Organic Spectroscopy

Prof. Basim H. Asghar

COURSE CODE: 4023561-3
INTRODUCTION Chapter
1

2
 What is the spectroscopy?

Spectroscopy is the study of interaction

of electromagnetic radiation with atoms
and molecules

3
 Spectroscopy

IR Spectroscopy UV Spectroscopy

Mass Spectroscopy NMR Spectroscopy

4
Topics to be covered:

1. Infrared spectroscopy - IR

2. Ultraviolet- Visible spectroscopy – UV-Vis

3. Nuclear magnetic resonance spectroscopy -

NMR

4. Mass spectroscopy - MS

5
 STRUCTURAL DETERMINATION
Index of Hydrogen Deficiency (IHD)
• How can we use the index of hydrogen deficiency?
• Consider an unknown species of molecular formula C7H8
• How many double bond equivalents (rings + double bonds)
are there?

IHD = [max. no. of Hs possible - actual no. of Hs]

2

 max. number of Hs = 2n+2

= 16
 actual number of Hs = 8
  IHD = [16-8] / 2
= 4
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 STRUCTURAL DETERMINATION
Index of Hydrogen Deficiency
• Unknown species of molecular formula C7H8 contains has an IHD = 4 
4 double bond equivalents (DBE)

• Possibilities:

– 1 x aromatic ring
OR
– 2 x triple bonds
OR
– 1 x triple + 2 x double bonds
OR
– various cyclic compounds
What about atoms other than carbon and hydrogen?
7
 STRUCTURAL DETERMINATION
Index of Hydrogen Deficiency – Oxygen
• The incorporation of oxygen into a molecule has no effect on the
overall number of hydrogens
•  when calculating IHD ignore the number of oxygens

• Consider the molecular formula C3H6O

• Functional group possibilities for the “O”
alcohol (ROH)
ether (R-O-R’)
carbonyl (C=O)
IHD = [(3 x 2) + 2] – 6 / 2 = 1
8
 STRUCTURAL DETERMINATION
Index of Hydrogen Deficiency – Oxygen
• Consider the molecular formula C3H6O
• IHD = 1
•  could result from:

– 1 x double bond (alcohol or ether)

– 1 x alkyl ring (alcohol or ether)

– 1 x carbonyl

9
 STRUCTURAL DETERMINATION
Index of Hydrogen Deficiency – Halogen

• A halogen occupies a similar “space” to a hydrogen

• In the calculation of IHD, count any halogen as a ‘hydrogen
equivalent’
•  in the formula for every halogen present decrease the
maximum number of expected hydrogens by 1

• Consider the molecular formula C3H5Cl

• IHD = [(3 x 2) + 2 – 1] – 5 / 2 = 1

10
 STRUCTURAL DETERMINATION
Index of Hydrogen Deficiency – Nitrogen
• Incorporation of nitrogen into a molecule increases the number of
expected hydrogens by 1
•  when calculating IHD for each nitrogen present increase the
expected number of hydrogens by 1

• Consider the molecular formula C5H14N2

• IHD = [(5 x 2) + 2 + 2] – 14 / 2 = 0

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 STRUCTURAL DETERMINATION
Index of Hydrogen Deficiency (IHD)
How to calculate IHD:

(2C + 2) – H – X + N
IHD =
2

Where:
C = number of Carbons
H = number of Hydrogens
X = number of Halogens
N = number of Nitrogens

12
 Index of Hydrogen Deficiency (IHD)

Alternatively:

IHD =

Where:
N = number of tetravalent atoms, ie. C, Si
M = number of monovalent atoms, ie. H, F, Cl, Br, I
T = number of trivalent atoms, ie, N, P

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Index of Hydrogen Deficiency (IHD)

Example 1:
C3H7NO

(2x3 + 2) – 7 + 1
IHD =
2
(8-7+1)/2
= 1

14
 Index of Hydrogen Deficiency (IHD)

Example 1:
C3H7NO

(2x3 + 2) – 7 + 1
IHD =
2
(8-7+1)/2
= 1

15
Index of Hydrogen Deficiency (IHD)

Example 2:
C7H11ClO

(2x7 + 2) – 11 – 1
IHD =
2
(16-12)/2
= 2

16
 Index of Hydrogen Deficiency (IHD)

Example 2:
C7H11ClO

(2x7 + 2) – 11 – 1
IHD =
2
(16-12)/2
= 2

17
 Index of Hydrogen Deficiency (IHD)

Example 3:
C8H6Cl2O3

(2x8 + 2) – 6 – 2
IHD =
2
(18-8)/2
= 5

18
 Index of Hydrogen Deficiency (IHD)

Remember:

Double bond = 1 p-bond (IHD = 1)

Triple bond = 2 p-bonds (IHD = 2)

Benzene ring = 3 delocalized p-bonds

and 1 ring (therefore IHD = 4)
Ring =(IHD = 1)

19
 Chapter
UV Spectroscopy
2
COURSE NAME: Organic Spectroscopy
COURSE CODE: 4023561-3
20
Ultraviolet (UV) Spectroscopy

• Measurement of interaction of molecules over the

range of UV radiation.

• Molecules absorb selected frequencies (energies)

of UV radiation.

• The energy range of the UV region corresponds to that

required to cause changes in electronic energy
within the molecule.

21
UV-Visible Spectrophotometer

22
 Ultraviolet (UV) Spectroscopy
UV radiation: l = 190-400 nm
(nanometers, where 1nm = 10-9 m)

Vis. l = 400-800 nm

UV-Vis. l = 10-800 nm

UV l = 10-200 (not important in study of organic compounds).

• Applicable only to conjugated π electrons systems:

( presence of conjugated unsaturation , and conjugation
with nonbonding electrons ).

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 Electronic Energy levels

C O C C C C

24
 Electronic Transitions

σ→ σ* l =10-190 nm
π →π*
n →π*

25
 Ultraviolet Spectrum
• On irradiation with UV light ( h ) , an electron is excited
to a higher level , therefore energy is absorbed

Io
A = log
I
A = absorbance
I0 = intensity of the incident light
I = intensity of the transmitted light

• This absorption is detected and displayed on a chart

versus wavelength ( UV Spectrum).

26
 Ultraviolet Spectrum (UV)
• The exact amount of UV light absorbed is expressed as
Molar absorptivity (ε )

A A = Absorbance
ε= C = Concentration in mol / L
C l L = Sample pathlength in cm

• The solvent must be transparent within the wavelength range

being examined.

27
 Terminology
• Chromophore: Any group of atoms that absorbs light whether
or not a color is produced.
• Auxochrome: A group which extends the conjugation of a
chromophore by sharing of nonbonding electrons.
• Bathochromic shift: The shift of absorption to a longer
wavelength.
• Hypsochromic shift: The shift of absorption to a shorter
wavelength.
• Hyperchromic effect: An increase in absorption intensity.
• Hypochromic effect: A decrease in absorption intensity .

28
 Some important definitions
Chromophore is a covalently unsaturated group responsible for
electronic transition due to light absorption e.g., C=C, C=O, N=N, …
Auxochrome: A saturated group with non-bonded electrons which when
attatched to a chromophore alter both the wavelength and the intensity of
absorption e.g., OH, NH2, and Cl
the shift of absorption
An increase in to a longer wavelength
Hyperchromic
absorption intensity due to substitution or
solvent effect

Hypsochromic Bathochromic
(Blue Shift) (Red Shift)

the shift of absorption Hypochromic

to a shorter wavelength
100 200 300 400Adecrease
500 in
due to substitution or
solvent effect absorption intensity

29
• The relationship between wavelength (λ) and frequency
(v) for a light wave is:

 =
C
l
Where C is the velocity of light (C = 3.0 x l08 m/s or
3.0 x 1010 cm/s or 3.0 x 1010 cm s-1)

30
 Example:
• Calculate frequency (v) and the period (r) of light with a
wavelength of λ = 2.0 x 105 cm.

31
 Example:
• If the period of a light wave is 2.0 x.10-17 s, what is the length
of this wave in nanometer units. (1 nm = l0-9 m = l0-7 cm).

