NMR

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 Introduction
• NMR spectroscopy – the preeminent technique for
determining the structure of organic compounds
• An NMR spectrum provides information about
chemical structures that would be difficult if not
impossible, to obtain by any other method
• Measures the interaction of electromagnetic radiation
(radiofrequency) with nuclei (nmr active) in a strong
external magnetic field
• Nuclei (positively charged) are part of atoms that are
in turn assemble into molecules
Characteristics of NMR active Nuclei
 NMR active nuclei have either
Even mass number (i.e. number of neutrons and
protons are both odd) e.g. 14N
Odd mass number (i.e. number of neutrons plus
protons is odd) e.g. 1H and 13C
1H and 13C are of importance to organic chemist
This lecture will focus on 1H and 13C
 Basic principles of 1H and 13C NMR
• Nuclear spins are oriented randomly in the absence of an external
magnetic field but have a specific orientation in the presence of
an external field, B0
Some aligned parallel to the external field (Lower energy
orientation)
Some aligned antiparallel to the external field (Higher energy
orientation)

When nuclei aligned parallel with an external magnetic field are

irradiated with electromagnetic radiation ( radio frequency
region), energy is absorbed and the nuclei “spin-flips” to the
higher-energy antiparallel alignment
Nuclei that spin flips in response to the applied radiation is said to
be in resonance with the radiation – Nuclear Magnetic Resonance
Basic principles of NMR – contd.
The NMR spectrophotometer detects and records this
absorption of energy in the form of chemical shifts/
signals
Signals appear at different places in a spectrum – Due to
the influence of deshielding or shielding
• This would apply to an isolated proton, but real protons have other
things around them - especially electrons.
• This electrons cut down the size of the external magnetic field felt by
the hydrogen nucleus.
• Each hydrogen atom will need a slightly different magnetic field to
bring it into the resonance condition depending on what exactly it is
attached to.
Informations obtained from 1H NMR

• 1. Different kind of protons

• 2. Number of each kind of protons
• 3. Number of neighbouring protons
1. Different kind of protons

• This is determined by the number of signals in the spectrum

• The signals appear in different regions because of effect of shielding
and deshielding/ chemical shift
CHEMICAL SHIFT/Sheilding and
desheilding
• When a cpd is placed in a uniform magnetic field the electrons
sorrounding its nucleus are made to circulate.
• In the process they generate their own magnetic field which oppose
the external magnetic field.
• So the strength of external magnetic field around the nucleus is
reduced
• This reduction is called shielding and the nucleus is said to be shielded
• In some cases, the proton may be under the influence of an increasing
magnetic field and this is called deshielding
• This variation give rise to differences in chemical shift positions.
• The difference in the absorption position of a particular proton from the
absorption position of a reference proton as a result of sheilding and desheilding
is called the chemical shift of the particular proton
• The number of absorptions( signals) in an NMR spectrum tells how many
different types of hydrogens a molecule contains.
• The amount of shielding for each NMR signal also allows us to deduce the
structural features of the molecule in the region of each of the protons.
CHEMICAL SHIFT
• Is the position of a peak in the spectrum which is as a result of
sheiding and deshielding.
• It is measured in delta scale
• It is divided on scale of part per million (ppm) 1-10 ppm
• 3. It increases from right to left
• 4. It is expressed relative to the peak due to ref solvent called
tetramethylsilane, TMS, (CH3)4Si
• In practice, a small amount of TMS is usually added to the sample so
that a standard reference absorption line is produced.
TMS AS INTERNAL STANDARD
• In TMS, the silicon shields the methyl protons more than almost any
other organic compound.
• TMS does not react with the compound under study
• TMS evaporates easily.
• All the hydrogens in TMS are equivalent so it gives only one peak.
• The position of TMS on an NMR spectrum is always assigned a value
of zero.
TERMS/ Chemical Shifts

The NMR Chart

The downfield, deshielded side is on the left, and requires a lower
field strength for resonance
The upfield, shielded side is on the right, and requires a higher
field strength for resonance
The tetramethylsilane (TMS) absorption is used as a reference point
Chemical shift of some protons
The Number of Signals in the NMR
Spectrum
• Protons in same environment are called chemically equivalent protons Eg 1-
bromopropane has three different sets of chemically equivalent protons.

