Nuclear Magnetic Resonance

(NMR) Spectroscopy
Part 1
Carbon 13 NMR
 Theory of NMR
• The positively charged nuclei of certain elements (e.g.,
13C and 1H) behave as tiny magnets.

• In the presence of a strong external magnetic field (Bo),

these nuclear magnets align either with ( ) the applied
field or opposed to ( ) the applied field.

Bo
• The latter (opposed) is slightly higher in energy than
aligned with the field.

Energy DE is very small

 Theory of NMR
• The small energy difference between the two alignments
of magnetic spin corresponds to the energy of radio
waves according to Einstein’s equation E=hn.

hn

• Application of just the right radiofrequency (n) causes the

nucleus to “flip” to the higher energy spin state
• Not all nuclei require the same amount of energy for the
quantized spin ‘flip’ to take place.
• The exact amount of energy required depends on the
chemical identity (H, C, or other element) and the
chemical environment of the particular nucleus.
 Theory of NMR
• Our department’s NMR spectrometer (in Dobo 245)
has a superconducting magnet with a field strength
of 9.4 Tesla. On this instrument, 1H nuclei absorb
(resonate) near a radiofrequency of 400 MHz;
13C nuclei absorb around 100 MHz.

e-
• Nuclei are surrounded by electrons.
The strong applied magnetic field (Bo)
induces the electrons to circulate Bo
around the nucleus (left hand rule).
(9.4 T)
 Theory of NMR
• The induced circulation of electrons sets up a secondary
(induced) magnetic field (Bi) that opposes the applied
field (Bo) at the nucleus (right hand rule).

Bi

e-

Bo
• We say that nuclei are shielded from the full applied
magnetic field by the surrounding electrons because the
secondary field diminishes the field at the nuclei.
 Theory of NMR
• The electron density surrounding a given nucleus
depends on the electronegativity of the attached atoms.
• The more electronegative the attached atoms, the less
the electron density around the nucleus in question.
• We say that that nucleus is less shielded, or is
deshielded by the electronegative atoms.
• Deshielding effects are generally additive. That is, two
highly electronegative atoms (2 Cl atoms, for example)
would cause more deshielding than only 1 Cl atom.
H H H
 
H C H H C Cl H C Cl
H H Cl
C and H are deshielded C and H are more deshielded
 Chemical Shift
• We call the relative position of absorption in the NMR
spectrum (which is related to the amount of deshielding)
the chemical shift. It is a unitless number (actually a
ratio, in which the units cancel), but we assign ‘units’ of
ppm or  (Greek letter delta) units.
• For 1H, the usual scale of NMR spectra is 0 to 10 (or 12)
ppm (or ).
• The usual 13C scale goes from 0 to about 220 ppm.
• The zero point is defined as the position of absorption of
a standard, tetramethylsilane (TMS): CH3
• This standard has only one type CH3 Si CH3
of C and only one type of H. CH3
 Chemical Shifts
C13 Chemical Shift ( ) vs. Electronegativity
CH3 F
90
80
70
CH3 O
C13 Chemical Shift

60
CH3 N
50
40 CH3 C
30
20 CH3 Si
10
0
-10 1.5 2 2.5 3 3.5 4

Electronegativity
 Chemical Shifts
• Both 1H and 13C Chemical shifts are related to three
major factors:
– The hybridization (of carbon)
– Presence of electronegative atoms or electron attracting groups
– The degree of substitution (1º, 2º or 3º). These latter effects
are most important in 13C NMR, and in that context are usually
called ‘steric’ effects.
• First we’ll focus on Carbon NMR spectra
(they are simpler)
 CMR Spectra
• Each unique C in a structure gives a single peak in the
spectrum; there is rarely any overlap.
– The carbon spectrum spans over 200 ppm; chemical shifts only
0.001 ppm apart can be distinguished; this allows for over 2x105
possible chemical shifts for carbon.
• The intensity (size) of each peak is NOT directly related
to the number of that type of carbon. Other factors
contribute to the size of a peak:
– Peaks from carbon atoms that have attached hydrogen atoms
are bigger than those that don’t have hydrogens attached.
• Carbon chemical shifts are usually reported as downfield
from the carbon signal of tetramethylsilane (TMS).
 13C Chemical Shifts

CH3
CH2

CH
C X (halogen)
C N
C N
Aromatic C
C O TMS
C O C C
C C

220 200 180 160 140 120 100 80 60 40 20 0

13C Chemical shift ( )
downfield upfield
 Predicting 13C Spectra
• Problem 13.6 Predict the number of carbon resonance
lines in the 13C spectra of the following (= # unique Cs):
CH3 CH3 CH3
C
C C
C C
4 lines

plane of symmetry
CH3 CH3
C c
CH3 CH3 CH3 C CH3 5 lines
O O O

CH3
C CH3 5 lines
CH3 C
H
 Predicting 13C Spectra
• Predicte the number of carbon resonance lines in the 13C
spectra of the major product of the following reaction:
CH3 CH3 CH2
Cl
KOH
or ???
ethanol, heat

CH3 CH3 CH2 CH2 CH2

C C
C C C C
c C 7 lines C C
c c
5 lines
plane of symmetry
 Predicting 13C Spectra
CH3 H3C CH3 H3C CH3
CH3 C C
C C 4 lines
C C

CH3 CH3 CH3 CH3

C C C C 2 lines
CH3 CH3 CH3 CH3

Symmetry Simplifies Spectra!!!

 O
CH3CCH3

CH3

O
CDCl3 (solvent)
C
 OCH3

O CH3

CH3COCH3
CDCl3 (solvent)

O
C
 CH3
OCH2

O
CH3
CH3COCH2CH3

CDCl3 (solvent)

O
C
 CH3
OCH2 CH3
O CH2

CH3CH2COCH2CH3

CDCl3 (solvent)

O
C
 O
CH3C6H212
CH CH O22COCH2CH3

ethyl butanoate

CH3
CDCl3 (solvent) CH2 CH2
OCH2 CH3
O
C
 O CH2
CH3
CH3CCH2CH3
CH3

CDCl3 (solvent)
O
C
 H
C H
C C
C C
H C H CH3
O H
CDCl3 (solvent)
C

expanded below

H H
O C and C

CH3C H
C

C H H
 CH2

CH3

CH2 Br
CH3CH2CH2Br
CDCl3 (solvent)
CH3CH2CH2OH CH2
CH3
CH2 OH

CDCl3 (solvent)
 CH2
CH2
CH3
CH3CH2CH2CH2OH CH2 OH

CDCl3 (solvent)
 CH2
CH2
CH3CH2CH2CH2CH2OH
CH2 OH CH2
CH3

CDCl3 (solvent)
 CH3
C H
C
CDCl3 (solvent)

C CDCl3 (solvent)

C
.
2-methyl-1-hexene

CDCl3 (solvent) CH3

and
CH2 CH2
CH2
CH2 CH3

CH2
C
CH3 CH2CH2CH2CH3