1 1
r= then  =  =1 / 2.0 x 1017 s
 r
16 −1
= 5 x 10 s
3.0 x 1010 cm s −1 −7
l = c/= 16 −1
= 6.0 x 10 cm = 6 nm
5.0 x 10 s

32
• Light which, can be described as a wave may also be
considered as a stream of energy packets or particles
traveling with a high velocity (3x1010 cm/s). These
energy packets are called photons.

• The frequency (v) (according to the wave theory) can

be related to the energy of the photons (E); (according
to the particle theory) through Planck's equation.

E=hv
33
• Where h is the Planck's constant, a proportionality
factor whose value is 6.63 x 10-34 joule second (J s).

• The wave number, is the wave characteristic that is

proportional to energy and it is defined as the number
of waves per one centimeter.

• From the equations

c
E = h ,  =
l
34
• we can derive an equation which relates energy to
wave length

hc
E=
l

35
Example:
E = hv = hc/λ
λ = 0.05 nm = 5 x 10-9 cm, c = 3 x 1010 cm/s

6.63 x10 −34 10

Js 3.0 x10 cm
E= X
− 9
5.0 x10 cm s

E = 4.0 x 10-15 J
36
• Show that is proportional to the energy E

E = h v and v = c / λ therefore E = hc / λ

=1/λ
therefore E = hc 
hc = constant

37
 Example:
• Calculate the energy of photons, which have a wave
number of 2.5x 10-5 cm-1.

According to the equation:

E = 6.63 x 10-34 J s x 3.0 x 1010 cm s-1 x 2.5 x 10-5 cm-1

E = 5.0 x l0-28J

38
 Electromagnetic radiation (Spectrum)

• Electromagnetic radiation is divided into several regions

called cosmic rays, gamma rays, X-rays, ultraviolet (UV),
visible (Vis), infrared (IR), microwave, radar, television,
nuclear magnetic resonance, radio waves and electric
current.

• The wavelengths, frequencies and energies associated

with each of these regions are shown in figure. 1.2.

39
Figure 1.2 :The electromagnetic spectrum.
40
 Example 1:
• An atom interacts with light by absorbing an amount of
energy equivalent to a given wavelength of light. If an
atom has a spectral line at 400 nm, what energy has this
atom absorbed?

From:

E = hv and v = c/λ then E= hc/λ

1 nm = 10-7 cm = 10-9 m

41
c = 3.0 x 1010 cm s-1, h = 6.63 x 10-34 Js

λ= 400 nm = 400 x 10-7 cm

E= hc/λ
E = 6.63 x 10-34 Js x 3.0 x 1010 cm s-1 / 400 x 10-7 cm

Then:
E= 5.0 x 10-19 J

42
Figure 1.3: Energy transition for the absorption of
light or other electromagnetic radiation.
43
43
• The factor determines the wavelength of light absorbed in a
spectrum is the differences between the various energy levels in
the atom or molecule.
• Each atom or molecule has unique differences between its energy
levels.
• Wavelength is inversely proportional to transition energy.
• The longest wavelength absorption would be due to the E2 – E1
transition. Wave number is directly proportional to the transition
energy.
• The E2 – E1 transition would require light of the largest wave.

44
 Example:
• In the diagram of Figure. 1.3 assume that the
difference in energy between the E2 and E1 levels is 6
x 10-18 J. What is the wavelength of light in A needed
to accomplish this transition?

E2 – E1 = hc / λ λ = hc /ΔE
λ = 6.63 x 10-34 Js x 3.0 x 1010 cm s-1 / 6.0 x 10-18 J
Where 1 nm = 10-7 cm
λ = 33.0 nm
45
 Beer-Lambert Law
• Because light absorption is a function of the
concentration of the absorbing molecules, a more
precise way of reporting intensity of absorption is by use
of the Beer-Lambert Law:
• Absorbance = -log(P / P0) = e.c.l
where:
e = molar absorptivity
c = molar concentration of solute
l = length of sample cell (cm)

46
 Ultraviolet Spectrum
UV spectrum = plot of wavelength versus the absorption intensity

47
 Ultraviolet Spectrum
• Number of double bond can be determined
• The longer the conjugation the maximum wavelength of the absorption

48
 Ultraviolet Spectrum
• conjugated carbonyl compound can be distinguished
from non conjugated
• The longer the conjugation the maximum wavelength of the absorption

49
 Ultraviolet Spectrum
• Extent of the aromatic p system can be distinguished
• The longer the conjugation the maximum wavelength of the absorption

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Examples:

51
Examples: UV spectrum of 2-Methyl-1,3- butadiene, lmax= 222.5 nm

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53
Examples

54
55
 Empirical Rules for Calculating UV/Vis
Absorptions

• Woodward-Fieser Rules for Dienes

• Woodward's Rules for Conjugated Carbonyl Compounds
• Mono-Substituted Benzene Derivatives

56
 Woodward-Fieser Rules for Diene
Homoannular Heteroannular
(cisoid) (transoid)
l = 214 nm
Parent l = 253 nm
= 217 (acyclic)
Double bond
Increments
extending 30 30
for:
conjugation
Alkyl substituent
5 5
or ring residue
Exocyclic double
5 5
bond
Polar
-OC(O)CH3 0 0
groupings:
-OR 6 6
-Cl, -Br 5 5
-NR2 60 60
57
Application of Woodward-Fieser Rules
for Dienes

58
 Woodward's Rules for Conjugated Enones

Base
6-membered ring or acyclic
values: l = 215 nm
enone

5-membered ring parent

l = 202 nm
enone
Acyclic dienone l = 245 nm

Increments
Double-bond-extending 30
for:
conjugation
Alkyl substituent
a 10
or ring residue
b 12
g or higher 18
59
Woodward's Rules for Conjugated Enones - continue
Polar groupings: -OH a 35
b 30
d 50
-OCOCH3 a,b,g,d 6
-OCH3 a 35
b 30
g 17
d 31
-Cl a 15
b,g,d 12
-Br b 30
a,g,d 25

-NR2 b 95
Exocyclic double bond 5
Homocyclic double bond 39
60
Application of Woodward's Rules for
Conjugated Enones
Example 1: Example 2:

61
Application of Woodward's Rules for
Conjugated Enones
Example 3: Example 4:

62
Application of Woodward's Rules for
Conjugated Enones
Example 5:

63
Application of Woodward's Rules for
Conjugated Enones
Example 6:

Example 7:

64
Empirical Rules For Unsaturated Aldehydes

65
Empirical Rules For Unsaturated Acids and
Esters

66
Absorption for Mono-Substituted
Benzene Derivatives

67
 Chapter
IR Spectroscopy
3
COURSE NAME: Organic Spectroscopy
COURSE CODE: 4023561-3
68
 Spectroscopy and the
Electromagnetic Spectrum
Frequency,  in Hz
~1019 ~1017 ~1015 ~1013 ~1010 ~105

Wavelength, l
~.0001 nm ~0.01 nm 10 nm 1000 nm 0.01 cm 100 m

Energy (kcal/mol)
> 300 300-30 300-30 ~10-4 ~10-6

g-rays X-rays UV IR Microwave Radio

nuclear core electronic molecular molecular Nuclear Magnetic
excitation electron excitation vibration rotation Resonance NMR
(PET) excitation (p to p*) (MRI)
(X-ray
cryst.)

Visible
69
 Energy considerations
• Energy of a photon of light is given by Planck-Einstein:
• E=h=hc/l
E : energy of photon
h : Plank’s constant (4 x 10-13 kj / mol)
c : speed of light 3 x 1010 cm / s
 : frequency of light (s-1)
l : wavelength of light (cm)

 Energy involved: IR ~ 1 to 10; UV ~ 80 to 140 kcal mol-1

 Hence energy gained by molecules may bring about increased
vibration (IR) or raise electrons to higher energy

70
 Basic Theory of Absorption

• Infrared: exciting from one vibrational level to another.

• UV/Vis: exciting from one electronic level to another.