• Each set of chemically equivalent protons in a compound gives rise to a

signal in the NMR spectrum of that compound.
• 1-bromopropane has 3 sets of chemically equivalent protons, it has 3 signals
in its NMR spectrum.
FACTORS THAT AFFECT CHEMICAL
SHIFT
• ELECTRONEGATIVITY
• Within a molecule, an electronegative substituent affects the
resonance of nearby protons by pulling the electrons toward itself
and decreasing the electron density around the proton( amount of
shielding felt by the protons). This electronegative pull is call
deshielding
INDUCTIVE EFFECT

• electron-withdrawing substituents will decrease the electron density

around the proton and cause less shielding. So chemical shift will
appear at a lower field.

• For electron-releasing substituents the shielding will be increased.

The proton resonances will appear at high field.
Mesomeric effect
• All the ring protons of benzene are equal, they resonate at around
7.27 ppm as a singlet.
• By attachment of a substituent to the benzene ring, the electron
density in the ring will either increase or decrease depending on the
nature of the substituents.
• For example, electron-withdrawing substituents will decrease the
electron density in the ring leading to decreased shielding.
• Electron-releasing substituents (-NH2, -OH, etc.) will increase the
electron density, and all protons will be more strongly shielded than
those in benzene.
Anisotropic effect

When an aromatic compound is placed in an external magnetic

field, the pi electrons of the ring circulate around the ring and
generate a ring current.
This ring current in turn induces a local secondary magnetic field
which leads to two current loops: one above and one below the
plane of the pi-bonds.
The induced field opposes the applied field in the middle of the ring
(above and below), but reinforces the applied field outside the ring.
Anisotropy
• This ring current generated by the pi-electrons is called the
diamagnetic ring current.
Vander waal effect
• This is observed in a rigid molecule like steroids and alkaloids.
• It is possible for a proton to occupy a sterically hindered position
• As a result the electron cloud of the hindering group will tend to repel
the electron cloud of surrounding proton
• Such proton will be deshielded and appear at higher ppm than will be
predicted in the absence of the effect
Hydrogen bonding
• This diminishes shielding in protons that participates in H- bonding
like OH and NH
• These protons tends to have variable delta value depending mainly on
sample concentration
• In non hydrogen bonded solvent H signals in ROH and NH2 move
down field as the sample is concentrated bc hydrogen bonding is
enhanced
Deuterium leveling
• This is a confirmatory test to show the presence of any acidic proton
in organic sample
• Sample containing acidic proton is treated with D2O the D exchanges
with the labile proton
• The peak previously observed with the labile proton disappeared and
a peak corresponding to D appeared at around 5.0
EXERCISE
• There are three isomeric dichlorocyclopropanes. Their
NMR spectra show one signal for isomer 1, two signals for
isomer 2, and three signals for isomer 3. Draw the
structures of isomers 1, 2, and 3.
EXERCISE
• How many signals would you expect to see in the H NMR spectrum
of each of the following compounds?
EXERCISE
• In each of the following compounds which of the underline proton
has the highest chemical shift

• In each of the following pair of compounds which of the following

underlined protons has greater chemical shift
2. Number of each kind of protons

• This is obtained from integration of each signal

• Integration Is the size or the area of peak
• 2. The area is proportional to the number of identical hydrogen atoms
• 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 methyl propane because both compounds would
show an integral ratio of 1:3
 3. Number of neighbouring protons

• It is determined from Splitting of the Signals (Multiplicity)

• Splitting is caused by protons bonded to adjacent carbons.

• The splitting of a signal is described by the n+1 rule where n is the number of
equivalent protons bonded to adjacent or neighboring carbons.
• The number of peaks in a signal is called the multiplicity of the signal and tells
about how many hydrogen atoms are attached to a neighboring carbon.
Multiplicity of the Signal and Relative Intensities of the Peaks
the Signal
SPIN-SPIN COUPLING CONSTANTS
• The spacing of line observed in the multiplicities is called the
coupling constant.
• It provides information about the position of substituents in a
molecule.
• Coupling constants give an indication of how strongly one group is
coupled to another
general rules
• (1) Chemically equivalent protons do not exhibit spin-spin splitting. The equivalent
protons may be on the same or on different carbon atoms, but their signals do not split.

