaks is labeled J. This is given the unit of cycles per
second or Hertz. J is coupling constant between two protons and J values gives
further information on molecular structure and stereo chemical features.
Eg: J-value between adjacent axial hydrogen’s in a cyclohexane is 10-13 Hz while J

between axial and equatorial or between two equatorial hydrogen is 3-5 Hz.

CHEMICAL SHIFT
The number of signals in an NMR spectrum tells the number of the sets of
equivalent protons in molecules. The position of signals in the spectrum helps us to know
the nature of protons via aromatic, aliphatic, acetylenic, vinylic adjacent to some electron
attracting or electron releasing group etc.
Each of these types of protons will have different environments and thus they
absorb at different applied field strengths. It is important to note that it is the electronic
environment which tells where a proton shows absorption in the spectrum when molecule
is placed in a magnetic field. The presence of magnetic field electrons are caused to
circulate and thus they produce secondary magnetic field that is induced magnetic field in
each a way that at the proton, it opposes the applied field. Thus the field experienced by
the proton is diminished and the proton is said to be shielded. Rotation of electrons about
nuclei generates a field that can either oppose or reinforce the applied field at the proton.
If the induced field reinforces the applied field, the protons feel higher field strength and
thus such a proton is called deshielded.
Shielding shifts the absorption up field and deshielding shifts the absorption
down field to get effective field strength necessary for absorption. Such shifts in the
positions of NMR absorption which arises due to the shielding or deshielding of protons
by the electrons are called chemical shifts. This difference in the absorption position of
the proton with respect to TMS signal is called Chemical Shift δ or τ (tau) scales are
commonly used to express chemical shift.
In majority of organic compounds, protons resonate at a lower field than the

protons of tetra methyl silane (TMS) thus aligning delta (δ) value for TMS equal zero.
Since TMS has internal standard in NMR spectroscopy because it is chemically inert,
non-toxic, cheap, volatile, low boiling point and soluble in most of organic solvents.
The value of δ is expressed in parts/million. Most chemical shifts values between

0 and 12. In the τ scale signal for the standard reference TMS is taken as 10ppm.

i.e., τ = 10 - δ
The NMR signal is usually plotted with magnetic field. Thus signals for TMS
appears at the extreme right spectrum of δ = 0 ppm. Greater the deshielding of protons,
larger will be the value of δ.
Proton Chemical Shift Ranges*

Type of proton. Chemical shift ( ppm)
Alkyl, RCH3 0.8-1.0

Alkyl, RCH2CH3 1.2-1.4
Alkyl, R3CH 1.4-1.7
Allylic, R2C=CRCH3 1.6-1.9
Benzylic, ArCH3 2.2-2.5
Alkyl chloride, RCH2Cl 3.6-3.8
Alkyl bromide, RCH2Br 3.4-3.6

Alkyl iodide , RCH2I 3.1-3.3
Ether, ROCH2R 3.3-3.9
Alcohol, HOCH2R 3.3-4.0
Ketone, RCOCH3 2.1-2.6

Aldehyde, RCOH 9.5-9.6
Vinylic, R2C=CH2 4.6-5.0
Vinylic, R2C=CRH 5.2-5.7
Aromatic, ArH 6.0-9.5
Acetylenic, RC=CH 2.5-3.1
Alcohol hydroxyl, ROH 0.5-6.0a
Carboxylic, RCOOH 10-13a
Phenolic, ArOH 4.5-7.7a
Amino, R-NH2 1.0-5.0a

CHAPTER – 3
Factors Influencing Chemical Shift

FACTORS INFLUENCING CHEMICAL SHIFT
1. Effect of substituent
A proton is said to be deshielded. If it is attached to an electronegative atom or
group. Greater the electro negativity of the atom or group greater is the deshielding
caused to the proton. If the deshielding is more than its  value will also be more.
b a b a
1. CH3 CH2 F 2. CH CH2 Cl
3
 Two signals are expected for each of the two compounds. Deshielding for protons
‘a’ in compound (1) is more than that for similar protons in compound (2).
 As the distance from the electronegative atom increases, the deshielding effect
due to it diminishes. Protons ‘b’ is comparatively less deshielded and hence will
resonate at comparatively at lower δ value.
CH3F CH3Cl CH3Br CH3I.
 4.26  3.1  2.7  2.16
Increasing deshielding of the hydrogen atoms of the methyl group with

increasing electro negativity of the halogen.