• Microwaves: exciting from one rotational level to another.

71
The IR Spectrophotometer

72
 IR Spectroscopy
• In IR spectroscopy, there is interaction between molecules
and radiations from the IR region of the EMR spectrum (IR
region = 4000 - 400 cm-1)
• IR radiation causes the excitation of the vibrations of covalent
bonds within that molecule. These vibrations include the
stretching and bending modes
• In practice, it is the polar covalent bonds that are IR "active"
and whose excitation can be observed in an IR spectrum
• Generally, it is convenient to split an IR spectrum into two
approximate regions:
▪ Functional group region: 4000-1000 cm-1
▪ Fingerprint region: < 1000 cm-1 (more complex and much
harder to assign).

73
 Basic Theory of IR Absorption
◼ We need to talk about
 IR energy modes (Types of vibration in molecules)
 Band positions
 Band Intensity

74
 Infrared Energy Modes
• IR energy absorption corresponds to specific modes,
corresponding to combinations of atomic movements,
such as bending (change in bond angle) and stretching
(change in bond length) of bonds between groups of
atoms
• Energy is characteristic of the atoms in the group and their
bonding
• Corresponds to vibrations and rotations

75
 Bands Position: Hookes' Law
• A vibrating bond In IR can be compared to the physical
model of a vibrating spring system that can be described by
Hooke's Law of harmonic oscillation.

• Using the force constant k (which reflects the stiffness of

the spring) and the two masses m1 and m2, then the
equation indicates how the frequency, u, of the absorption
should change as the properties of the system change.

76
 Bands Position: Hookes' Law
• Hooke’s Law can be used to estimate the wavenumber () of
light that will be absorbed by chemical bonds
•  = 4.12 * (K / m)1/2
K is the force constant (in dynes / cm) and for:
single bond: K = 5 x 105 dynes/cm
double bond: K = 10 x 105 dynes/cm
triple bond: K = 15 x 105 dynes/cm
• m = reduced mass
• For example in C=C bond:
 = 4.12 * (10 x 105 / [12 * 12 / (12 + 12)])1/2 = 1682 cm-1
(calculated) compare to experimental value1650 cm-1

77
 Factors affecting Absorption
Frequency
• Strength of chemical bond
• Masses of attached atoms to the bond
• Hydrogen bonding
• Resonance
• Bond angle or ring strain
• Hybridization
• Polarity of bonds
• External factors: eg. state of measurements, conc., temp., solvent
used etc.

78
 Factors Affecting Absorption
Frequency: Bond Strength
• For a stronger bond (larger k value), u increases Compare
(increasing bond strength) :
– CC bonds : C-C (1000 cm-1),C=C (1600 cm-1) and CC(2200 cm-1)
– CH bonds: C-C-H (2900 cm-1), C=C-H (3100 cm-1) and CC-H
(3300 cm-1)
• Strength of the chemical bond:
1 k
 (cm −1 ) =
2pc m

m1m2
m=
m1 + m2

79
 Factors Affecting Absorption
Frequency: Masses of Atoms
• Masses of the attached atoms to the bond
• For heavier atoms (larger m value), u decreases compare
(increasing reduced mass):
– C-H (3000 cm-1)
– C-C (1000 cm-1)
– C-Cl (800 cm-1)
– C-Br (550 cm-1)
– C-I (500 cm-1) R F R Cl R Br


m1m2
 (cm ) =
−1 1 k
m=
2pc m m1 + m2

80
 Factors Affecting Absorption
Frequency: Hydrogen Bonding
• H-bonding
• For example: free −OH is observed at 3600cm-1 while H-bonded –
OH is observed at 3400cm-1

81
Factors Affecting Absorption Frequency:
Resonance
◼ Resonance: electronic factors
◼ Conjugation lowers the energy to vibrate bond
◼ isolated ketones: 1710 cm-1
◼ a,b-unsaturated ketones: 1690 cm-1
◼ a,b,g,d-unsaturated ketones: 1675 cm-1

82
Factors Affecting Absorption Frequency:
Bond Strain
• Internal factors: Bond angle or ring strain

83
Factors Affecting Absorption Frequency:
Hybridization
• Hybridization:

• Bonds are stronger in the order sp > sp2 > sp3

• C-H (sp): 3300 cm-1

• C-H (sp2): 3100 cm-1

• C-H (sp3): 2900 cm-1

84
 Factors Affecting Absorption
Frequency: Polarity of Bond
• The more polar a chemical bond is, the higher the intensity of the
band.
• Low dipole moments results in a weak bands.

85
 Band intensity
▪ Symmetrical bonds have no dipole moments and thus no IR bands
observed in the spectrum (ie. infrared inactive)

▪ Band intinsity is qualitatively described as: very strong (vs),

strong (s), medium (m), weak (w) and variable (var).

86
 Regions of the Infrared Spectrum
• 4000-2500 cm-1 N-H, C-H, • 2000-1500 cm-1 double
O-H (stretching) bonds (stretching)
3300-3600 N-H, O-H C=O 1680-1750
3000 C-H C=C 1640-1680 cm-1
• 2500-2000 cm-1 CC • Below 1500 cm-1
and C  N (stretching) “fingerprint” region

87
Regions of the Infrared Spectrum

88
Regions of the Infrared Spectrum

89
 Differences in Infrared Absorptions
• Molecules vibrate and rotate in normal modes, which are
combinations of motions (relates to force constants)

• Bond stretching dominates higher energy modes

• Light objects connected to heavy objects vibrate fastest: C-H,

N-H, O-H

• For two heavy atoms, stronger bond requires more energy: C 

C, C  N > C=C, C=O, C=N > C-C, C-O, C-N, C-halogen.

90
Infra-red Spectra of Hydrocarbons

91
 Infrared Spectra of Some Common
• n-Alkanes
Functional Groups
- look for stretching and bending of C–H and C–C bonds
• C–C bends: ca. 500 cm–1 (out of spectral window)
• C–C stretches: 1200–800 cm–1, weak bands not of
value for interpretation (fingerprint)
More characteristic
• C–H stretches: occurs from 3000 - 2840 cm–1
CH3: 2962 cm–1, asymmetrical stretch
2872 cm–1, symmetrical stretch
CH2: 2926 cm–1, asymmetrical stretch
2853 cm–1, symmetrical stretch
• C–H bends:
CH3: ca. 1375 cm–1
CH2: ca. 1465 cm–1
92
 n-Alkanes
• n-Hexane CH3(CH2)4CH3

C-H
Bends
C-H
Stretches
CH3 (s)

CH3 (as)
CH3 (as) CH3 (s)

93
 Finger printing

The IR of
C10H22
C10H22 and
C12H26
are
Similar
but Not
Identical

C12H26

94
 Unconjugated Alkenes
• Linear alkenes:
▪ C=C–H stretch: ≥ 3000 cm-1
▪ C=C–H bending in the range 1000-650 cm-1
▪ C=C stretch: moderate to weak at 1680-1600 cm-1

95
 Unconjugated Alkenes
• Example: 1-Hexene

96
 Cyclic Alkenes
• The C=C stretch is sensitive to ring strain (size)

97
 Conjugated alkenes
• often conjugation moves C=C stretch to lower frequencies and
increases the intensity
• The alkene bond stretching vibrations in alkenes without a center
of symmetry, e.g. 1-methylbutadiene, gives to two C=C stretches
• For symmetrical molecules, e.g. butadiene, only the asymmetric
stretch is observed

Me
–1
1650 cm (as) 1600 cm –1 (as)
1600 cm –1 (s)

98
 Conjugated alkenes
• 2-methylbutadiene

Symmetrical
C=C stretch
C-H stretch 1640 cm–1 Out of plane
3090 cm–1 (weak) C=C–H bends
Asymmetrical
C=C stretch
1598 cm–1 (strong) 990, 892 cm–1

99
 Alkynes
• C C-H bend: 700-610 cm-1: broad, strong
• C C-H stretch: 3333–3267 cm-1, strong and narrow (as
compared to OH or NH)

• C C stretch: weak absorption at 2260-2100 cm-1

▪ not observed for symmetrical alkynes
▪ terminal alkynes (R-C C-H) absorptions are stronger than
internal (R-C C-R) absorptions
▪ Disubstituted or symmetrically substituted triple bonds
give either no absorption or weak absorption

100
 Terminal Alkynes
• Example: 1-octyne

Alkyne
CC stretch
Alkyne
2119 cm–1
C-H bend overtone
1260 cm–1

Alkyne
C-H stretch
Alkyne
3310 cm–1
C-H bend
630 cm–1

101
 Aromatic Rings
• C=C-H stretch occurs at value 3100-3000 cm-1
• C=C-H out of plane bending occurs at 900–690 cm-1
▪ intense bands, strongly coupled to adjacent hydrogens on the
ring
▪ position and number of bands gives information about the
ring substitution pattern
• C=C stretch occurs in pairs: 1600-1585; 1500-1400 cm-1
• C=C out of plane ring bending: 600-420 cm-1

102
 Aromatic rings
• Example: Toluene

Overtone bands
2000-1650 cm–1

Aromatic
C-H Stretches Aromatic C-H in plane bends out of
3087, 3062, 1300-1000 cm–1 plane
3026 cm–1 ring
bending
Aromatic
428 cm–1
C-H out of
Plane bends
Aromatic C-C Stretches
728 cm–1
1600-1585; 1500-1400 cm–1
694 cm-1

103
 Alcohols and phenols
• The value is strongly dependent on hydrogen-bonding
▪ Free non-hydrogen bonded
OH
O-H groups absorb strongly in not H-bonded
even when 'neat'
the 3700-3600 cm-1 range too hindered

▪ H-bonded O-H band is broad at 3400-3300 cm-1

• C-O-H bending appears at 1440-1220 cm-1 as broad and weak
peak often obscured by CH3 bending
• C-O (alcohol) stretching at 1260-1000 cm-1. Used to assign
primary secondary and tertiary alcohols)
• C-O (phenol) stretching at 1800-1260 cm-1

104
 C–O stretching Vibrations of Alcohols
• Primary alcohol: 1050-1085 cm-1
• Secondary alcohol: 1085-1125 cm-1
• Tertiary alcohol: 1125-1200 cm-1

OH
1073 cm-1

OH 1110 cm–1

OH
1202 cm–1

105
 Ethers
• C–O–C stretching bands are very prominent (1300-1000 cm-1) due to
strong dipole moment. C=O and O-H must be absent to ensure C-O
stretch is not due to ester or alcohol
• aliphatic ethers:
– strong band due to asymmetrical stretching, 1150-1085 cm-1
(usually 1125 cm-1)
– weak band due to symmetrical stretching (lower freq)
• Alkyl aryl ethers:
– asymmetrical stretch at 1275-1200 cm-1/9
– symmetrical stretch at 1075-1020 cm-1
• Vinyl alkyl ethers:
– asymmetrical stretch at 1225-1200 cm-1
– symmetrical stretch at 1075-1020 cm-1

106
 C=O In Aldehydes
• C=O stretch appears at 1740-1725 cm−1 for normal aliphatic
aldehydes
• Conjugation of C=O with a,b C=C: 1700-1680 cm−1 for C=O and
1640 cm−1 for C=C
• Conjugation of C=O with phenyl: 1700-1660 cm−1 for C=O and
1600-1450 cm−1 for the ring
• C-H stretch of aldehyde H ( in CHO): show pair of weak bands at
2860-2800 cm−1 and 2760-2700 cm−1

107
 C=O in Ketones
• C=O stretch: 1720-1708 for aliphatic ketones
• Conjugation of C=O with a,b C=C: 1700-1675 cm-1 for C=O and
1644-1617 cm−1 for C=C
• Conjugation of C=O with phenyl: 1700-1680 cm-1 for C=O and
1600-1450 cm-1 for the ring
• In strained rings, interaction with the adjacent C-C bonds increases
the frequency of C=O stretching

108
 C=O in Ketones
• 2-Heptanone

109
 C=O in Carboxylic Acids

O-H stretch usually very broad (H-bonding) occurs at 3400-2400

cm−1 and often overlaps the C-H absorptions

C=O stretch, strong broad, occurs at 1730-1700 cm−1

C-O stretch occurs in the range 1320-1210 cm−1 in medium intensity

110
 C=O in Carboxylic Acids

Hexanoic acid •

111
 C=O in Esters
◼ C=O stretch appears in range 1750-1735 for normal
aliphatic esters
◼ Conjugation of C=O with a,b C=C: 1740-1715 cm−1 for
C=O and 1640-1625 cm−1 for C=C
◼ Conjugation of C=O with phenyl: 1740-1715 cm−1 for C=O
and 1600-1450 cm−1 for the ring
◼ C-O stretch in two or more bands, one stronger and
broader than the other, occurs at 1300-1000 cm−1

112
 O
C=O in Esters O

1763 cm–1

1199, 1164, 1145 cm–1 C–O

113
 C=O in Amides
• C=O stretch appears in range 1680-1630 cm−1

• N-H stretch in primary amides (NH2) gives two bands near 3350
and 3180 cm−1. Secondary amides have one band ca. 3300 cm−1

• N-H bending occurs at ca. 1640-1550 cm−1 for primary and

secondary amides

O
O O
NH
NH NH

114
 C=O in Amides
O
H
Et N
H
1662 cm-1

O
CH3
H3C N
H 1565 cm-1 (II)
1655 cm-1 (I)

115
 Acid Chlorides
▪ C=O stretch appears in range 1810-1775 cm−1 in unconjugated
chlorides. Conjugation lowers the frequency to 1780-1760 cm−1

▪ C-Cl stretch occurs in the range 730-550 cm−1

116
 Alkyl Halides
• C-F: Stretch (strong) at 1400-1000 cm-1

• C-Cl: Stretch (strong) in aliphatic chlorides at 785-540 cm-1

• C-Br: Stretch (strong) in aliphatic bromides at 650-510 cm-1. Aryl

bromides absorb between 1075 and 1030 cm-1

• C-I: Stretch (strong) in aliphatic iodides at 600-485 cm-1

• CH2-X bending at 1300 -1150 cm-1

117
 Anhydrides
• C=O stretch always has two bands at 1830-1800 cm−1 and

• 1775-1740 cm−1 with variable relative intensities

• C-O stretch (multiple bands) occurs in the range 1300-900 cm−1

O O
O O O O O
O
alkyl O alkyl
R R
1818; 1750 cm –1 1775; 1720 cm –1
1865; 1782 cm –1

118
 Amines
• N-H stretch ca. 3500-3300 cm-1
• Primary amine have two bands, secondary amines have one band
while tertiary amines have no N-H stretch
• N-H bend in primary amines results in a broad band ca. 1640-1560
cm-1. Secondary amines absorbs near 1500 cm-1
• C-N stretch occurs near 1350-1000 cm-1

119
 Amines
• Example: Propylamine

120
 Others
• Nitrile: C N medium intensity, sharp absorption at 2250 cm−1

• Imine -C=N- at ca. 1690 -1640 cm-1

• Aliphatic nitro compounds: strong asymmetrical stretch at 1600-

1530(s) cm-1 and medium symmetrical stretch 1390 -1300(s) cm-1

• Aromatic nitro compounds: strong asymmetrical stretch at 1550-

1490(s) cm-1 and strong symmetrical stretch 1355 -1315(s) cm-1

121
Analysis of IR spectrum: What To Do!
• Look if a C=O group is present (1820-1660 cm-1)
• If present look for:
– Is O-H also present? (3400-2400 cm-1): acid
– Is N-H also present? (ca. 3400 cm-1): amide
– Is C-O also present? (1300-1000 cm-1): Ester
– Two C=O present? (1810-1760 cm-1): anhydride
– Is aldehyde C-H present? (2840 & 2720 cm-1): aldehyde
– If all of the above absent, then think of ketone!
• If C=O is absent:
– Is O-H (3400-3300 cm-1) and C-O (1300-1000 cm-1) present?
Alcohol C-O-H
– Is N-H (~3400 cm-1) present? amine
– Is C-O (1300-1000 cm-1) present? ether
122
 Analysis of IR spectrum: Remember..
• Double bonds/aromatic rings:
– C=C (~1650 cm-1)
– aromatic C=C (1600-1450 cm-1)
– vinyl C-H (>3000 cm-1)
• Triple bonds
– C,N triple bond (~2250 cm-1)
– C,C triple bond (~2150 cm-1)
– acetylenic C-H (~3300 cm-1)
• Nitro groups
– N-O(1600-1530 & 1390-1300 cm-1)
• Hydrocarbons

123
 Remember…..
• The C-H absorption(s) 3100 - 2850 cm-1
• Absorption above 3000 cm-1 indicates C=C, either alkene or
aromatic
• Confirm the aromatic ring by finding peaks at 1600 and 1500 cm-1
and C-H out-of-plane bending to give substitution patterns below
900 cm-1
• Confirm alkenes with an absorption at 1640-1680 cm-1
• C-H absorption between 3000 and 2850 cm-1 is due to aliphatic
hydrogens
• If the main absorptions are approximately 2935 and 2860 cm-1 and
there are also absorptions at 1470 and 720 cm-1 then the
compound probably contains a long linear aliphatic chain

124
 Remember…..
• Hydroxy or Amino groups appear at 3650–3250 cm-1 while the C-H
stretch of a terminal alkyne (acetylene) exhibits a relatively narrow
absorption at 3300 cm-1 .
• If the main absorption band in the area is broad, the compound
probably contain a hydroxyl or amino group. For -NH2 a doublet will
be observed.
• The C-O absorption between 1080 and 1300 cm-1. These peaks are
normally rounded like the O-H and N-H peak and are prominent.
Carboxylic acids, esters, ethers, alcohols and anhydrides all
containing this peak.
• A methyl group may be identified with C-H absorption at 1380 cm-1.
This band is split into a doublet for isopropyl(gem-dimethyl) groups

125
 NMR Spectroscopy Chapter
4
COURSE NAME: Organic Spectroscopy
COURSE CODE: 4023561-3
126
Nuclear Magnetic Resonance (NMR) Spectroscopy

Background
◼ Most helpful spectroscopic technique in organic chemistry

◼ Maps carbon-hydrogen framework of molecules

◼ Used to determine relative location of atoms within a

molecule

◼ NMR spectroscopy detect specific ISOTOPES, such as

protons or 13C nuclei

127
 Nuclear Spin
◼ Example: each 1H (proton) can assume 2 possible
orientations corresponding to 2 energy levels under the
action of an external applied magnetic field B0:

128
 The NMR phenomena is not observed in the absence of
an applied magnetic field, a magnet plays as heart of any
NMR instrument.

Types of magnets:
1. Permanent magnets (as in many low field instruments).
2. Electromagnet.
3. Superconducting.

129
130
 NMR: Reference Material
◼ A small amount of a reference material may be added
◼ The usual choice is tetramethylsilane (TMS) (CH3)4Si
◼ It is chosen because:
 It is non-reactive

 It is extremely volatile

 It gives a single signal, usually at one end of a spectrum

◼ The reference is calibrated as 0.00 ppm

131
 The Shielding
◼ Protons are shielded by valence electrons surrounding and
circulating around them
◼ The electrons moving around the nuclei produce tiny local
magnetic field in the opposite direction to the applied external
magnetic filed. This effect is called diamagnetic shielding or
diamagnetic anisotropy

132
 Key Information Obtained From NMR
◼ Key information obtainable:

1) Chemical Shifts Provides information on the chemical

environment of nuclei

2) Chemical Provide the number of different types of

equivalence protons in a compound

3) Integration (area Provide information on the number of

under resonance protons in a particular chemical
band) environment
4) Spin-couplings Provide information on number of
neighboring protons

133
 Chemical Shifts
◼ Chemical shift: The relative energy of resonance of a nucleus
resulting from its local environment
◼ NMR spectra show applied field strength increasing from left
to right. Left part is downfield and right part is upfield
◼ Nuclei that absorb on upfield side are strongly shielded
◼ Chart calibrated versus a reference TMS, set as 0.00

134
 Factors Influencing Chemical Shifts
◼ Proton signals range from d 0 to d 15.
◼ Different types of proton will occur at different chemical
shifts.
◼ The magnetic field experienced by a proton is influenced by
various structural factors.
◼ Factors:
1. Electronegativity effects
2. Hybridization effects (sp3, sp2, sp)
3. Hydrogen bonding effects
4. Magnetic anisotropy effects

135
 Factors Influencing Chemical Shifts -
Electronegativity Effects
◼ Electronegative atoms pull electron density away from the
protons making them "deshielded“ & cause downfield shift

Compound CH3X CH3H CH3I CH3Br CH3Cl CH3F

Element X H I Br Cl F
Electronegativity of X 2.1 2.5 2.8 3.1 4.0
Chemical Shift d 0.23 2.16 2.68 3.05 4.26

Compound CH4 CH3Cl CH2Cl2 CHCl3

d / ppm 0.23 3.05 5.30 7.27

136
 Factors Influencing Chemical Shifts -
Hybridization Effects
◼ H’s attached to sp3 C resonate 0 – 2.5 ppm
◼ H’s attached to sp2 C
 Vinylic Hydrogens 4.5 – 6.5 ppm

 Aromatic Hydrogens 6.5 - 8 ppm

◼ H’s attached to sp C resonate between 2 - 3 ppm

137
 Factors Influencing Chemical Shifts -
Hydrogen Bonding Effects
◼ Protons involved in H-bonding (-OH or -NH) are observed
over a large range of chemical shift values (d 0.5 - 5 ppm)
since H-bonding effects are solvation, acidity, concentration
and temperature dependent

138
 Factors Influencing Chemical Shifts -
Magnetic Anisotropy Effects
◼ Magnetic anisotropy: "non-uniform magnetic field”
◼ Electrons in p systems (e.g. aromatics, alkenes, alkynes,
carbonyls etc.) interact with the B0 which induces a magnetic
field that causes the anisotropy.
◼ As a result, the nearby protons will experience 3 fields: the
applied field, the shielding field of the valence electrons and
the field due to the p system.
◼ Depending on the position of the proton in this third field, it
can be either shielded (smaller d) or deshielded (larger d).

139
 Factors Influencing Chemical Shifts -
Magnetic Anisotropy Effects
◼ In aromatic rings: The "ring current" generates a local magnetic field
which opposes B0.
◼ However, on the periphery of the ring, the flux lines are in the
direction of B0.
◼ Thus, protons attached to the aromatic ring "feel" a larger magnetic
field than protons elsewhere in the molecule.
◼ Aromatic protons will exhibit a downfield shift (7 - 8 ppm).

( + ) = shielding; ( - ) = deshielding

140
 Factors Influencing Chemical Shifts -
Magnetic Anisotropy Effects
◼ The p electrons in a triple bond circulate around the bond axis to
produce a magnetic field directly opposing the applied magnetic
field.
◼ The acetylenic hydrogen is shielded by this induced field, and
will therefore resonate at lower frequency (2 -3 ppm).

( + ) = shielding; ( - ) = deshielding
141
 Chemical Shifts in 1H NMR
◼ Typical d /ppm values for protons in different chemical
environments are shown below:

142
 Chemical Equivalence
◼ NMR spectrum will tell us the number of different types of
protons in the compound
◼ Protons found in chemically identical environments are
chemically, and usually also magnetically, equivalent
◼ These equivalent protons will resonate at the same chemical
shift

143
 Nonequivalent H’s
◼ Replacement of each H with “X” gives a different constitutional
isomer.
◼ Then the H’s are in constitutionally heterotopic environments
and will have different chemical shifts – they are nonequivalent
under all circumstances.

144
 Equivalent H’s
◼ Two H’s that are in identical environments (homotopic) have
the same NMR signal

◼ Test by replacing each with X

 if they give the identical result, they are equivalent.

