Tufts University Chem 51 Summer 2013

Lecture 9 (Chapter 9, NMR only)

Mon, June 10
Lecture 9 will cover sections 9.1-9.8, 9.9 (except 9.9D), 9.10-9.11. The dependence of coupling
constant on dihedral angle, 2D NMR, and mass-spectrometry will be omitted.
It is recommended that you read the above-mentioned sections of Chapter 9 and do in-text
review problems 9.1-9.9, 9.14.
After-chapter problems that are relevant and useful: 9.23-9.28, 9.30, 9.40, 9.42-9.47. For the last
four problems, use the following molecular formulas: 9.44 C
6
H
8
O; 9.45 C
10
H
12
O; 9.46 C
15
H
24
;
9.47 C
10
H
12
O
3
(there is a typo in the molecular formula in 9.47 in the textbook).
Also useful are questions 9.1-9.5 on Quiz 9 from the Study Guide.


Ch. 9 - 2
1. Introduction
General steps for structure elucidation
1. Elemental analysis
Empirical formula (e.g. C
2
H
4
O)
2. Mass spectroscopy
Molecular weight
Molecular formula
e.g. C
2
H
4
O, C
4
H
8
O
2
etc.

Ch. 9 - 3
General steps for structure elucidation
3. From molecular formula
Index of Hydrogen Deficiency
(IHD)
4. Infrared spectroscopy (IR)
Identify some specific
functional groups
e.g. C=O, OH, COOH, NH
2
5. NMR
Full structure determination


Ch. 9 - 4
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 - 5



Ch. 9 - 5

Ch. 9 - 6
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 - 7
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 - 8
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
1
H NMR
spectrum indicates, at a first approximation,
the number of distinct types of hydrogens in
in a molecule






Ch. 9 - 11
Reference compound
TMS = tetramethylsilane
as a reference standard (0 ppm)
Reasons for the choice of TMS as
reference
Resonance position at higher field
than most organic compounds
Unreactive and stable, not toxic
Volatile and easily removed
(B.P. = 28
o
C)
Me
Si Me Me
Me


Ch. 9 - 12
NMR solvent
Normal NMR solvents should not
contain hydrogen
Common solvents
CDCl
3
C
6
D
6
CD
3
OD
CD
3
COCD
3
(d
6
-acetone)

Ch. 9 - 13
The 300-MHz
1
H NMR spectrum of
1,4-dimethylbenzene


Ch. 9 - 14
2B. Integration of Signal Areas
Integral Step Heights
The area under each signal in a
1
H
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 - 15
O
H
a
H
a
H
b
H
b
H
b R
H
a
H
b
2 H
a
3 H
b


Ch. 9 - 16
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 Hs) has n neighbors of
magnetically equivalent protons, its
multiplicity is n + 1

Ch. 9 - 17
Examples
H
b
C C Cl
H
a
H
b
H
b
H
a
H
a
: multiplicity = 3 + 1 = 4 (a quartet)
H
b
: multiplicity = 2 + 1 = 3 (a triplet)
(1)
Cl C C Cl
H
b
H
a
Cl H
b
H
a
: multiplicity = 2 + 1 = 3 (a triplet)
H
b
: multiplicity = 1 + 1 = 2 (a doublet)
(2)

Ch. 9 - 18


Ch. 9 - 19
Examples
Note: All H
b
s are chemically and
magnetically equivalent.
H
b
C C Br
H
a
H
b
H
b
H
a
: multiplicity = 6 + 1 = 7 (a septet)
H
b
: multiplicity = 1 + 1 = 2 (a doublet)
(3)
H
b
H
b
H
b

Ch. 9 - 20
For
For
Br C C Br
H
b
H
a
Cl Cl
Due to
symmetry, H
a
and H
b
are
identical
a singlet
Cl C C Br
H
b
H
a
Cl Br
H
a
H
b
two doublets


Ch. 9 - 21
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 - 22
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 - 23
Example:
1
H NMR (300 MHz) of an
unknown compound with molecular
formula C
3
H
7
Br



Ch. 9 - 24
4. Nuclear Spin:
The Origin of the Signal
The magnetic
field associated
with a spinning
proton
The spinning
proton
resembles a tiny
bar magnet

Ch. 9 - 25


Ch. 9 - 26
Proton in spin state may absorb energy
E and turn into spin state

Ch. 9 - 27
5. Detecting the Signal: Fourier
Transform NMR Spectrometers



Ch. 9 - 28
All protons do not absorb energy at the
same frequency in a given external
magnetic field
Lower chemical shift values correspond to
lower frequency
Higher chemical shift values correspond to
higher frequency
6. Shielding & Deshielding of Protons
15 -10
ppm
"upfield" (more shielded)
"downfield" (deshielded)
(high field
strength)
(low field
strength)

Ch. 9 - 29
Deshielding by electronegative groups
CH
3
X
X = F OH Cl Br I H
Electro-
negativity
4.0 3.5 3.1 2.8 2.5 2.1
(ppm) 4.26 3.40 3.05 2.68 2.16 0.23
Greater electronegativity
Deshielding of the proton
Larger