O CH3 N CH3 C CH3 Si CH3
 3.3  2.2  0.9  0
Increasing electro negativity of the group bonded to methyl group deshields

nearby hydrogen resulting in a down field shift.
2. Vander Waal’s Deshielding
In over crowded molecules, it is possible that some proton may be occupying
sterically hindered position. Clearly, electron cloud of a bulky group (hindering group)
will tend to repel the electron cloud surrounding the proton. Thus, such a proton will be
deshielded and will resonate at slightly higher value of  than expected in the absence of
this effect.
3. Hybridization Effect
SP3 Hydrogen
 It is noted that hydrogens attached to purely sp3 hybridized carbon atoms
(C-CH3, , C-CH2C ) have resonance in the limited range from 0-2 ppm
provided that no electronegative elements or π bonded groups are nearby..
 Hydrogen attached to carbons to highly strained rings live in cyclopropyl
hydrogen appears at 0-1 ppm.

 Most methyl group appears near 1 ppm. If they are attached at greater chemical
shifts 1.2 to 1.4 ppm.
CH3 H H
H
HC3 H HC3 H HC3 H
H
CH3 CH3 H
3 > 2 > 1 > Stained ring
2 1 0 
SP2 Hydrogen
 Simple vinyl hydrogen (C-C=C-H) have resonance in the range fro 4.5 to 7. Here
vinyl hydrogen has greater chemical shift than aliphatic hydrogen on sp3 carbon.
 Aromatic hydrogen appears in the range further downfield (6.5-8 ppm).
 The downfield positions of vinyl and aromatic resonances are however greater
than one would expect on there hybridization difference called Anisotropy is
responsible for the largest part of there shifts.
Sp Hydrogen
 Acetylenic hydrogens (C-H; sp- 1s) appear anomalously at 2 to 3 ppm owing to
anisotropy. On the basis of hybridization alone, as already discussed one would
expect the actylenic proton have a chemical shift greater then that of the vinyl

proton. An sp carbon should behave as if it were more electro negative than sp2
carbon.
4. Hydrogen Bonding
Hydrogen bonding involves electron cloud transfer from hydrogen atom to
neighboring electronegative atoms. The electron withdrawal from a proton, involved in
H-bonding, thus causes deshielding of the proton. The greater the degree of hydrogen
bonding of a proton the greater the downfield shift (higher  value) of its resonance.
The positions of resonance of OH, NH and SH protons of alcohols, amines and
thiols is unpredictable because the extent to which the hydrogen atoms are involved in
hydrogen bonding will depend critically on concentration, solvent and temperature.
H H
O O O O
C
OR
Salicylates -Diketone (enol form)
 OH = 10-12 ppm  OH = 10-16 ppm
5. Anisotropic Effect
The deshielding effect on proton attached to C = C is higher than that can be
accounted for by the inductive effect alone. Aldehydic and aromatic protons are much
more deshielded. The values of  in each case can be justified by explaining the manner
in which the -electrons circulate the influence of the applied field.

Alkynes
In alkynes, electronic circulation around triple bond shielding in such a way that
the protons experience diamagnetic shielding effect when the axis of the alkynes group
lies parallel to the direction of the applied field. The -electrons are induced to circulate
around the axis in such a way that the induce field opposes the applied field. Then
protons feel smaller field strength (shielding) and hence resonance occurs at higher
applied field (low  value).
Benzene
In case of benzene, loops of -electrons are delocalized cylindrically over the
aromatic ring these loops of electrons are induced to circulate in the presence of the
applied field producing ring current. The induce current is diamagnetic (opposing the
applied field) in the centre of the ring and in paramagnetic outside the ring then, the
aromatic protons experience, a magnetic field greater in magnitude than the applied field.
Such a protons are said to be deshielded and hence smaller applied field (higher value of
) will be require to bring them to resonance. It may be noted that the protons held above
and below the plane of the ring resonate at low  value.