145
 Molecules With One Type of Protons

◼ Look at elements of symmetry within the structure.

◼ Since there is only one type of protons in each of the

structures below, the protons will all resonate at the same
frequency and will give only one signal (singlet)

146
 Integration of 1H NMR Absorptions:
Proton Counting
◼ The relative intensity of a signal (integrated area) is proportional
to the number of protons causing the signal
◼ For narrow peaks, the heights are the same as the areas and can
be measured with a ruler
◼ Example: in methyl 2,2-dimethylpropanoate integral ratio is 3:9
or 1:3

147
 Integration of 1H NMR Absorptions:
Proton Counting
◼ Integration is used to deduce the structure. The area under the
peaks gives a ratio of the number of H for each signal.
◼ Measure the height of each trace and derive a whole number ratio

148
 Spin-Spin Splitting in 1H NMR Spectra
◼ Peaks are often split into multiple peaks due to interactions
between nonequivalent protons on adjacent carbons, called
spin-spin splitting (multiplicity or coupling pattern).

◼ Simple coupling patterns (obey the n+1 rule, see later).

 protons are only coupled to one other set of neighboring

protons or, protons are coupled to multiple sets of

neighboring protons by identical coupling constants.

◼ If the neighbors are not all equivalent, more complex patterns

arise.

149
 The n+1 rule
◼ The signal resulting from a group of chemically equivalent
protons that has n equivalent neighbors, will be split into n+1
peaks.

◼ A neighbor is defined as any proton on a neighboring atom.

150
Spin-Spin Splitting: Simple
◼ Example: 1,1-dichloroethane

151
 Coupling 1
in H NMR Spectra
◼ Coupling arises because the magnetic field of vicinal protons
influences the field that the proton experiences
◼ Consider: effect of -CH group on the adjacent -CH3
◼ The methine -CH can adopt two alignments and as a result,
the signal for the adjacent methyl -CH3 is split in two lines,
of equal intensity, a doublet

152
 Coupling in 1H NMR Spectra
◼ Consider: effect of -CH3 group on the adjacent -CH
◼ The methyl -CH3 protons give rise to 8 possible combinations
with respect to the applied field
◼ Some combinations are equivalent and there are four
magnetically different effects.
◼ As a result, the signal for the adjacent methine -CH is split
into four lines, of intensity ratio 1:3:3:1, a quartet

153
 Simple Spin-Spin Splitting
◼ An adjacent CH3 group can have four different
spin alignments as 1:3:3:1.
◼ This gives peaks in ratio of the adjacent H
signal.
◼ An adjacent CH2 gives a ratio of 1:2:1.
◼ The separation of peaks in a multiplet is
measured is a constant, in Hz.
 J (coupling constant)

154
 Spin-Spin Splitting Patterns
◼ The relative intensities, given by Pascal's triangle, are due to
interactions between nuclear spins that can have two possible
alignments with respect to the magnetic field.
◼ To derive Pascal's triangle, start at the apex, and generate each
lower row by creating each number by adding the two numbers
above and to either side in the row above together.

155
1H NMR spectrum of 1-methyl-4-nitrobenzene, 4-CH3C6H4NO2

156
1H NMR spectrum of 1,3-dihromopropane.
BrCH2CH2CH2Br
157
 Coupling Constant
◼ For the peaks of bromoethane, the coupling constant J = 7.0 Hz
◼ J calculation: take the distance (in ppm) between any two
adjacent split peaks and multiply it by the frequency of the
NMR machine.

158
 Example
◼ How to distinguish between A and B?

159
 Basics of Nuclear Coupling
◼ Coupling between two nuclei can be:
1
 Homonuclear: between same nuclei (e.g. H-C-C- H)
1
1 13
 Heteronuclear: between different nuclei (e.g. H- C)

◼ Factors affecting spin-spin couplings : the nuclei involved,

the distance between the two nuclei, the angle of interaction

between the two nuclei, and the nuclear spin of the nuclei
◼ Distance Dependence

one-bond (1J) > two-bond > (2J) three-bond (3J) > long-range (4J - nJ)

110 - 270 Hz 9 - 15 Hz 6 - 8 Hz 1 - 7 Hz

160
 Basics of Nuclear Coupling
◼ Geminal coupling or two-bond coupling (2J).

 Dependent upon the bond angle between the nuclei

Generally, the smaller the angle the bigger the coupling
constant

161
 Basics of Nuclear Coupling
◼ Vicinal coupling or three-bond coupling (3J).

 Dependent upon the dihedral angle between the nuclei.

Generally, the more eclipsed or antiperiplanar the nuclei

the greater the coupling constant

162
13C NMR Spectroscopy: Background
◼ Like 1H, 13C has I = ½.
◼ For 12C, I = 0, no NMR signal observed
◼
13C has only about 1.1% natural abundance. As a result, C is

about 400 times less sensitive than H nucleus to the NMR

phenomena
◼ 13C resonances are 0 to 220 ppm downfield from TMS

◼ Similar factors affect the chemical shifts in 13C as seen for

1H NMR

◼ Long relaxation times (excited state to ground state) mean

no integrations.

163
Characteristics of 13C NMR Spectroscopy
◼ Provides a count of the different types of environments of
carbon atoms in a molecule
◼ Number of peaks indicates the number of types of C
◼ Spectrum of 2-butanone is illustrative: signal for C=O
carbons on left edge

164
 Proton-Coupled 13C Spectra
◼ Due to low natural abundance of 13C (1.1%), any 13C is
unlikely to have another 13C nucleus as a neighbour in natural
material. Therefore:
 we do not usually see
13C-13C coupling in “normal” 13C

spectra

13C–1H couplings are observed in “normal” 13C spectra

unless the interactions are “decoupled”

 As a result H’s split the carbon peaks into multiplets

165
 Proton-Broad Band Decoupled 13C Spectra
◼ 13C Broad Band Decoupled (BBD) spectra are normally obtained as
proton-decoupled spectra to remove all interaction between 13C
nuclei and protons
◼ In the proton-decoupled spectra, each carbon atom gives a singlet
◼ Proton-decoupled spectra are much easier to interpret but it dose not
indicate the number of hydrogen atoms attached to each carbon
atom
◼ From BBD spectrum you know:
 number of chemically non-equivalent carbons, and

 chemical shift (environment of each type of carbon)

166
 How would you determine the nature of
the carbon?
◼ The good news is (as you know): both 13C and 1H have nuclear
spin quantum numbers I = 1/2
 Therefore: coupling (and J) can be observe between
13C and 1H

◼ Spin-spin splitting between 13C and 1H follows the same rules as

1H–1H splitting

◼ The n+1 Rule can be applied:

singlet doublet triplet quartet

167
Proton-Coupled Viz Proton-Decoupled
13C Spectra
◼ Example: ethyl phenylacetate

168
13C NMR Chemical Shifts
◼ Similar factors affect (electronegativity, hybridization,
anisotropy) the chemical shifts in 13C as seen for 1H NMR
◼ Since C is more electronegative than H, A 13C atom linked to
more C atoms and therefore fewer 1H atoms will be deshielded
& is at a lower field (i.e. higher d value)

a) Saturated C 8 - 60 ppm
b) C attached to electronegative atoms 40 - 70 ppm
c) Alkene/ aromatic C 100-150 ppm
d) Carbonyl carbons 155-220 ppm

169
Simplified 13C Correlation Charts

170
SOME SAMPLE SPECTRA-EQUIVALENT CARBONS

• Consider the proton-decoupled carbon spectrum for 2,2-

dimethylbutane. Although this compound has a total of six
carbons, there are only four peaks in the 13C NMR spectrum.

171
172
13CNMR spectrum of cyclohexanol shows only
four carbon resonances

173
In the l3C NMR spectrum of cyclohexene, we
observe only three absorption peaks.

174
In the l3C NMR spectrum of toluene, shows five
signals.

175
• Depending on the mode of substitution, a symmetrically

disubstituted benzene ring can show two, three, or four

peaks in the proton-decoupled 13C spectrum. The following

drawings illustrate this for the isomers of dichlorobenzene.

176
 Chapter
Mass Spectrometry
5
COURSE NAME: Organic Spectroscopy
COURSE CODE: 4023561-3
177
178
 Mass Spectroscopy
▪ Effectively measures the mass of a compound and its
fragment ions.

▪ Allows determination of molecular weight and molecular

formula and the presence of certain structural features.

▪ Performed using a mass spectrometer

▪ trace/recording is mass spectrum

▪ Ordinary mass spectra tell us the molecular weight of

the molecule (MW) .

179
➢ Applications
A- To measure the molecular weights with very high
accuracy.
B- To detect the places of preferable fragmentation; to deduce
the presence of recognizable groupings within the molecule.
C- To investigate the isotope abundance (isotope effect).

Mass Spectrometry is based on a single principle: it’s possible to

determine the mass of an ion in the gas phase
Mass Spectrum: consist of a plot of relative abundance against
the ratio mass/charge (the m/z value).

180
What Is This?

181
 Mass Spectroscopy
How the mass spectrometer works?

1. Sample is vaporized in an evacuated chamber

M(l) or M(s) → M(g)

2. The gaseous molecules are then bombarded with a stream of high

energy electrons (50-70 eV) to give a radical cation (M+, a
molecular ion) in the ionization chamber

M(g) + e- → M+(g) + 2e-

182
3. These ions are focused to an ion beam by electric fields (in the
electrostatic sector)

4. The ions beam enters the magnetic field of the mass analyzer
(magnetic sector)
5. Ions are deflected in the magnetic sector of the mass spectrometer
depending upon their mass/charge (m/z) ratio

m/z = H2r2
2V
▪ Ions are focused on the collector plate by scanning the magnetic
field (H) or the acceleration voltage (V).
▪ The mass spectrum is a plot of abundance (intensity) versus m/z
ratio.
▪ The most intense peak in the mass spectrum is given a value of
100% abundance and is called the base peak
183
 Isotope Abundances
Definition:
The term “Isotope” is used to describe atoms of an element with
varying number of neutrons e.g. carbon naturally occurring in
two isotopes 12C contain 6 protons & 6 neutrons and 13C contain
6 protons & 7 neutrons.
Classification of isotopes:
Isotopes may be radioactive or non-radioactive. The isotope which is
non-radioactive is called stable isotope.
Classification of elements according to the No. of their isotopes
Element (A) which contain one isotope such as H, F, P, I
Element (A + 1) which contain two isotopes such as C, N, O, Cl, Br
Element (A + 2) which contain three isotopes such as Si, S, Se

184
185
 e
+

e +
R O H R O H

O e O+ O
+

e +
R NH2 R NH2

e
+

186
 Mass spectra of methane CH4 ; MW= 16

- Mass spectrum is relatively simple because few fragmentations

are possible.
- Base peak has m/z = 16 ; parent peak or the molecular ion ( M+).
- Other peaks correspond to the cleavage of the molecular ion.

187
 Mass spectrum of propane C3H8 ; MW= 44

- Spectrum for larger molecules are usually complex and the

molecular ion is often not the base peak
- Molecular ion; m/z = 44 ; 30%
Base peak; m/z = 29 ; 100%
- Other fragment ions are observed

188
 Nitrogen-containing compounds
(Nitrogen Rule)
Compounds containing odd number of nitrogen
must have odd molecular weight and the
compounds possess no nitrogen or even number of
nitrogen have even molecular weight. That due to
the fact that the ions which have odd atomic
weight have odd valence and ions which have even
atomic weight possess even valence, but nitrogen
have even atomic weight (14) and odd valence (3).

189
Atom Mass valence Atom Mass valence
C 12 4 Br 79 1
H 1 1 I 127 1
O 16 2 P 31 3
F 19 1 S 32 2
Cl 35, 37 1 Si 28, 30 4
N 14 3

190
 Molecular Formula from the Molecular
Ion

No. of atoms X atomic weight

Percentage of Element (%) = X 100
Mol. Weight

Percentage of atom X Mol. Weight

No. of Atoms =
Atomic mass X 100

191
e.g. for Chemical formula CxHyNzOn
C (%) X [M]
x =
12 X 100

H (%) X [M]
y =
1 X 100

N (%) X [M]
z =
14 X 100

O (%) X [M]
n =
16 X 100

192
e.g. : C % = 77.8 , H % = 7.5 , O % = 14.7 , Mol. Wt. = 108

77.8 X 108
no. of carbon atoms = = 7
12 X 100

7.5 X 108
no. of hydrogen atoms = = 8
1 X 100

14.7 X 108
no. of oxygen atoms = = 1
16 X 100

So, the chemical formula is C7H8O

193
 Fragmentation Processes
Representation of Fragmentation Processes
If a molecular ion loses a methyl radical (CH3.) the mass
spectrum will show an ion 15 mass units below the molecular
ion: we can write this process as:

M ⎯→ CH3 + (M - 15)+
An alternative is to write the fragment ion as M – CH3.
Throughout this chapter we shall use this convention
frequently, referring to ions as
M - 18, M - 24, M - CO, M – H2S, etc.

194
 Basic Fragmentation Types and Rules

Factors governing fragmentation process:

1- Week bond tend to broken.
2- Stable fragments (not only ions, but also the
accompanied radicals and molecules) tend to be
formed.
3- Some fragmentation process depend on the ability
of molecule to assume cyclic transition state
(McLafferty rearrangement) .

195
Alkanes and alkane groups

dodecane
CH3(CH2)10CH3
M+, 170

196
 Cycloalkanes
▪ Complex fragmentations usually occur for cycloalkanes,
ring size obviously being important in relation to ion stability.
Typically for the simple members the molecular ion peak will
be easily seen, its intensity reducing as branching increases.

▪ Common fragmentations are loss of alkenes or alkenyl ions

and the splitting off of the side-chains with charge retention
by the ring remnant; side-chain loss is simply a special case
of fragmentation at a branching point.

▪ Figure : is the mass spectrum of n-propylcyclohexane,

which should be interpreted with these points in mind.

197
198
 Alkenes and alkenyl groups

▪ Molecular ion peaks for simple alkenes are normally

distinctly seen.

▪ The commonest fragmentation in alkene groups

involves rupture of the allylic bond (b - 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.

199
 CH CH CH2 R
e e
or
+ +
CH CH CH2 R CH CH CH2 R

+
CH CH CH2 + R or CH CH CH2 + R+

+
CH CH CH2 CH CH CH2

200
A McLafferty rearrangement may occur provided
the g-carbon has hydrogen on it.

201
 Cycloalkenes
Fragmentation of cycloalkenes is directed by the double
bond and by the nature of any acyclic alkane residues
present, so that allylic rupture and McLafferty
rearrangements are common.
In addition, cyclohexene derivatives give the important
retro-Diels-Alder reaction.

+ +

+ etc.

202
 Alkynes
No simple pattern emerges for the fragmentation of
alkynes, which can be applied to complex molecules.

Thus for 1-butyne and 2-butyne the molecular ion peak is

the base peak, but the molecular ion peak for higher
members is weak.

Loss of alkyl radicals gives prominent peaks in many cases

(at M-15, M - 29, etc.) and extrusion of alkenes may give
M — 28 and M — 42 peaks, etc.

203
 Aromatic hydrocarbon groups
The molecular ions of aromatic hydrocarbons are
always abundant, and M is commonly the base
peak; accordingly, M + 1 and M + 2 peaks are
easily seen.
Alkylbenzenes, I, are the commonest hydrocarbons
in this class; here, the dominant fragmentation is
at the benzylic bond, for reasons analogous to
those discussed under allylic fission in alkenes.