• (2) Resonance lines are split by neighboring protons and the multiplicity of the split is
determined by the number of protons. The signal of a proton that has n equivalent
neighboring protons is split into a multiplet of n+1 peaks.

• (3) The relative intensities of the peaks and multiplicity can be directly determined from
Pascal's triangle.

• (4) The distances between the split lines are equal and correspond to the coupling
constant between the coupled nuclei.
• (5)Protons that are farther than two carbon atoms apart do not
usually couple

• 6)No spin-spin splitting between proton on carbon and that on hetro

atom
INSTRUMENTATION
• The basic requirements for all high-resolution NMR spectrometers are
as follows:
• (1) a magnet capable of producing a very strong static and
homogeneous field;
• (2) a stable radiofrequency generator;
• (3) a radiofrequency receiver;
• (4) a detector.
The Schematic
Nature operation
of NMR Absorptions
of a basic NMR spectrometer
Solvents for NMR
• Ideal solvent should not contain proton
• Inert
• Low boiling point
• Inexpensive
CARBON-13 NMR
• 13C is NMR active bc it has odd no of neutrons
• Both 1H and 13C are obtained from same spectrophotometer, but bc
they absorb at different frequencies proton signals do not appear on
C-13 NMR spectrum
• It is not as sensitive as 1HNMR bc of low abundance of 1.108%
• So to run 13C one require a relatively higher concn of the sample
• Information
• Position of various carbons
• Types of carbons
Chemical Shift:
• Is the position of the peak in the spectrum.
• Factors like hybridisation and change in electron density have significantly
higher effect on 13C nuclei than on 1H NMR
• So the chemical shift ranges bw 0- 250 ppm
CARBON 13
The The
Nature of NMR Absorptions
C spectrum of methyl acetate shows three peaks, one for each
13

of the three chemically distinct carbon atoms in the molecule

• TMS is also used as internal standard the methyl carbon is assign
value of 0 all other cabons are measured from it
• Integration
• The peak intensity in13C NMR does not reflect the no of carbon
nucli giving rise to the signal.
• So it is not possible to integrate C-13 signals directly
Spin- spin coupling
• Spin-spin coupling bw adjacent C-13 is not observed
• This is due to low abundance of carbon-13, the chances of getting 2
carbon-13 next to each other is practically nil, so there is no
significant multiplicity in C-13 NMR
• How ever spin- spin coupling between carbon-13 and attached
hydrogen may be observed
Advances in NMR spectroscopy
• APT and DEPT
2DNMR
Homonuclear
Heteronuclear
APT and DEPT
• Using Attached proton test (APT) and distortionless enhancement by
polarization transfer (DEPT), the carbon-13 peaks can be classified as
CH3, CH2, CH, and C.
APT(attached proton test)
• APT(attached proton test) spectra provide information about the
number of the attached protons to a C atom.
• In APT spectra, carbon atoms having an odd number of protons such
as CH and CH3 appear as negative signals.
• carbon atoms with an even number (0 or 2) of protons such as C or
CH2 appear as positive signals.
• The APT spectrum of 1-acetylcycloheptatriene is as shown .
Distortionless enhancement by polarization
transfer(DEPT)
• it is a useful method to determine the multiplicity of the carbon
atoms.
• The DEPT measurements allow 4 generation of subspectra for the CH,
CH2 and CH3 groups.
Two-Dimensional (2D) NMR
Spectroscopy
• This has simplify the interpretation of NMR spectra of very complex
molecules
• 1Homonuclear correlation spectroscopy
• (COSY) and NOESY1, one can easily obtain information concerning
the spin-coupled systems.
• 2The relation or the connectivity between protons and carbons are
determined by heteronuclear correlation spectroscopy (HSQC,
HMBC).
H-H COSY
• COSY spectrum shows cross peaks between neighbouring protons
with scalar couplings
• Homo-nuclear spectrum or homonuclear correlations
Nuclear Overhauser Effect SpectroscopY(NOESY)

• Appears in the same format as the COSY experiment –1H spectra on axes and a
diagonal

• Rather than coupling through bonds NOESY spectra show coupling through space
• Couplings are related to how close one proton is to another
• A proton that is close in space to the irradiated proton is affected by NOE whether
or not it is coupled to the irradiated protons.
• NOE operates through the bonds as well as through the space.
• NOE application determines the correct stereochemistry of the compounds
HETERONUCLEAR CORRELATION
SPECTROSCOPY
• one-bond interactions between the C and H nuclei
• 1 bond 1H-13C correlation spectroscopy

• longer range interactions.