6. Solvent Effect
A substance free from proton should be used as a solvent i.e., which does not give
absorption on its own in NMR spectrum. The solvent should be capable of dissolving at
least 10% of the substance under the investigation. Following solvents are commonly
used in NMR spectroscopy.
1. Carbon tétrachloride - CCl4.
2. Carbon disulphide - CS2.
3. Deuterochloroform - CDCl3.
4. Hexa chloroacetate - (CCl3)2 CO etc.
These solvents differ considerably as regards their polarity. Clearly, NMR
spectrum of a compound measured in one solvent may be slightly differing from that
measured in another solvent of different polarity. Hence, its important to mention the
solvent used in NMR spectrum. Hydrogen bonding involves electron cloud transfer from

hydrogen atom to a neighboring electronegative atom (O.N.S. etc.) the hydrogen atom
experience a net deshielding effect. At higher concentration of –OH, -NH compounds
(strong inter molecular hydrogen bonding) dshielding proton is greater and signal appear
at higher  value than that at low concentration. For a compound showing intramolecular
hydrogen bonding, the concerned  values remain unchanged even if the solution is
diluted.

CHAPTER –4
Splitting

Spin-Spin Splitting or (n+1) Rule
Another type of information to be found that in the NMR spectrum is that derived
fro the spin-spin splitting phenomenon. The interaction between the spins of neighboring
magnetic nuclei in a molecule may cause the splitting of NMR signal in the spectrum.
This is known as spin-spin coupling which occurs through bonds by means of a slight
unpairing of the bonding electrons. The spin of the nearby nucleus affects the magnetic
environment of the nucleus we are observing and the signal is not a simple, singlet, but a
multiplet. The complexity of the multiplate depends upon the nature and number of the
nearby atoms. However, chemically equivalent protons do not show spin-spin coupling
due to interactions among themselves.
For example: Cl – CH2 – CH2 – Cl (1,2, dichloromethane).

Consider an example : Ethyl bromide.
Then spin of two protons (-CH2-) can couple with the adjacent methyl group (-
CH3) in three different ways relative to the external field. The different ways are
i.  ii.  iii. 
Thus, a triplet of peaks with the intensity ratio of 1:2:1 which corresponds to the
distribution ratio of alignment. Also the spin of three protons (Ch3-) can couple with the
adjacent methylene group (-CH2-) n four different ways relative to external field.
i.  ii.    iii.    iv. 
Similarly, a peak is split by ‘n’ identical protons into components whose sizes are
in the ratio of the nth row of Pascal’s triangle. This triangle helps to predict peak
intensities of the various multiplets.
Multiplicity Intensity Ratio

Singlet (s) 1
Doublet (d) 1:1
Triplet (t) 1:2:1
Quartet (q) 1:3:3:1
Quintet 1:4:6:4:1
Sextet 1:5:10:10:5:1
Septet 1:6:15:20:15:6:1

Coupling Constant (J)
The spacing of adjacent lines in the multiplet is a direct measure of the spin-spin
coupling of the protons and known as coupling constant J or the distance between the
peaks in a single multiplet is called the coupling constant. The value of J is independent
of the external field. It is expressed in Hertz (Hz). The value of J decreases with distance.
The number of bonds intervening between the coupling nuclei is important, since
coupling is transmitted via the electrons of these bonds. It is a convient notation to
indicates this number as a super script to the symbol for the coupling constant. Thus
direct coupling (13C- 1H) would be one bond coupling 1J, the coupling between proton on
a CH2 group would symbolized by 2J and so on.


CHAPTER –5
Applications

APPLICATIONS OF NMR SPECTROSCOPY
NMR Spectra provide an important tool for the characterization of a compound

when used in conjugation with infrared, ultraviolet and Mass spectra. A few application
of NMR spectroscopy are as follows,
1. Structural Diagnosis
Consider the following data of compounds with NMR data
i. C3H3Cl5 Proton (a) 1H exhibits triplet at 4.52 
Proton (b) 2H exhibits singlet at 6.07 
ii. C10H4 Proton (a) 9H exhibits singlet at 1.3 
Proton (b) 2H exhibits singlet at 7.28 
In the compound C3H3Cl5 it is evident that CH and CH2 groups are adjacent that
spitted into doublet and triplet respectively. The τ values can be compared with standard
values for each protons the following structure are suggested.
Cl
Cl Cl
Cl Cl Cl
Cl Cl Cl
Cl 1,1,1,2,3-pentachloropropane

In the compound C10H4 two singlets shows the absence of spin-spin coupling the
singlet with low tau value corresponds to aromatic protons of alkyl substituted benzene.
The higher tau value is due to alkyl protons. Thus following structure is possible.
H3C CH3
H3C
tert-butylbenzene
2. Detection of Hydrogen bonding
Proton signal is shifted down field in case of Hydrogen bonding. This reveals that
Hydrogen bond formation results in decrease in the electron shielding of the proton. The
extent of Hydrogen bonding varies with solvent temperature and concentration of the
solution. An upfield signal is ascribed to the breaking of intermolecular Hydrogen bonds.
This can be seen in case of ethanol on increasing temperature or diluting it.
Schneider and Bernstein have considered that the Shifts associated with Hydrogen
bonding arise from,
a. Changes in long range shielding of the acceptor group.
b. The electronic effect of the donor atom.
c. The diamagnetic anisotropy of the donor atom or group in the molecular and
intramolecular Hydrogen can be distinguished as the latter is not concentration
dependent.