204
 + +
CH2 CH2 CH2

+
91

I m/z 91
m/z 91
II Tropylium ion III

+
loss of
m/z 65 CH CH
IV

205
phenyl cation. C6H5+, at m/z 77 is produced from many
aromatics by rupture of the bond a to the ring, and this ion
extrudes C2H2 (acetylene) to give m/z 51.
This fragmentation gives rise to a metastable ion at
(51)2 /77 = m/z 33.8.
X X X
+
+
e loss of
C 4H3+
CH CH

m/z 77 m/z 51

206
 Halides
➢ The appearance of the mass spectrum of a halogen-containing
compound is profoundly affected by the number of halogen
atoms present because of isotopic abundances. Fluorine and
iodine, being monoisotopic, present no problems in this
respect.

➢ The fragmentation of mixed halogen compounds is very

complicated, and we shall deal here with compounds
containing only one of the halogens.

➢ Aliphatic fluorine compounds, apart from fragmentations

appropriate to the alkyl chain, show principally a peak at M
- HF (M — 20).

207
➢ Aliphatic chlorine compounds fragment mainly by
loss of HCl ( M − 36 and M − 38): HC1 peaks may
also be seen at m/z 36 and 38.

➢ Loss of chlorine as Cl+ or Cl gives rise to low-

abundance peaks at m/z 35 and 37, and at M - 35
and M - 37.

➢ Aliphatic bromine compounds fragment similarly

to chloro compounds, but loss of Br is the preferred
fragmentation, giving abundant M - 79 and M - 81
peaks.

208
➢ Aliphatic iodine compounds show peaks
corresponding to I+ (m/z = 127), M – I (M - 127),
and M – H2I (M - 129).
➢ Aryl halides, with halogen directly attached to
the ring, show abundant molecular ion peaks,
but the fragmentation is dominated by the
relative stability of the aryl cations.
Consequently halogen is mainly expelled as a
radical, and the (M — X)+.
➢ Acyl halides are discussed with carboxylic acid
derivatives

209
 Alcohols
▪ Molecular ion peaks for primary and secondary alcohols
are weak; for tertiary alcohols the M+ peak is usually absent.

▪ The fragmentations of alcohols, depends on whether the

alcohol is primary, secondary, tertiary, aliphatic or aromatic;
the most important fragmentation is rupture of the bond b to
oxygen.

▪ Alcohols of low volatility can be converted into .their

trimethylsilyl ethers (ROH ⎯→ ROSiMe3), which are much
more volatile because of the loss of hydrogen bonding present
in the alcohols themselves.

210
 Primary aliphatic alcohols
▪ (alkanols) show M — 18 peaks corresponding to loss of
H2O.
▪ An accompanying loss of water together with an alkene is
shown by alcohols with more than four carbons in the
chain, and this simultaneous elimination of an alkene and
water can be indicated mechanistically as shown below.

▪ Peaks corresponding to this process appear at (M - 18 –

CnH2n), for example (M - 18 - 28) for loss of water and
C2H2, etc.

211
 H H H2O
H H +
+ O
O
+ +

Long-chain members may show peaks corresponding to

successive loss of H radicals at M - 1, M - 2 and M - 3;
this can be represented as shown below.
H H H
+ + + +
C O H C O H C O C O
H
+
M M 1 M 2 M 3

212
 Secondary and tertiary aliphatic alcohols

preferentially fragment by loss of alkyl radicals, the ease of

elimination increasing with increased size and branching
in the radical, i.e. peak at M-C4H9 > M-C3H7 > M-C2H5.

+ +
OH OH
C 4H9 C C3 H 7 C 4H9 + C C3 H 7
C 2H5 C 2H5

213
▪ 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. The peak at m/z 107 given by these alcohols
(the base peak in the case of 1-phenylethanol) is best
represented as the hydroxytropylium ion.

▪ Loss of CO from this ion gives m/z 79, and loss of

H leads on to the phenyl cation at m/z 77, which
loses C2H2 to give m/z 51.

214
 OH
CH CH3

1-phenylethanol
OH
H H

CO
+ + C6H5+ C4H3+

m/z 107 m/z 79 m/z 77 m/z 51

hydroxytropylium ion

215
 Phenols
Simple phenols give strong molecular ion peaks.
The commonest fragmentation is loss of CO (M -
28) and CHO (M - 29), which can only be
represented as shown below.

OH + O + +
H H
H
H CO H
+

M 28 M 29

216
Phenols with alkyl side-chains also undergo
benzylic fission, leaving variants of the
hydroxytropylium ion.

OH OH
+

R
CH2 R +

X X
m/z 107 when X = H

217
 Ethers, Acetals and Ketals
On the whole, molecular ion peaks for these classes are
weak.
Aliphatic ethers principally fragment at the bond p to
oxygen, and the largest group is expelled preferentially as
a radical (compare alcohols). Peaks appear therefore at M
– CH3, M – C2H5, etc.

R O R' O R'
-R HC
CH

218
Where b-hydrogen is present, the oxonium ion
may fragment further to eliminate an alkene.

H H

HC O HC O +

R'
R'

219
Fission of the C—O bond (the a bond) occurs to a small
extent, charge retention by carbon being favored over
retention by oxygen.

Acetals and ketals show simple extensions of the ether

fragmentation processes, rupture of the β- bond being
favored over the a-bond.
+ OR
R+ + RO b-rupture C
or (preferred) OR
R O R
R + RO + a-rupture

220
Aromatic ethers other than methyl ethers commonly
fragment by variants of the β-hydrogen transfer discussed
above for ahphatic ethers: a peak at m/z 94 is formed, which
extrudes CO giving m/z 66.

H
+ CHR
+ O H
O CHR + CH2
CH2

m/z 94
CO

H H
m/z 66

221
Methyl phenyl ethers undergo two main fissions at the C—O bonds:
loss of HCHO (giving M - 30) and loss of CH3 (giving M - 15), the
latter process giving an ion that further splits out CO, leaving m/z 65.

+ +
O CH3
+ HCHO

m/z 78
CH3

O +
CO +

m/z 65

222
 Carbonyl Compounds
Before discussing the idiosyncratic behavior of individual
carbonyl classes, we should draw attention to the important
similarities in their fragmentation modes.
α-Cleavage: This occurs in all classes; the bonds at the
carbonyl group rupture, and the ion abundance can be
roughly predicted on the basis of resonance stabilization,
etc.

223
 In summery:

+ .
Y + XCO
+
X . or .
+
Y + XCO
or
CO
+ + YCO.
or X
Y . +
X + YCO

224
For Aldehydes

H C O + R

C O R + H C O

R C O + H

225
For Carboxylic acids

HO C O + R

HO

C O R + HO C O

R C O + OH

226
For Aromatic Carboxylic acids

HO

C O Ph C O + OH

Ph m/z 105

- CO

-C2H2 C4H3
Ph
m/z 77 m/z 51

227
 b-Cleavage with McLafferty rearrangement
This is very much more common, provided -g-
hydrogen is present.
H H
O+ O+
+
X X
R
R
H
O+

228
 Carboxylic acid derivatives
R C O + X

C O X + R C O

X C O + R

X = OR' , OCOR' , NHR' , Halogen

In addition to McLafferty rearrangement

229
 Amines and nitrogen heterocycles
An odd number of nitrogen atoms in the molecule means
an odd relative molecular mass (molecular weight).

For primary aliphatic amines, the base peak is CH2=NH2

(at m/z 30) formed by expulsion of alkyl radical from M .

Higher homologues may also appear at m/z 44, 58, etc.,

but these are less abundant ions. Loss of an alkene (for
example, loss of C2H4) may give peaks at M — 28, etc.

230
Secondary and tertiary amines behave analogously,
and loss of the substituent alkyl radicals is also
observed. Primary aryl amines principally fragment
by loss of H (M — 1) and HCN (M - 27): thus aniline
gives rise to an ion at m/z 66 (93 -27) whose
structure can be represented as the cyclopentadienyl
radical cation. For N-alkyl-anilines, α-cleavage of
the alkyl group is common.

231
Aromatic heterocyclic bases give rise to
abundant M peaks, and for pyridine and
quinoline the principal fragmentation is loss of
HCN (M — 27).

Alkyl-substituted derivatives fragment at the

‘benzylic’ bond as for alkyl-benzenes, and loss
of HCN commonly follows on this process.

232
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