1 bond H-C correlation spectroscopy

• Examples used are of HSQC spectra

• This experiment shows which protons are attached to which carbon

• Known as one bond H-C correlation
2 and 3 bond 1H-13C co.spectroscop

• Main experiment in this area is Heteronuclear Multi Bond Coherence

(HMBC) Spectroscopy
• HMBC spectra show correlations between protons and carbons that
are two and three bonds distant
• This is sometimes referred to as 2J and 3J correlations
• This is very useful as it allows partial fragments to be assembled
• Like HMQC it is a heteronuclear experiment with 1H spectrum on top
axis and 13C spectrum on left axis.
•
 Applications of NMR

•Structural (chemical) elucidation

•i) Natural product chemistry. •
•ii) Synthetic organic chemistry. •

•Study of dynamic processes. •

•i) Reaction kinetics. •

•ii) Study of equilibrium (chemical or structural).

•Structural (three-dimensional) studies

•i) Proteins; DNA; Polysaccharides. ii) Protein/DNA complexes.

•Drug design

•Medicine -MRI
Worked Example
Assigning a Chemical Structure from a 1H NMR Spectrum

Propose a structure for a compound, C5H12O, that fits the

following 1H NMR data:
• 0.92 d (3 H, triplet, J = 7 Hz)
• 1.20 d (6 H, singlet)
• 1.50 d (2 H, quartet, J = 7 Hz)
• 1.64 d (1H, broad singlet)
• 1. Propose a structure consistent with the following data:
• A)
• Molecular formula C9H10O
• 1HNMR data; 1.4(t, 3H), 3.95(quartet,2H) and 6.8-7.3(m, 5H)
• B)
• C5H10
• 6H, d at 0.95,
• 3H singlet at 2.1
• 1H,m at 2.43
• C. C10H14, 9H,s at 1.30, 5H singlet at 7.3

• D. C4H6Cl2
• 3H,s at 2.18
• 2H,d at 4.16 J=7Hz
• 1H,t at 5.71 J= 7Hz
• A C9H18O compound has a strong infrared absorption at 1710 cm-1. Its
1
H NMR spectrum has a single sharp peak (a singlet) at δ 1.2 ppm. Its
13
C NMR spectrum shows three lines at δ210, 45 and 25 ppm. Suggest
a structure for this compound.
MASS SPECTROMETRY(MS)
• Mass spectrometry(MS) is a technique for studying the masses of
molecules separated according to their mass to charge ratio
• Block Diagram

• 3 fundamental parts of MS are

• –ionisation source, mass analyser and the detector.

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BASIC PRINCIPLES OF ELECTRON
IMPACT MS
• The commonest MS is electron impact
• organic molecules are bombarded with high energy
electrons and converted to highly energetic positively
charged ions (molecular ions or parent ions),
• An electron is dislodged from the molecule producing
a positive molecular ion
•
• Molecular ion can break up into smaller ions
(fragment ions, or daughter ions)
• The molecular ions and the fragment ions are separated by deflection
in a magnetic field according to their mass and charge and generate a
current (the ion current) at the collector in proportion to their relative
abundances.
• The lower the mass the more easily is the ion deflected in the
magnetic field.
• A plot of relative abundance against the ratio mass/charge (the m/z
value) is called mass spectrum .
• The intensity of the peak describe the relative abundance of a
particular ion.
• The most intense peak in the MS is called the base peak and is assign
a value of 100%
• The peak formed by loss of one electron from the molecule is called
molecular ion or parent ion
• Any peaks of less mass than the molecular ion is called fragment peak
Sample Introduction
• Direct injection into the ionisation source
• Sample may undergo some type of chromatography en route to the
ionisation source
High pressure liquid chromatography (HPLC)
 Gas chromatography (GC)
 Capillary electrophoresis (CE)
Method for sample ionisation
• Ionization can be accomplished in several ways.
• The most common method is electron impact,
• This bombards the vaporized molecules with a beam of high-energy
electrons about 70 eV
• Most organic molecules form molecular ions when the energy of the
electron beam reaches 10-15 eV .
• fragmentation of the molecular ion reaches substantial proportions at 70
eV
• This technique is applicable to all volatile compounds and give
reproducible mass with fragmentation to give structural information
ALTERNATIVES TO ELECTRON-
IMPACT IONIZATION
• Chemical ionization
• This is carried out by mixing the sample with a reactant gas and
subjecting this mixture to electron bombardment.
• The reactant gas most commonly used is methane, although other
gases such as ammonia or isobutane have also been used:
• on electron impact, the methane is ionized not the sample