3. Identification of Structural Isomers
The identification between following isomer can be easily made from their NMR
Spectra.
H3C
H3C CH3
Cl Cl
a b
In the isomer (a) 3 signals are observed where as we see only 2 signals in spectrum for
(b) which is a clear distinction between the above isomers . the 3 signals for isomer (a) in
order of decreasing δ values are
i. A three protons triplet (CH3 -)
ii. A two proton sextet (-CH2-)
iii. A two proton triplet (-CH2-Cl)
Similarly, distinction between isomer of (b), two signals have their multiplicities as
i. Doublet (6H) – upfield
ii. Septet (1H) - downfield
Similarly, distinction between the positions of isomers like proponal-1 and propanol-2
can be explained as follows.
H3C CH3
c a b a
H3C
a
d OH OH
b
A B

For ‘A’ isomer propanol-1 For ‘B’ isomer propanol-2
Four Signals Three Signals
i a – Singlet (1H)  Value i a – doublet (6H)  Value

decreases increases
ii b – triplet (2H) ii b – septet (1H)
iii C – Sextet (2H) iii C – Singlet (1H)
iv d – Triplet (3H)
4. Detection of Aromaticity
Protons attached to the benzyl, polynuclear and heterocyclic compounds whose

parallel electrons follow Hackle’s rule [i.e., (4n+2)] parallel electrons where n = 1, 2,
3,…. are extremely deshielded due to the circulating sextet (ring current) of π electrons.
As a result of this the signal of aromatic protons appears at a very low field than that
observed even for benzene. From this the aromatic character of the compound under
investigation can be predicated.
5. Distinction between Cis-Trans isomers and conformers
The Cis and Trans isomers of a compound can be easily distinguished as the
concerned protons have different values of the chemical shifts as well as coupling
constants.
H3C CH3 H3C Hb
Ha Hb Ha CH3
Jcis = 7-12 HZ Jtrans= 13-18 HZ

Similarly, the various conformations of compound the axial and equatorial

positions of the proton or group carrying a proton can be distinguished from their
different values of the coupling constant.
6. Conformational Analysis
The measurement of relative populations of various conformations of a molecule

can be done at different temperature from the relative stability and energies of the
conformations can be deduced the following ways provide this information’s.
a) From coupling constants
The value of J between the protons on a pair or adjacent carbons depends on the
dihedral angle between the protons. In case of cyclohexane derivatives it is found that J is
2-3 times as large between antiprotons as between gauche protons.
b) A chemical Shift ()
For a particular proton is the weighted average of various chemical shifts for that
proton in the various conformations. For axial and equatorial protons τ = Ne τ +Na. τa,
where N is the mole fraction of a conformation.
7. Detection of Electronegative atom
Presence of electronegative atom in the neighborhood of the proton causes

desheilding and the signal is shifted downfield. Greater the electro negativity of the
adjacent atom, smaller is the  value of absorption for the concerned proton, fluorine
causes more downward shift than nitrogen and so on.
8. Detection of double bond character
In some compounds the molecule acquires a little double bond character due to
resonance. Hence two signals can be expected for equivalent protons it is due to hindered
rotation which changes the geometry of the molecules.

Let us consider dimethyl formamide
In the following structure (I) since two methyl groups are exactly equivalent, So
two singlet should be expected.
In structure (II) the pressure of double bond restricts rotation and the two methyl
group remains no longer equivalent (geometrical isomers). Thus two signals appear for
two methyl groups.
a Hc a
Hb CH CH3
.. 3 +
N N
O CH3
O CH3 b
a -
II
I
9. Keto – enol Tautomerism
The NMR spectra give qualitative evidence of the two forms as well as
proportions of the two at equation from the relative signal in tensties the following
equation is observed in acetyl acetones.
b
O O
O OH
b a d
H3C CH3
a a H3C CH3
c
ketonic form enolic form
A two proton singlet at δ 3.65 due to ketonic form where as four signals due to all
eight protons in the enolic form are observed thus enol protons, Keto protons = 8:2 or 4:1
Hence 80% of the enolic form and 20% of the Ketonic form are present in the
equilibrium mixture of acetyl acetone.

10. Quantitative Analysis
Equilibrium mixtures can be analyzed when the proton signals of the components,
are well separated. In the NMR spectrum of pure ethanol, a triplet is observed for the –
OH proton when water is added to ethanol, then due to proton exchange the triplet
collapses to a singlet from the values of the chemical shift the ratio of water and alcohol
can be estimated by comparing with the known results.
11. Applications of NMR in inorganic compounds
 Oxyacids of phosphorous have been distinguished by NMR techniques.
 The Spin-Spin interaction between P31 and H1 (both have I – 1/2) provide the
O
distinction between P-O-H and HP
 NMR Studies of various Co (III) complexes revel large chemical shifts because of
second order paramagnetic effect.
 Nuclei with Quadrapole moments undergo spin-lattice relaxation when such a

nucleus is attached to another atom whose spectra are to be recorded, extensive
line broadening occurs and some times no spectrum obtained. Since the
Quadrapole moments arises between of an asymmetric distribution of charge in
the nucleus coupling with external field might give direct asymmetry of the field
which is of significance in providing detailed information about bonding and
electron distribution in molecules.

CHAPTER –6
Illustrative Examples

ILLUSTRATIVE EXAMPLES
1
H NMR absorption that may be expected for compounds in each of the most
common classes of organic compounds as follows.
A. Alkanes
Alkanes have three different types of Hydrogen methyl, methylene and methane
each of which appears in its own region of the NMR spectrum.
CHEMICAL SHIFTS
R – CH3 0.7 – 1.3 ppm Methyl groups are often

recognizable as a tall singlet,
doublet or triplet even when
overlapping outer CH
absorption.
R-CH2-R 1.2 – 1.4 ppm In long chains all of the

methylene (CH2) absorptions
may be overlapped in an un
resoluble groups
R3CH 1.4 – 1.7 ppm Note that methane hydrogens

(CH) have a larger chemical
shift than those in methylene
and methyl groups.
COUPLING BEHAVIOUR
-CH-CH- 7-8Hz In Hydrocarbon chains

adjacent hydrogen will
generally couple with the spin-
spin splitting following the
n+1 rule

In alkanes all of the CH Hydrogen absorptions are typically found from about 0.7
to 1.7ppm. Hydrogen in methyl groups are the most highly shielded type of proton and
are found at chemical shift values lower (0.71-3ppm) then methylene (1.2-1.5ppm) or
methane Hydrogen (1.4-1.7ppm)
In long chains Hydrocarbons all of the CH and CH2 absorptions may overlap in
an irresoluble group methyl group peaks are usually separated from other types of
hydrogen’s being found at lower chemical shifts. However even when methyl Hydrogens
are located with in an un resolved cluster of peaks can often be recognized as tall singlets
doublets or triplets clearly emerging from the absorptions of the other types of protons.
Methine protons are usually separated from the other being shifted further downfield.
Eg. Propane

B. Alkenes
Alkenes have two types of Hydrogens Vinyl (those attached directly to the double
bond) and alkylic hydrogens (those attached to the -carbon, the carbon atom attached to
the double bond) each type has a characteristic chemical shift region.
CHEMICAL SHFITS
C=C-H 4.5 – 6.5ppm Hydrogen attached to a double bond (vinyl
hydrogens) are deshielded by anisotropy of
the adjacent double bond.
C=C-C-H 1.6 – 2.6 ppm Hydrogens attached to a carbon adjacent to a

double bond (alkylic hydrogens) are also
deshielded by the anisotropy of the double
bond but between the double is more distant
the effect is smaller
H-C=C-H The Splitting protons of Vinyl may be

3
Jtrns =11-18 Hz complicated by the fact that they may not be
3
Jcis = 6-15 Hz
equivalent even when located on the same
carbon of the double bond.
-C=C-H When allylic hydrogen are present in alkene

2
J= 0-1 Hz they may show long range alkylic coupling to
4
J=0-3 Hz
hydrogen on the for double bond carbon as
well as the usual splitting due to the hydrogen
on the adjacent carbon.

Example : 1H Spectrum of 2-methyl – 1- pentane.
C. Alkynes
Terminal alkynes (those with a triple bond at the end of chain) will show an
acetylenic hydrogen as well as the -hydrogens found on carbon atoms next to the triple
bond. The acetylenic hydrogen will be absent if the triple bond is in the middle chain.
CHEMICAL SHIFTS
CC-H 1.7-2.7 PPM The terminal or acetylene hydrogen as a chemical shift
near 1.8ppm due to anisotropic shielding by the
adjacent π bonds.
CC-H- 1.6-2.6 PPM Protons on a carbon next to the triple bond are also
affected by the π system
Coupling Behavior
4
H-CC-C-H J = 2-3Hz “Allylic Coupling” is often observed in alkynes but it
will often be quite small or even non-existent

Example : 1H spectrum of 1-penyne
D. Aromatic Compounds
Aromatic compounds have two types of hydrogens aromatic hydrogen’s (benzene

ring hydrogens) and benzylic (those attached to an adjacent carbon atom).
CHEMICAL SHFITS
6.5 – 8.0ppm Hydrogen attached to an aromatic (benzenoid
ring have large chemical shift equally near 7.0
H
ppm they are deshielded by the anisotropic
field generated by e- is in the ring π system.
2.3 -2.7 ppm Benzylic hydrogen are also deshielded by the
anisotropic field of the ring but they are more
CH2
distant from the ring and the effect is smaller.
COUPLING BEHAVIOR
Splitting patterns for the protons on a benzene
3 ring are discussed it is often possible to
Jortho=7-10 Hz
determine the position of the subsisting on the
4
Jmeta=2-3 Hz ring form these splitting patterns and the
H
5
Jpara=0-1 Hz magnitude of the coupling constants.

Example: 1H spectrum of  - chloro – P – xylene
E. Alkyl Halides
In alkayl halides the -hydrogen (the one attached to the same carbon as the
halogen) will be deshielded.
Chemical Shifts
-CH-I 20.0–4.0 ppm The chemical shift of H atom attached to the lane carbon as
a halide atom.
-CH-Br 2.7-4.1 ppm Will increase (move further downfield)
-CH-Cl 3.1-4.1ppm This deshielding effect is due to the electronegativity of the

attached.
-CH-F 4.2-4.8 ppm Halogen atom the extent of the shift is increased as the
electrongativity of the attached atom increases with largest
shift found in compounds containing fluorine.

Coupling Behavior
2
-CH-F J=50 Hz Compounds containing fluorine will
3
-CH-CF- J=20Hz Show spin-spin splitting due to coupling between the
fluorine and hydrogens on either the same or the adjacent
carbon atom. Fluorine has a spin of ½ the other halogens
(I.Cl.Br) do not show coupling.
Ex : 1H Spectrum of 1-Chlrobutane

F. Alcohols:
In Alcohols both the hydroxyl proton and the -hydrogens (those on the same
carbon as the hydroxyl group) have characteristic chemical shifts.
Chemical Shifts
C-OH 0.5-5.0ppm The chemical shift of the –OH hydrogen in variable. Its
position depending on concentration, solvent of
temperature. The peak may be broadened at its base by the
CH-O-H 3.2-3.8 ppm
same set of factors.
Protons on the  carbon are dshielded by the

electronegative oxygen atom and are shifted down field in
the spectrum.
Coupling Behavior
CH-OH No coupling or Because of the rapid chemical exchange of the –OH proton
3
J=5Hz in many solutions coupling is not usually observed
between the –OH proton and those hydrogens attached to
the -carbon.
Example: 1H Spectrum of 2-methyl-l-propanol

G. Ethers
In ethers, the -hydrogen (those attached to the -carbon, which is the carbon
atom attached to the oxygen) are highly deshielded.
Chemical Shifts
R-O-CH- 3.2-3.8 ppm The Hydrogens on the carbons attached to the oxygen are
deshielded due to the electro negativity of the oxygen
Example : 1H spectrum of butyl methyl ether.
H. Amines :
Two characteristics types of Hydrogens are found in amines those attached to

nitrogen (the hydrogens of the amine group) and those attached to the -carbon (the same
carbon to which the amino group is attached).

Chemical Shifts
R-N-H 0.5-4.0 ppm Hydrogen attached to a nitrogen have a variable chemical

shift depending on the temperature, acidity amount of
hydrogen bonding of solvent.
-CH-N- 2.2-2.9 ppm The -hydrogen is slightly deshielded due to the Electro
negativity of the attached nitrogen.
3.0-5.0 ppm This hydrogen is desheilded due to the anisotropy of the

N H
ring and the resonance that removes electron density from
nitrogen and changes its hybridization.
1
-N-H J=50Hz Direct coupling between nitrogen and attached hydrogen
is not usually observed, but is quite large when it occurs.
More commonly this coupling is observed by quadrapole
broadening by nitrogen or by proton exchange

Example : 1H spectrum of propylamine.
I. Nitriles:
In nitriles only the -hydrogens (those attached to the same carbon as the Cyano
group) have a characteristic chemical shift.
Chemical Shifts
-CH-CN 2.1-3.0 ppm The -hydrogens are slightly deshielded by the cyano group
Hydrogens on the adjacent carbon of a nitrile are slightly deshielded by anisotropic field
of the π-bonded electrons appearing in the range 2.1-3.0 ppm.

Example: 1H spectrum of Valeronitrile.
J. Aldehydes:
Two types of hydrogens are found in aldehydes. the aldehyde hydrogen and the
-hydrogens (those hydrogens attached to the same carbon as the aldehyde group).
Chemical Shifts
R-CHO 9.0-10.0 ppm The aldehyde hydrogen is shifted for downfield due toe the
anisotropy of the (Carbonyl group CC=O)
R-CH-CH=O 2.1-2.4 ppm Hydrogen on the carbon adjacent to the C=O group are also
deshielded due to the carbonyl group, but they are more
distant and effect is smaller.
Coupling Behavior
3
-CH-CHO J=1-3 Hz Coupling frequently occurs between the aldehyde hydrogen
and hydrogens on the adjacent carbon, but J is small

Example : 1H spectrum of 2-methylbutyraldehyde.
K. Ketones:
Ketones have only one distinct of hydrogen atoms – those attached to the -
carbon.
Chemical Shifts
2.1-2.4 ppm The -hydrogens in ketones are deshielded by the

anisotropy of the adjacent C=O group.
Example: 1H spectrum of 3-methyl -2-pentanone.

L. Esters:
Two distinct types of hydrogens are found in esters those on the carbon atom
attached to the oxygen atom in the alcohol part of the ether and those on the -carbon in
the acid part of the ester (attached to the carbon next to the C=O group).
Chemical Shifts
R-CH- 2.1-2.5 ppm The -hydrogens in ester are deshielded by the anisotropy of
COOR
the adjacent (C=O) group
R-COO- 3.5-4.8 ppm Hydrogen on the carbon attached to the oxygen are
CH-
deshielded due to electro negativity of oxygen.
Example: Isobutyl acetate
M. Carboxylic acids:
Carboxylic acids have the acid proton (the one attached – COOH gp) and the -
hydrogen those attached to the same carbon as the carboxyl group.

Chemical Shifts
R-COOH 11.0-12.0 ppm This hydrogen is deshielded by the attached oxygen and it is
highly acidic. This is a very characteristic peak for
carboxylic acids.
-CH- 2.1-2.5 ppm Hydrogen adjacent to the carbonyl group are slightly
COOH
deshielded.
Example: 1H spectrum of ethyl malonic acid.
N. Amides
Amides have three distinct types of hydrogens, those attached to nitrogen, -

hydrogen attached to the carbon atom on the carbonyl side of the amide group and
hydrogens attached to carbon atom that is also attached to the nitrogen atom.

Chemical Shifts
R(CO)-N-H 5.0-9.0 ppm Hydrogens attached to amide nitrogen are variable in

chemical shift, the value being dependent on the
temperature, concentration and solvent.
-CH-CONH 2.1-2.5ppm The -hydrogens in amides absorb in the same range

as other acyl hydrogens they are slightly deshielded
by the carbonyl group.
R(CO)-N-CH 2.2-2.9 ppm Hydrogens on the carbon next to the nitrogen of the
amide are slightly deshielded by the electro
negativity of the attached nitrogen.
Example : 1H spectrum of butyramide.

Conclusion
NMR is a technique that enables use to study the shape and structure of the
molecule. It reveals the different chemical environment of the various forms of hydrogen
present in the molecule since over a fast 50 years NMR as become the preeminent
technique for determining the structure of organic compounds of all the spectroscopic
methods. It is the only one for which a complete analysis and interpretation of entire
spectrum is normally expected and NMR is non-destructive may be obtained from
samples weighing cell than a milligram. Hence NMR as a wide range application both in
qualitative &quantitative analysis these are used to study both organic and inorganic
compounds also it find application in medical fields.

Bibliography
 Introduction to Spectroscopy, Third Edition

Author : D L Pavia, G M Lampman
Year of Publication : 2008
Published by : Sourabh Printers
Page No.s : 139-154, 121-125, 102
 Spectroscopy of organic compounds, Sixth Edition

Author : P.S. Kalsi
Published by : New Age international (P) Ltd.
Page No.s : 183-225
 Organic Spectroscopy, Third Edition
Author : William Kemp.

Published by : Palgrave Publications
Page No.s : 119-127, 131.
 Elementary Organic Spectroscopy, Fourth Edition
Author : Y R Sharma
Published by : S Chand & Company Pvt. Ltd.
Page No’s : 182-190, 194-200, 213-222
 Instrumental methods of chemical analysis, Fifth Edition
Author : Dr.H. KAUR

Published by : Pragati Prakashan
Page No.s : 364-365, 372-443
 www.google.com

Final

Caricato da

Informazioni sul documento

Descrizione originale:

Titolo originale

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Final

Caricato da

Copyright:

Formati disponibili

Proton NMR and Its Applications in Structural Determination

Department of Chemistry Page 1

Nuclear magnetic resonance spectroscopy is based on measurement of absorption

Department of Chemistry Page 2

Principal of NMR Spectroscopy

The nucleus of hydrogen atom behaves as a spinning bar magnet because it

Department of Chemistry Page 3

Ho.(applied magnetic field)

This can be expressed by the equation-

Where, h = Plank’s constant

Ho. = Applied magnetic field

Fundamental NMR equation which correlates electromagnetic frequencies with

Where, Ho. = Applied magnetic field

Department of Chemistry Page 4

γ = Gyromagnetic ratio is a fundamental nuclear constant it is the proportionality

v= Frequency of electromagnetic radiation

The value of frequency v is inserted is called precessional frequency

Natural % Magnetic Magnetogyric

Department of Chemistry Page 5

Proton NMR and Chemical Shift

Department of Chemistry Page 6

Proton NMR is the application of nuclear magnetic resonance in NMR

Eg: J-value between adjacent axial hydrogen’s in a cyclohexane is 10-13 Hz while J

Department of Chemistry Page 7

In majority of organic compounds, protons resonate at a lower field than the

The value of δ is expressed in parts/million. Most chemical shifts values between

Department of Chemistry Page 8

Proton Chemical Shift Ranges*

Department of Chemistry Page 9

Type of proton. Chemical shift ( ppm)

Alkyl, RCH3 0.8-1.0

Alkyl chloride, RCH2Cl 3.6-3.8

Alkyl bromide, RCH2Br 3.4-3.6

Alcohol, HOCH2R 3.3-4.0

Ketone, RCOCH3 2.1-2.6

Department of Chemistry Page 10

Factors Influencing Chemical Shift

Department of Chemistry Page 11

FACTORS INFLUENCING CHEMICAL SHIFT

A proton is said to be deshielded. If it is attached to an electronegative atom or

resonate at comparatively at lower δ value.

CH3F CH3Cl CH3Br CH3I.

 4.26  3.1  2.7  2.16

Increasing deshielding of the hydrogen atoms of the methyl group with

Department of Chemistry Page 12

O CH3 N CH3 C CH3 Si CH3

 3.3  2.2  0.9  0

Increasing electro negativity of the group bonded to methyl group deshields

2. Vander Waal’s Deshielding

In over crowded molecules, it is possible that some proton may be occupying

 It is noted that hydrogens attached to purely sp3 hybridized carbon atoms

provided that no electronegative elements or π bonded groups are nearby..

 Hydrogen attached to carbons to highly strained rings live in cyclopropyl

hydrogen appears at 0-1 ppm.

Department of Chemistry Page 13

shifts 1.2 to 1.4 ppm.

3 > 2 > 1 > Stained ring

 Aromatic hydrogen appears in the range further downfield (6.5-8 ppm).

than one would expect on there hybridization difference called Anisotropy is

responsible for the largest part of there shifts.

 Acetylenic hydrogens (C-H; sp- 1s) appear anomalously at 2 to 3 ppm owing to

anisotropy. On the basis of hybridization alone, as already discussed one would