15-1

Organic Chemistry I, CHM 3140, Dr. Laurie S. Starkey, Cal Poly Pomona
Nuclear Magnetic Resonance (NMR) Spectroscopy - Chapter 15 (Klein)

The Electromagnetic Spectrum

wavelength: wavelength:
longer/shorter longer/shorter
Energy: Energy:
higher/lower higher/lower
frequency: frequency:
higher/lower higher/lower
(Image Credit: NASA's Imagine the Universe)

Infrared (IR) spectroscopy reveals which functional groups are present in a molecule. When
certain wavelengths of IR light are absorbed, specific bonds are vibrationally excited: they
stretch or bend. For example, ~1700 cm-1 light will cause a carbonyl (C=O) bond to stretch, so
an absorption in that region indicates the presence of a ketone or aldehyde functional group.
bending: O symmetric O asymmetric O
stretching: stretching:
H H H H H H

Acquiring an NMR spectrum (15.1, 15.2) Like all spectroscopic methods, NMR involves the
use of electromagnetic energy to excite a molecule. By observing this interaction, we can learn
something about the structure of the sample. In NMR spectroscopy, radio frequency waves are
used (60,000,000 Hz or 60 MHz, also 200, 360, 500, etc.) and the result is a change in the spin
of a nucleus. The nuclei which can be observed include 1H "proton NMR," 13C "C-13 NMR," 15N,
19
F, 31P. These all have magnetic moments (like tiny magnets) and will interact with an applied
magnetic field. Each of these nuclei has a spin quantum number I=1/2 and has two spin states
of equal energy. When a magnetic field is applied, these spin states will align with ( ) or
against ( ) the field. Those aligned with the field are lower in energy than those aligned against
the field; the difference in energy between and is proportional to the strength of the magnet
used. Application of radio waves at just the right frequency will cause certain nuclei to absorb
energy and "flip" from the to the spin state. As the excited nucleus relaxes back to the
ground state, a signal is recorded and an NMR spectrum can be obtained. The frequency of this
energy transition depends on the electronic environment of the nucleus.
aligned
applied against field
magnetic (higher E)
field, Bo
60-900+ MHz
aligned
frequency
with field
nuclear spins random nuclear spins aligned with or against the field (lower E)
(all have equal energy) (these two states have different energy)

energy energy
E varies with absorbed released
strength of
magnetic field
 IR spectrum shows 15-2
functional groups
(see Klein Chapter 14
& CHM 3140L lab)

13
C NMR spectrum shows how many different types of carbons are in a molecule,
and whether each carbon is in an electron-rich or electron-deficient environment.

200 150 100 50 0

PPM

1
H NMR (Proton NMR) spectrum

CH3

CH3 Si CH3

CH3

0.0 PPM

tetramethylsilane
(TMS) serves as a
Information obtained from a 1H "Proton" NMR spectrum (15.3): reference, = 0

1) # of signals indicates the number of different types of hydrogens (chemical equivalence).

2) Integration or peak area indicates how many hydrogens are in each signal. It is given as a ratio.
3) Chemical shifts are given as (delta) values, in ppm (~0-10). The chemical shift indicates the
electronic environment of the hydrogens (electron-rich/shielded or electron-poor/deshielded).
4) Splitting patterns indicate the # of neighboring hydrogens. The magnitude of the coupling
constants (given as J values) depend on the spatial relationship (dihedral angle) of the two protons.
 15-3
1) Number of NMR Signals: chemical equivalence of protons (or carbons) (15.4)
How many unique H's (label a, b, c...) and C's (label 1, 2, 3...) are on each compound?

8 H atoms, so 8 signals?
CH3 CH2 CH3 CH3 O CH2 CH2

H H
H H
H H
O
H H
H H
H

homotopic H's: equivalent in NMR (same chemical shift/ value)

enantiotopic H's: equivalent in NMR (same chemical shift/ value)

diastereotopic H's: not equivalent in NMR (different values, J values, split each other, etc.)

2) Peak Integration: number of protons giving rise to signal (15.6)

3H 6H

4H

1H

25.2 25.2 23.5 37.7

see SkillBuilders 15.1, 15.2, 15.4

 15.1, 15.2,
3) Chemical Shift ( value): where signal occurs on spectrum (15.5) 15-4
Delta values are given in parts per million (ppm) relative to the reference compound
tetramethylsilane (TMS) which resonates at = 0.0 ppm. CH3 O
R CH3
H
O
H R2C CR ROCH3 CH3 RH
C H R H

O
NH2 RNH2
N H R NH2

O
OH ROH
R OH
O H
(ppm) 11 10 9 8 7 6 5 4 3 2 1 0

Protons on Carbon Protons on Oxygen/Nitrogen*

Type of C-H (ppm) Description of Proton
Type of H (ppm) Description
R CH3 0.9 alkyl (methyl) 0.5-5 alcohol
ROH

R CH2 R 1.3 alkyl (methylene)

ArOH 4-7 phenol
R3C H 1.5-2 alkyl (methine) O
R C OH 10-13 carb. acid
CH3 1.8 allylic (C is next to a pi bond)
RNH2 0.5-5 amine
O
R C CH3 2-2.3 to carbonyl (C is next to C=O)
ArNH2 3-5 aniline
Ar CH3 2.3 benzylic (C is next to a benzene ring) O
R C NHR 5-9 amide
RC C H 2.5 alkynyl
*Protons on N or O typically have wide ranges of
R2N CH3 2-3 to nitrogen (C is attached to N) expected chemical shifts; the actual value
depends on the solvent used, the concentration,
R CH2 X 3-3.5 to halogen (C attached to Cl/Br/I) etc. Because these protons are acidic and
therefore, exchangeable, they may be broad peaks
RO CH3 3.8 to oxygen (C is attached to O) and usually have no splitting (they don't couple
with neighboring protons. Typically, OH and NH
appear as broad singlets. If a deuterated protic
R CH2 F 4.5 to fluorine (C is attached to F)
solvent is used (e.g., D2O or CD3OD), then the NH
H and OH protons will exchange with deuterium and
R2C CR 5-5.3 vinylic (H is attached to alkene C) the peaks shrink or disappear entirely, because D
(2H) does not show up in the 1H NMR spectrum.
Ar H 7.3 aromatic (H is on a benzene ring)
O R = alkyl group
9.7 aldehyde (H is on C=O)
R C H Note: aldehyde proton (-CHO) has small coupling with Ar = aromatic ring, such as benzene
neighboring H's, so it usually appears as a singlet
 neighboring usually appears singlet
Electron-withdrawing effects are additive 15-5
H H Cl Cl
(Why no CCl4 listed?)
H C H H C Cl H C Cl H C Cl
H H H Cl

0.9 3.1 5.5 7.3

(ppm)

O O O

1.2 2.4 3.6

(ppm)

Effects of pi electrons on chemical shift (anisotropy)

Type of C-H (ppm) