Chapter 9

Nuclear Magnetic
Resonance and Mass
Spectrometry

Created by
Professor William Tam & Dr. Phillis Chang
Ch. 9 - 1
About The Authors
These PowerPoint Lecture Slides were created and prepared by Professor
William Tam and his wife Dr. Phillis Chang.

Professor William Tam received his B.Sc. at the University of Hong Kong in
1990 and his Ph.D. at the University of Toronto (Canada) in 1995. He was an
NSERC postdoctoral fellow at the Imperial College (UK) and at Harvard
University (USA). He joined the Department of Chemistry at the University of
Guelph (Ontario, Canada) in 1998 and is currently a Full Professor and
Associate Chair in the department. Professor Tam has received several awards
in research and teaching, and according to Essential Science Indicators, he is
currently ranked as the Top 1% most cited Chemists worldwide. He has
published four books and over 80 scientific papers in top international journals
such as J. Am. Chem. Soc., Angew. Chem., Org. Lett., and J. Org. Chem.

Dr. Phillis Chang received her B.Sc. at New York University (USA) in 1994, her
M.Sc. and Ph.D. in 1997 and 2001 at the University of Guelph (Canada). She
lives in Guelph with her husband, William, and their son, Matthew.

Ch. 9 - 2
1.  Introduction
  Classic
methods for organic structure
determination
●  Boiling point
●  Refractive index
●  Solubility tests
●  Functional group tests
●  Derivative preparation
●  Sodium fusion (to identify N, Cl, Br, I &
S)
●  Mixture melting point
●  Combustion analysis Ch. 9 - 3
  Classic
methods for organic structure
determination

●  Require large quantities of

sample and are time consuming

Ch. 9 - 4
  Spectroscopic methods for organic
structure determination
a)  Mass Spectroscopy (MS)
●  Molecular Mass & characteristic
fragmentation pattern
b)  Infrared Spectroscopy (IR)
●  Characteristic functional groups
c)  Ultraviolet Spectroscopy (UV)
●  Characteristic chromophore
d)  Nuclear Magnetic Resonance (NMR)

Ch. 9 - 5
  Spectroscopic methods for organic
structure determination
●  Combination of these
spectroscopic techniques provides
a rapid, accurate and powerful tool
for Identification and Structure
Elucidation of organic compounds
●  Rapid
●  Effective in mg and microgram
quantities

Ch. 9 - 6
  General steps for structure elucidation
1.  Elemental analysis
●  Empirical formula
●  e.g. C2H4O
2.  Mass spectroscopy
●  Molecular weight
●  Molecular formula
●  e.g. C4H8O2, C6H12O3 … etc.
●  Characteristic fragmentation
pattern for certain functional
groups
Ch. 9 - 7
  General steps for structure elucidation
3.  From molecular formula
●  Double bond equivalent (DBE)

4.  Infrared spectroscopy (IR)

●  Identify some specific
functional groups
●  e.g. C=O, C–O, O–H, COOH,
NH2 … etc.

Ch. 9 - 8
  General steps for structure elucidation
5.  UV
●  Sometimes useful especially
for conjugated systems
●  e.g. dienes, aromatics, enones

6.  1H, 13C NMR and other advanced

NMR techniques
●  Full structure determination

Ch. 9 - 9
  Electromagnetic spectrum

cosmic micro- radio-

X-rays ultraviolet visible infrared
& γ-rays wave wave

λ: 0.1nm 200nm 400nm 800nm 50µm

UV IR NMR
X-Ray
Crystallography
1Å = 10-10m
1nm = 10-9m
1µm = 10-6m

Ch. 9 - 10
2.  Nuclear Magnetic Resonance
(NMR) Spectroscopy
  A graph that shows the characteristic
energy absorption frequencies and
intensities for a sample in a magnetic
field is called a nuclear magnetic
resonance (NMR) spectrum

Ch. 9 - 11
Ch. 9 - 12
1.  The number of signals in the
spectrum tells us how many different
sets of protons there are in the
molecule

2.  The position of the signals in the

spectrum along the x-axis tells us
about the magnetic environment of
each set of protons arising largely
from the electron density in their
environment
Ch. 9 - 13
3.  The area under the signal tells us
about how many protons there are in
the set being measured

4.  The multiplicity (or splitting pattern)

of each signal tells us about the
number of protons on atoms adjacent
to the one whose signal is being
measured

Ch. 9 - 14
  Typical 1H NMR spectrum
●  Chemical Shift (δ)

●  Integration (areas of peaks ⇒ no.

of H)

●  Multiplicity (spin-spin splitting)

and coupling constant

Ch. 9 - 15
  Typical 1H NMR spectrum

1
Record as: H NMR (300 MHz, CDCl3):

δ 4.35 (2H, t, J = 7.2 Hz, Hc)

2.05 (2H, sextet, J = 7.2 Hz, Hb)
1.02 (3H, t, J = 7.2 Hz, Ha)
chemical coupling
shift (δ) constant
no. of H
in ppm
(integration) multiplicity in Hz

Ch. 9 - 16
2A. Chemical Shift
  The position of a signal along the x-axis of
an NMR spectrum is called its chemical
shift
  The chemical shift of each signal gives
information about the structural
environment of the nuclei producing that
signal
  Counting the number of signals in a 1H NMR
spectrum indicates, at a first approximation,
the number of distinct proton environments
in a molecule
Ch. 9 - 17
Ch. 9 - 18
Ch. 9 - 19
  Normal range of 1H NMR

"upfield" (more shielded)

"downfield" (deshielded)

15 -10
(low field δ ppm (high field
strength) strength)

Ch. 9 - 20
  Reference compound Me
●  TMS = tetramethylsilane Me Si Me
Me
as a reference standard (0 ppm)

●  Reasons for the choice of TMS as

reference
  Resonance position at higher field
than other organic compounds
  Unreactive and stable, not toxic
  Volatile and easily removed
(B.P. = 28oC) Ch. 9 - 21
  NMR solvent
●  Normal NMR solvents should not
contain hydrogen
●  Common solvents
  CDCl3
  C6D6
  CD3OD
  CD3COCD3 (d6-acetone)

Ch. 9 - 22
  The 300-MHz 1H NMR spectrum of
1,4-dimethylbenzene

Ch. 9 - 23
2B. Integration of Signal Areas

Integral Step Heights

  The area under each signal in a 1H
NMR spectrum is proportional to the
number of hydrogen atoms producing
that signal
  It is signal area (integration), not
signal height, that gives information
about the number of hydrogen atoms
Ch. 9 - 24
 Ha Ha
Hb
R O Hb
Hb 3H b
a
2H

b a
H H
Ch. 9 - 25
2C. Coupling (Signal Splitting)
  Coupling is caused by the magnetic
effect of nonequivalent hydrogen
atoms that are within 2 or 3 bonds of
the hydrogens producing the signal
  The n+1 rule
●  Rule of Multiplicity:
If a proton (or a set of magnetically
equivalent nuclei) has n neighbors
of magnetically equivalent protons.
It’s multiplicity is n + 1
Ch. 9 - 26
  Examples
(1) Hb Ha a
H : multiplicity = 3 + 1 = 4 (a quartet)
Hb C C Cl
Hb: multiplicity = 2 + 1 = 3 (a triplet)
Hb Ha

(2) Ha Hb
Ha: multiplicity = 2 + 1 = 3 (a triplet)
Cl C C Cl
Hb: multiplicity = 1 + 1 = 2 (a doublet)
Cl Hb

Ch. 9 - 27
Ch. 9 - 28
  Examples
(3) Hb Ha
Ha: multiplicity = 6 + 1 = 7 (a septet)
Hb C C Br
Hb Hb Hb: multiplicity = 1 + 1 = 2 (a doublet)
Hb b
H

Note: All Hb’s are chemically and

magnetically equivalent.

Ch. 9 - 29
  Pascal’s Triangle
●  Use to predict relative intensity of
various peaks in multiplet
●  Given by the coefficient of
binomial expansion (a + b)n
singlet (s) 1
doublet (d) 11
triplet (t) 121
quartet (q) 1331
quintet 14641
sextet 1 5 10 10 5 1
Ch. 9 - 30
  Pascal’s Triangle

Ha Hb Due to
symmetry, Ha
●  For Br C C Br
and Hb are
Cl Cl identical
⇒ a singlet

Ha Hb
Ha ≠ Hb
●  For Cl C C Br
⇒ two doublets
Cl Br

Ch. 9 - 31
3.  How to Interpret Proton NMR
Spectra
1.  Count the number of signals to
determine how many distinct proton
environments are in the molecule
(neglecting, for the time being, the
possibility of overlapping signals)

2.  Use chemical shift tables or charts to

correlate chemical shifts with possible
structural environments Ch. 9 - 32
3.  Determine the relative area of each signal,
as compared with the area of other
signals, as an indication of the relative
number of protons producing the signal
4.  Interpret the splitting pattern for each
signal to determine how many hydrogen
atoms are present on carbon atoms
adjacent to those producing the signal and
sketch possible molecular fragments
5.  Join the fragments to make a molecule in a
fashion that is consistent with the data
Ch. 9 - 33
  Example: 1H NMR (300 MHz) of an
unknown compound with molecular
formula C3H7Br

Ch. 9 - 34
  Three distinct signals at ~ δ3.4, 1.8
and 1.1 ppm
⇒
δ3.4 ppm: likely to be near an
electronegative group (Br)
Ch. 9 - 35
δ (ppm): 3.4 1.8 1.1

Integral: 2 2 3

Ch. 9 - 36
δ (ppm): 3.4 1.8 1.1
Multiplicity: triplet sextet triplet

2 H's on 5 H's on 2 H's on

adjacent C adjacent C adjacent C
Ch. 9 - 37
Complete structure:
most upfield signal
most downfield
signal CH2 CH3
Br CH2

•  2 H's from •  2 H's from •  3 H's from

integration integration integration
•  triplet •  sextet •  triplet
Ch. 9 - 38
4.  Nuclear Spin:
The Origin of the Signal
The magnetic The spinning
field associated proton
with a spinning resembles a tiny
proton bar magnet

Ch. 9 - 39
Ch. 9 - 40
Ch. 9 - 41
  Spin quantum number (I)
1H: I = ½ (two spin states: +½ or -½)
⇒ (similar for 13C, 19F, 31P)

12C, 16O, 32S:

I=0
⇒ These nuclei do not give an NMR
spectrum

Ch. 9 - 42
5.  Detecting the Signal: Fourier
Transform NMR Spectrometers

Ch. 9 - 43
Ch. 9 - 44
6.  Shielding & Deshielding of Protons
  All protons do not absorb energy at the
same frequency in a given external
magnetic field
  Lower chemical shift values correspond with
lower frequency
  Higher chemical shift values correspond
with higher frequency
"upfield" (more shielded)
"downfield" (deshielded)

15 -10
(low field δ ppm (high field
strength) strength) Ch. 9 - 45
Ch. 9 - 46
  Deshielding by electronegative groups

CH3X

X= F OH Cl Br I H
Electro-
4.0 3.5 3.1 2.8 2.5 2.1
negativity
δ (ppm) 4.26 3.40 3.05 2.68 2.16 0.23

●  Greater electronegativity
  Deshielding of the proton
  Larger δ
Ch. 9 - 47
  Shielding and deshielding by circulation
of π electrons
●  If we were to consider only the
relative electronegativities of carbon
in its three hybridization states, we
might expect the following order of
protons attached to each type of
carbon:

(higher (lower
sp < sp < sp
2 3
frequency) frequency)
Ch. 9 - 48
 ●  In fact, protons of terminal alkynes
absorb between δ 2.0 and δ 3.0,
and the order is

(higher (lower
sp < sp < sp
2 3
frequency) frequency)

Ch. 9 - 49
●  This upfield shift (lower frequency)
of the absorption of protons of
terminal alkynes is a result of
shielding produced by the
circulating π electrons of the triple
bond

Shielded
(δ 2 – 3 ppm)
Ch. 9 - 50
 ●  Aromatic system
Shielded region

Deshielded region

Ch. 9 - 51
●  e.g.
Hc
Hd

b
H
Ha

δ (ppm)
a b
H & H : 7.9 & 7.4 (deshielded)
c d
H & H : 0.91 – 1.2 (shielded)
Ch. 9 - 52
●  Alkenes

Deshielded
(δ 4.5 – 7 ppm)

Ch. 9 - 53
●  Aldehydes

R
O
H

Electronegativity effect + Anisotropy effect

⇒ δ = 8.5 – 10 ppm (deshielded)

Ch. 9 - 54
7.  The Chemical Shift
  Reference compound Me
●  TMS = tetramethylsilane Me Si Me
Me
as a reference standard (0 ppm)
●  Reasons for the choice of TMS as
reference
  Resonance position at higher field
than other organic compounds
  Unreactive and stable, not toxic
  Volatile and easily removed
(B.P. = 28oC)
Ch. 9 - 55
7A. PPM and the δ Scale
  The chemical shift of a proton, when
expressed in hertz (Hz), is
proportional to the strength of the
external magnetic field
  Since spectrometers with different
magnetic field strengths are commonly
used, it is desirable to express chemical
shifts in a form that is independent of
the strength of the external field

Ch. 9 - 56
  Since chemical shifts are always very small
(typically 5000 Hz) compared with the total
field strength (commonly the equivalent of
60, 300, or 600 million hertz), it is
convenient to express these fractions in
units of parts per million (ppm)

  This is the origin of the delta scale for the

expression of chemical shifts relative to TMS
(observed shift from TMS in hertz) x 106
δ=
(operating frequency of the instrument in hertz)

Ch. 9 - 57
  For example, the chemical shift for benzene
protons is 2181 Hz when the instrument is
operating at 300 MHz. Therefore
2181 Hz x 106
δ= = 7.27 ppm
300 x 106 Hz
  The chemical shift of benzene protons in a
60 MHz instrument is 436 Hz:
436 Hz x 106
δ= = 7.27 ppm
60 x 106 Hz
  Thus, the chemical shift expressed in ppm is
the same whether measured with an
instrument operating at 300 or 60 MHz (or
any other field strength) Ch. 9 - 58
8.  Chemical Shift Equivalent and
Nonequivalent Protons
  Two or more protons that are in
identical environments have the same
chemical shift and, therefore, give only
one 1H NMR signal

  Chemicallyequivalent protons are

chemical shift equivalent in 1H NMR
spectra
Ch. 9 - 59
8A. Homotopic and Heterotopic Atoms
  Ifreplacing the hydrogens by a
different atom gives the same
compound, the hydrogens are said to
be homotopic

  Homotopic hydrogens have identical

environments and will have the same
chemical shift. They are said to be
chemical shift equivalent
Ch. 9 - 60
 Br H H Br
H C C H H C C H

same compounds
same compounds

H H H H

H H H H H H
Br C C H H C C H H C C Br
H H H H H H
Ethane
H H H H
H C C H H C C H
Br H H Br
  The six hydrogens of ethane are homotopic
and are, therefore, chemical shift equivalent
  Ethane, consequently, gives only one
signal in its 1H NMR spectrum Ch. 9 - 61
  If
replacing hydrogens by a different
atom gives different compounds,
the hydrogens are said to be
heterotopic

  Heterotopic
atoms have different
chemical shifts and are not
chemical shift equivalent

Ch. 9 - 62
same Cl Br
compounds H C C H
⇒ these 3 These 2 H’s
H H
H’s of the are also
H Br H Br
CH3 group homotopic
are Cl C C H H C C H
to each
homotopic H H H H other
⇒ the CH3 H Br
group gives H C C H
only one 1H H Br H Br
Cl H
NMR signal H C C H H C C H
Cl H H Cl

different compounds
⇒ heterotopic
Ch. 9 - 63
 H Br
H C C H
H H
  CH3CH2Br
●  two sets of hydrogens that are
heterotopic with respect to each
other
●  two 1H NMR signals

Ch. 9 - 64
  Other examples
H CH3
(1) C C ⇒ 2 1H NMR signals
H CH3

H CH3

(2) H H ⇒ 4 1H NMR signals

H CH3
Ch. 9 - 65
  Other examples

H
H H
(3) CH3
H3C
H H
H
⇒ 3 1H NMR signals

Ch. 9 - 66
  Application to 13C NMR spectroscopy
●  Examples

(1) H3C CH 3 ⇒1 13C NMR signal

CH3

(2) ⇒4 13C NMR signals

CH3

Ch. 9 - 67
(3) ⇒5 13C NMR signals

HO OH

HO
(4) ⇒4 13C NMR signals

OH

Ch. 9 - 68
8B. Enantiotopic and Diastereotopic
Hydrogen Atoms

  Ifreplacement of each of two

hydrogen atoms by the same group
yields compounds that are
enantiomers, the two hydrogen atoms
are said to be enantiotopic

Ch. 9 - 69
   Enantiotopic
hydrogen atoms have the
same chemical shift and give only one
1H NMR signal:

H G

enantiotopic H3C Br

H H
enantiomer
H3C Br

G H

H3C Br
Ch. 9 - 70
 H OH
chirality H3C
centre CH3

diastereomers
Hb G
H OH
H3C
CH3
Hb Ha
H OH
diastereotopic H3C
CH3
G Ha

Ch. 9 - 71
 G
Br
Hb

diastereomers
Ha H
Br
Hb
H Ha

diastereotopic Br
G
H

Ch. 9 - 72
9.  Signal Splitting:
Spin–Spin Coupling
  Vicinal coupling is coupling between
hydrogen atoms on adjacent carbons
(vicinal hydrogens), where separation
between the hydrogens is by three σ
bonds
Ha Hb
3
J or vicinal coupling

Ch. 9 - 73
9A. Vicinal Coupling
  Vicinal coupling between heterotopic
protons generally follows the n + 1
rule. Exceptions to the n + 1 rule can
occur when diastereotopic hydrogens
or conformationally restricted systems
are involved
  Signal splitting is not observed for
protons that are homotopic
(chemical shift equivalent) or
enantiotopic
Ch. 9 - 74
9B. Splitting Tree Diagrams and the
Origin of Signal Splitting
  Splitting analysis for a doublet

Hb Ha
C C

Ch. 9 - 75
  Splitting analysis for a triplet

Hb H a
C C
Hb

Hb H a Hb
C C C

Ch. 9 - 76
  Splitting analysis for a quartet

b a
H H
Hb C C
Hb

Ch. 9 - 77
  Pascal’s Triangle
●  Use to predict relative intensity of
various peaks in multiplet
●  Given by the coefficient of
binomial expansion (a + b)n
singlet (s) 1
doublet (d) 11
triplet (t) 121
quartet (q) 1331
quintet 14641
sextet 1 5 10 10 5 1
Ch. 9 - 78
9C. Coupling Constants – Recognizing
Splitting Patterns

Ha Hb
X C C Hb
Ha Hb

Ch. 9 - 79
9D. The Dependence of Coupling
Constants on Dihedral Angle
  3J
values are related to the dihedral
angle (φ)
H φ
H

Ch. 9 - 80
  Karplus curve

  φ ~0o or 180o
⇒ Maximum
3J value

  φ ~90o
⇒ 3J ~0 Hz

Ch. 9 - 81
  Karplus
curve
●  Examples
b
H
b
a
H
H
Ha
(axial, axial) (equatorial, equatorial)
b
H
a
H
b
a
H
H
φ = 180º φ = 60º
Ja,b = 10-14 Hz Ja,b = 4-5 Hz
Ch. 9 - 82
  Karplus
curve
●  Examples b
H

Ha

(equatorial, axial)
Hb
Ha

φ = 60º
Ja,b = 4-5 Hz
Ch. 9 - 83
9E. Complicating Features
  The 60 MHz 1H NMR spectrum of ethyl
chloroacetate

Ch. 9 - 84
  The300 MHz 1H NMR spectrum of
ethyl chloroacetate

Ch. 9 - 85
9F. Analysis of Complex Interactions

Ch. 9 - 86
  The 300 MHz 1H NMR spectrum of 1-
nitropropane

Ch. 9 - 87
10.  Proton NMR Spectra and Rate
Processes
  Protons of alcohols (ROH) and amines may
appear over a wide range from 0.5 – 5.0 ppm
●  Hydrogen-bonding is the reason for this
range
in high dilution (free OH): in conc. solution (H-bonded):
− R
δ R
R O H H O
O
H
R
δ+ H O
δ = ~0.5-1.0 ppm
proton more deshielded
Ch. 9 - 88
  Why don’t we see coupling with the
O–H proton, e.g. –CH2–OH (triplet?)
●  Because the acidic protons are
exchangeable about 105 protons
per second (residence time 10-5
sec), but the NMR experiment
requires a time of 10-2 – 10-3 sec.
to “take” a spectrum, usually we
just see an average (thus, OH
protons are usually a broad
singlet)
Ch. 9 - 89
Trick:

●  Run NMR in d6-DMSO where H-

bonding with DMSO’s oxygen
prevents H’s from exchanging and
we may be able to see the coupling

Ch. 9 - 90
  Deuterium Exchange

●  To determine which signal in the

NMR spectrum is the OH proton,
shake the NMR sample with a drop
of D2O and whichever peak
disappears that is the OH peak
(note: a new peak of HOD appears)
D2O
R O H R O D + HOD

Ch. 9 - 91
  Phenols
●  Phenol protons appear downfield
at 4-7 ppm
●  They are more “acidic” - more H+
character
●  More dilute solutions - peak
appears upfield: towards 4 ppm

OH O H

Ch. 9 - 92
  Phenols
●  Intramolecular H-bonding causes
downfield shift

12.1 ppm
O
H
O

Ch. 9 - 93
11.  Carbon-13 NMR Spectroscopy
11A. Interpretation of 13C NMR
Spectra
  Unlike 1H
with natural abundance
~99.98%, only 1.1% of carbon,
namely 13C, is NMR active

Ch. 9 - 94
11B. One Peak for Each Magnetically
Distinct Carbon Atom
  13CNMR spectra have only become
commonplace more recently with the
introduction of the Fourier Transform
(FT) technique, where averaging of
many scans is possible (note 13C
spectra are 6000 times weaker than 1H
spectra, thus require a lot more scans
for a good spectrum)

Ch. 9 - 95
  Notefor a 200 MHz NMR (field strength
4.70 Tesla)

●  1H NMR ⇒ Frequency = 200 MHz

●  13C NMR ⇒ Frequency = 50 MHz

Ch. 9 - 96
 H
  Example:
●  2-Butanol CH3 C CH2 CH3

OH

Proton-coupled
13C NMR spectrum

Ch. 9 - 97
 H
  Example:
●  2-Butanol CH3 C CH2 CH3

OH

Proton-decoupled
13C NMR spectrum

Ch. 9 - 98
11C. 13C Chemical Shifts
  Decreased electron density around an
atom deshields the atom from the
magnetic field and causes its signal to
occur further downfield (higher ppm,
to the left) in the NMR spectrum
  Relatively higher electron density
around an atom shields the atom from
the magnetic field and causes the
signal to occur upfield (lower ppm, to
the right) in the NMR spectrum
Ch. 9 - 99
  Factors affecting chemical shift
i.  Diamagnetic shielding due to bonding
electrons
ii.  Paramagnetic shielding due to low-lying
electronic excited state
iii.  Magnetic Anisotropy – through space
due to the near-by group (especially π
electrons)
In 1H NMR, (i) and (iii) most significant;
in 13C NMR, (ii) most significant (since
chemical shift range >> 1H NMR)
Ch. 9 - 100
  Electronegative substituents cause
downfield shift

  Increase in relative atomic mass of

substituent causes upfield shift
13
X Electronegativity Atomic Mass C NMR: CH3X
Cl 2.8 35.5 23.9 ppm
Br 2.7 79.9 9.0 ppm
I 2.2 126.9 -21.7 ppm

Ch. 9 - 101
  Hybridization of carbon

●  sp2 > sp > sp3

e.g.

H2C CH2 HC CH H3C CH3

123.3 ppm 71.9 ppm 5.7 ppm

Ch. 9 - 102
  Anisotropy effect

●  Shows shifts similar to the effect

in 1H NMR
e.g.

C C C

shows large
upfield shift

Ch. 9 - 103
Ch. 9 - 104
Ch. 9 - 105
 (a) (b) (c)
Cl CH2 CH CH3
OH

1-Chloro-2-propanol

(c)
(b) (a)

Ch. 9 - 106
11D. Off-Resonance Decoupled Spectra
  NMR spectrometers can differentiate among carbon
atoms on the basis of the number of hydrogen
atoms that are attached to each carbon
  In an off-resonance decoupled 13C NMR spectrum,
each carbon signal is split into a multiplet of peaks,
depending on how many hydrogens are attached to
that carbon. An n + 1 rule applies, where n is the
number of hydrogens on the carbon in question.
Thus, a carbon with no hydrogens produces a
singlet (n = 0), a carbon with one hydrogen
produces a doublet (two peaks), a carbon with two
hydrogens produces a triplet (three peaks), and a
methyl group carbon produces a quartet (four
peaks) Ch. 9 - 107
 9 N
Off-resonance 8
7
2
decoupled 13C NMR N
3 6
4
1
5
O

Broadband proton-decoupled 13C NMR

Ch. 9 - 108
11E. DEPT 13C Spectra
  DEPT 13C NMR spectra indicate how
many hydrogen atoms are bonded to
each carbon, while also providing the
chemical shift information contained in
a broadband proton-decoupled 13C
NMR spectrum. The carbon signals in a
DEPT spectrum are classified as CH3,
CH2, CH, or C accordingly

Ch. 9 - 109
 (a) (c)
(b)
(a) (b) (c)
Cl CH2 CH CH3
OH
1-Chloro-2-propanol

Ch. 9 - 110
  The
broadband proton-decoupled 13C
NMR spectrum of methyl methacrylate

Ch. 9 - 111
12.  Two-Dimensional (2D) NMR
Techniques
  HCOSY
●  1H–1H correlation spectroscopy

  HETCOR
●  Heteronuclear correlation
spectroscopy

Ch. 9 - 112
  HCOSY of 2-chloro-butane
H1 H4
H3
H2

H4

H1

H3

H2

Ch. 9 - 113
  HETCOR of 2-chloro-butane
C3 C1 C4

C2

H4

H1
H3

H2

Ch. 9 - 114
13.  An Introduction to Mass
Spectrometry
  Partial MS of octane (C8H18, M = 114)

14 (CH2)
29 (CH3CH2)

57
85 M+
71 114

Ch. 9 - 115
  TheM+ peak at 114 is referred to as
the parent peak or molecular ion
-
e
C8H18 [C8H18] + 2 e-
70 eV
(M+)

  The largest or most abundant peak is

called the base peak and is assigned an
intensity of 100%, other peaks are
then fractions of that e.g. 114(M+,40),
85(80), 71(60), 57(100) etc.
Ch. 9 - 116
  Massesare usually rounded off to
whole numbers assuming:

H = 1, C = 12, N = 14, O = 16, F = 19 etc.

Daughter
fragmentation ions
[C8H18] [C6H13]
(M , 114) -CH3CH2 (29)
+
(85)

-CH3CH2CH2 (29+14) [C5H11]

Molecular ion (parent peak) (71)
Ch. 9 - 117
14.  Formation of Ions: Electron
Impact Ionization
  In the mass spectrometer, a molecule in the
gaseous phase under low pressure is
bombarded with a beam of high-energy
electrons (70 eV or ~ 1600 kcal/mol)
  This beam can dislodge an electron from a
molecule to give a radical cation which is
called the molecular ion, M+ or more
accurately
70 eV e-
M M
Ch. 9 - 118
  This molecular ion has considerable
surplus energy so it can fly apart or
fragment to give specific ions which
may be diagnostic for a particular
compound
- m1º - m2º - m3º
M A B C etc.

mº = neutral fragment radical

Ch. 9 - 119
15.  Depicting the Molecular Ion

CH 3CH 2 CH 3

Radical cations from ionization

of nonbonding on π electron

H3C OH H3C N CH3 H2C CHCH2CH3

CH3

Methanol Trimethylamine 1-Butene

Ch. 9 - 120
  Ionization potentials of selected
molecules
Ionization
Compound Potential (eV)
CH3(CH2)3NH2 8.7
C6H6 (benzene) 9.2
C2H4 10.5
CH3OH 10.8
C2H6 11.5
CH4 12.7
Ch. 9 - 121
16.  Fragmentation
1.  The reactions that take place in a mass
spectrometer are unimolecular, that is, they
do not involve collisions between molecules
or ions. This is true because the pressure is
kept so low (10-6 torr) that reactions
involving bimolecular collisions do not occur
2.  We use single-barbed arrows to depict
mechanisms involving single electron
movements
3.  The relative ion abundances, as indicated by
peak intensities, are very important
Ch. 9 - 122
16A. Fragmentation by Cleavage at a
Single Bond
  When a molecular ion fragments, it will
yield a neutral radical (not detected) and
a carbocation (detected) with an even
number of electrons
  The fragmentation will be dictated to
some extent by the fragmention of the
more stable carbocation:
+ + +
ArCH2 > CH2=CHCH2 > 3o > 2o > 1o > CH3
Ch. 9 - 123
  e.g.

R+ + CH3

R CH
X +
R + CH3

●  Site of ionization: n > π > σ

non-bonding

Ch. 9 - 124
  As the carbon skeleton becomes more
highly branched, the intensity of the
molecular ion peak decreases
  Butane vs. isobutane
a + CH3
a (43)
70eV
e-
b+ b + CH2CH3
M (58)
(29)

70eV
- + CH3
e (43)
M+(58)
Ch. 9 - 125
16B. Fragmentation of Longer Chain
and Branched Alkanes
  Octane vs. isooctane
(85) +

(71) +

(57) +
M+(114)
(43) +

+
M+(114) (57)
Ch. 9 - 126
16C. Fragmentation to Form
Resonance-Stabilized Cations
  Alkenes
●  Important fragmentation of
terminal alkenes
  Allyl carbocation (m/e = 41)

R +

(41)
Ch. 9 - 127
  Carbon–carbon bonds next to an atom
with an unshared electron pair usually
break readily because the resulting
carbocation is resonance stabilized
  Ethers
●  Cleavage α (to ether oxygen) C–C bonds

O O
CH3 +
(m/e = 59)
Ch. 9 - 128
  Alcohols
●  Most common fragmentation: - loss
of alkyl groups
OH OH
CH3 +
a
(m/e = 59)
a OH b

M+(74) b OH OH
CH3CH2 +

(m/e = 45)
Ch. 9 - 129
  Carbon–carbon bonds next to the
carbonyl group of an aldehyde or
ketone break readily because
resonance-stabilized ions called
acylium ions are produced

Ch. 9 - 130
  Aldehydes
●  M+ peak usually observed but may
be fairly weak

●  Common fragmentation pattern

  α-cleavage
H + R C O
O acylium ion

R H
R + H C O
(m/e = 29)
Ch. 9 - 131
  Ketones
●  α-cleavage
O
+
a (m/e = 71)

b O a

b O
+
(m/e = 99)

Ch. 9 - 132
  Alkyl-substituted benzenes ionize by
loss of a π electron and undergo loss
of a hydrogen atom or methyl group
to yield the relatively stable tropylium
ion (see Section 14.7C). This
fragmentation gives a prominent peak
(sometimes the base peak) at m/z 91

Ch. 9 - 133
  Aromatic hydrocarbons
●  very intense M+ peaks
●  characteristic fragmentation
pattern (when an alkyl group
attached to the benzene ring): -
tropylium cation

CH2 rearrangement
CH3
CH3 +

benzyl cation tropylium cation

(m/e = 91)

Ch. 9 - 134
16D. Fragmentation by Cleavage of
Two Bonds
  Alcoholsfrequently show a prominent
+
peak at M - 18. This corresponds to
●

the loss of a molecule of water

●  May lose H2O by 1,2- or 1,4-

elimination

Ch. 9 - 135
 OH
1,2-elimination: + H2O

M (M - 18)

1,4-elimination:
OH + CH3CH2
OH H
M

(M - 18) + H2O
Ch. 9 - 136
  Cycloalkenesshow a characteristic
fragmentation pattern which
corresponds to a reverse Diels-Alder
reaction
retro Diels-Alder
+

  e.g.

Ch. 9 - 137
  Aromatic hydrocarbons
●  e.g.

McLafferty Rearrangement

CH2
H +
H
(m/e = 92)

Ch. 9 - 138
  Ketones
●  McLafferty rearrangement
H
O OH OH
+

1st McL. Rearr. H

O OH

(m/e = 86)
2nd McL. Rearr.

OH
+
(m/e = 58)
Ch. 9 - 139
 OH OH

i 2º radical (m/e = 86)

H H
O observed
ii i

OH
ii OH

1º radical (m/e = 114)

NOT observed

Ch. 9 - 140
  Characteristic of McLafferty
rearrangement
1.  No alkyl migrations to C=O, only H
migrates
H R
O

H R
O

X R
O
H

Ch. 9 - 141
  Characteristic of McLafferty
rearrangement
2.  2o is preferred over 1o
H H OH
O
ii i

2º radical

OH
not

1º radical
Ch. 9 - 142
17.  How To Determine Molecular
Formulas and Molecular Weights
Using Mass Spectrometry
17A. Isotopic Peaks & the Molecular Ion

Ch. 9 - 143
  The presence of isotopes of carbon,
hydrogen, and nitrogen+ in a compound
gives rise to a small M + 1 peak
●

  The presence of oxygen, sulfur,

chlorine, or bromine
+
in a compound
gives rise to an M + 2 peak
●

M + 1 Elements: C, H, N

M + 2 Elements: O, S, Br, Cl

Ch. 9 - 144
 +
  TheM + 1 peak can be used to
●

determine the number of carbons in a

molecule
+
  TheM + 2 peak can indicate whether
●

bromine or chlorine is present

  Theisotopic peaks, in general, give us

one method for determining molecular
formulas

Ch. 9 - 145
  Example
●  Consider 100 molecules of CH4
1 1 1
H H H
1 12 1 1 13 1 1 12 2
H C H H C H H C H

H 1
H 1
H1

M : 16 M + 1 = 17

C12: 100 C13: 1.11

H1: 100 H2: 0.016

Ch. 9 - 146
 H1 H1 H1
1
H C12
H1
H 1
C13
H 1
H 1
C12 H2

H1 H1 H1

M : 16 M + 1 = 17

1.11 molecules 4x0.016 = 0.064 molecules

contain a 13C atom contain a 2H atom

+
Intensity of M + 1 peak:+
●

1.11+0.064=1.174% of the M● peak

Ch. 9 - 147
 +
M
●
relative ion abundance

100

+
M +1
●

≈ 1.17
m/z
Ch. 9 - 148
17B. How To Determine the Molecular
Formula

Intensity
m/z +
(% of M● )

72 73.0/73 x 100 = 100

73 3.3/73 x 100 = 4.5

74 0.2/73 x 100 = 0.3

Ch. 9 - 149
 +
  IsM odd or even? According to
●

the nitrogen rule, if it is even, then

the compound must contain an
even number of nitrogen atoms
(zero is an even number)
+
●
●  For our unknown, M is even. The
compound must have an even
number of nitrogen atoms

Ch. 9 - 150
  Therelative abundance of the
+
M +1 peak indicates the
●

number of carbon atoms.

Number of C atoms+
= relative
abundance of (M +1)/1.1
●

●  For our unknown

4.5
Number of C atoms = ~4
1.1
Ch. 9 - 151
 +
  The relative abundance of the M +2
●

peak indicates the presence (or

absence) of S (4.4%), Cl (33%), or Br
(98%) +
●  For our unknown M +2 = 0.3%; thus,
●

we can assume that S, Cl, and Br are

absent

  The molecular formula can now be

established by determining the
number of hydrogen atoms and adding
the appropriate number of oxygen
atoms, if necessary Ch. 9 - 152
 +
  Since M is m/z 72
●

⇒ molecular weight = 72
  As determined using the relative
+
abundance of M +1 peak, number of
●

carbons present is 4
  Using the “nitrogen rule”, this unknown
must have an even number of N. Since
M.W. = 72, and there are 4 C present,
(12 x 4 = 48), adding 2 “N” will be
greater than the M.W. of the unknown.
Thus, this unknown contains zero “N”
Ch. 9 - 153
  Fora molecule composed of C and H
only
H = 72 – (4 x 12) = 24
but C4H24 is impossible

  For a molecule composed of C, H and O

H = 72 – (4 x 12) – 16 = 8
and thus our unknown has the
molecular formula C4H8O
Ch. 9 - 154
17C. High-Resolution Mass Spectrometry

Ch. 9 - 155
  Example 1

●  O2, N2H4 and CH3OH all have M.W. of

32 (by MS), but accurate masses are
different
  O2 = 2(15.9949) = 31.9898

  N2H4 = 2(14.0031) + 4(1.00783) =

32.0375

  CH4O = 12.00000 + 4(1.00783) +

15.9949 = 32.0262
Ch. 9 - 156
  Example 2

●  Both C3H8O and C2H4O2 have M.W. of

60 (by MS), but accurate masses are
different

  C3H8O = 60.05754

  C2H4O2 = 60.02112

Ch. 9 - 157
18.  Mass Spectrometer Instrument
Designs

Ch. 9 - 158
19. GC/MS Analysis

Ch. 9 - 159
 END OF CHAPTER 9 

Ch. 9 - 160