• The CH5+ and C2H5+ ions then react with sample molecules,
inducing them to ionize, and these ions are separated magnetically
and electrostatically in the normal way.
• In chemical ionization, the actual molecular ion is not obtained but
there exist a quassi molcular ion is observed through acceptance of
proton or abstraction of hydride
advantages of chemical ionization
• (a) more abundant peaks related to the molecular ion,
• (b) simpler fragmentation patterns
• (c) easy application of gas chromatography-mass spectrometry
interfacing, since methane can be used not only as reactant gas (in
the chemical ionization), but also as the carrier gas in the gas
chromatograph
Other soft ionization methods
• Field ionization / field desorption
• Laser ionization mass analysis (LIMA)
• Plasma desorption (PD)
• Fast atom bombardment
• Matrix assisted laser desorption ionisation (MALDI)
• Electron spray ionisation
Molecular ion
• This provides the molecular mass of the analyte and is the first clue
used to interprete MS
• The mass of the molecular ion is based on the mass of most abundant
isotopes for each element in the molecule eg molecular ion of CHBr3
is observed at M/z at 250 not the Mwt of 253

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Characteristic of Molecular ion
• It must be the ion of highest mass in the spectrum
• The m/z value must correspond to a reasonable molecular formula
with proper isotopes abundance
• It must be capable of yielding the important ions in the high mass
region of the spectrum through the loss of logical neutral species
• Most compounds have an even molecular mass, The one common
exception is the Nitrogen rule

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Nitrogen rule
• Any compound with odd number of nitrogen atoms will have an odd
molecular mass.
• Any compound with even number nitrogen atoms will have an even
number molecular mass
• This is because nitrogen is the only common atom where the most
common isotopes has an odd valence and even mass isotopes
• CH4 16, NH3 17 , N2H4 32

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Fragmentation at Functional Groups

• Characteristic fragmentation patterns are associated with specific

functional groups;
• These can help identify a substance based on its mass spectrum.
• The patterns were recognized after the mass spectra of many
compounds containing a particular functional group were studied.
Types of bond cleavages
• One bond cleavage
(1) Cleavage at Branch Points.
(2) beta- Cleavage.
3. alpha cleavage
• Two bonds cleavage
1.Retrodiel Alders
2. Mc Lafferty rearrangement
beta- Cleavage.
• Chain cleavage tends to occur ß to heteroatoms, double bonds and
aromatic rings, because relatively stable delocalised carbocations
result in each case.
• Alkenes and aromatic substituted alkyl compounds undergo benzylic
or allylic cleavage
• An allylic or benzylic cation are formed which are stablised by
resonance
α-cleavage
• All carbonyl compounds can undergo α-cleavage and the ions
abundance can be predicted on the basis of resonance stablisation
Cleavage α to heteroatoms.
• Alcohols, thiol and primary amines have similar fragmentation pattern
• The initial charge is localized on N, O or S
• Characteristic ion result from the fission of alpha or beta bond and
such ions are stablised by mesomerism
• The largest alkyl group at the alpha position is preferentially lost
• The molecular ion may eliminate H2O and H2S
 Two-bond cleavages

– Retro Diels-Alder

–McLafferty rearrangement

need g-hydrogens
FRAGMENTATIONS ASSOCIATED WITH
FUNCTIONAL GROUPS
ALKANES AND ALKANE GROUPS

• The molecular ion will normally be seen in the mass spectra of the
lower n-alkanes, but its intensity decreased with increased size and
branching of the chain.
• Group peaks spaced by 14 au apart due to loss of CH2
(1) Cleavage at Branch Points.
• Branched-chain alkanes rupture predominantly at the branching points, and the
largest group attached to the branching point is often preferentially expelled as a
radical.
• The preference is for the formation of tertiary over secondary over primary cations.
• in the mass spectrum of 2,2-dimethylpentane
• (a) no molecular ion peak,
• (b) substantial peaks for C3H7+, C4H9+
• (c) a much higher abundance of C5H11 +
• (d) a reasonable peak for C6H13+ due to M - CH3.
• peaks would be observed at m/e =85 and m/e = 57
CYCLOALKANES
• for the simple members the molecular ion peak will be
easily seen, its intensity reducing as branching
increases.
• The most significant mode of cleavage invoves the loss
of ethene from the parent molcule
• Saturated rings or cyclic hydrocarbons lose alkyl side
chain α- to the ring to form a radical and a charge will
be localised to the ring carbon leading to a base peak.
• There could also be the splitting off of the side-chains
• M/Z= 83
ALKENES AND ALKENE GROUPS

• The commonest fragmentation

in alkene groups involves rupture
of the allylic bond (beta to the double bond), which gives
rise to the resonance-stabilized allylic cation .
• Since the allylic radical is also stabilized , the fragmentation may give
rise to peaks corresponding to charge retention by either of the
fragments.
• A McLafferty rearrangement may occur, provided that the Y-carbon
has hydrogen on it
• For alkyl substituted benzene beta cleavage occur to give benzyl cat
ion which undergo rearrangement to give stable trophyllium ion at
m/z= 91

• McLafferty rearrangement is observed in alkyl benzenes provided the

side chain has hydrogen on the gamma carbon
CYCLOALKENES

• McLafferty rearrangements are common.

• In addition, cyclohexene derivatives give the important retroDiels-
Alder reaction
HALIDES
• Aliphatic fluorine compounds, apart from fragmentations appropriate
to the alkyl chain, show principally a peak at M - HF (M - 20).
• Aliphatic chlorine compounds fragment mainly by loss of HCI
• Aliphatic bromine compounds fragment similarly to chloro
compounds, but loss of Br. is the preferred fragmentation .
• Aliphatic iodine compounds show peaks corresponding to I+ (m/z
127),M- I (M - 127)
ALCOHOLS
• Molecular ion peaks for primary and secondary alcohols
are weak;
• for tertiary alcohols the M+. peak is usually absent.
• the most important fragmentation is normally rupture of
the bond beta to oxygen.
• 10 aliphatic alcohols show M - 18 peaks due to loss of
H20
• Simultaneous loss of water together with an alkene is
shown by alcohols with more than 4 carbons in the chain
• Peaks corresponding to this process appear at (M - 18 -
CnH2n)
• 20 and 30aliphatic alcohols preferentially fragment by loss of alkyl
radicals
• The ease of elimination increases with increased size and branching in
the radical.
• Aromatic alcohols with the OH group in the benzylic position
fragment so as to favour charge retention by the aryl group; thus, in
1-phenylethanol the base peak corresponds to elimination of CH3 .
• Peaks corresponding to ArCO+ and Ar+ are also shown phenyl cation
at m/z 77 loses C2H2 to give mlz 51
CARBONYL COMPOUNDS
• There are important similarities in their fragmentation modes.
• 1. a-Cleavage. This occurs in all classes; the bonds alpha to the
carbonyl group rupture, and the ion abundance can be roughly
predicted on the basis of resonance stabilization
• 2. I3-Cleavage. This often occurs with expulsion of alkyl ions from
aliphatic aldehydes.
• 3.I3-Cleavage with McLafferty rearrangement.
• This is very much more common, provided that gamma-hydrogen is
present
Aldehydes
• Principal mode of fragmentations are alpha and beta cleavages
• If C chain attached to C=O contain at least three carbon atoms
Mclafferty rearrangement is also observed
• The peak due to loss of H is very characteristics of aldehydes
Butanal
• M-1 at 71
• HCO at 29
• Beta at 29
• Mclaf at 44
Ketone
• The pattern is similar to that of aldehyde
• There is loss of alkyl group through alpha cleavage
• The larger alkyl groups are more likely to be lost
• Eg 2-butanone
• M/Z 43 due to loss of C2H5 is more intense than
peak at 57 due to loss of CH3
Esters
• The most important of the alpha cleavage involves loss of alkoxyl
group to form acylium ion
• Loss of alkyl from the acyl portion
• McLafferty rearrangement
• It preferably lost alkoxy group to form C6H5CO+ at M/z 105
• This ion loses CO to form C6H5+ at m/z= 77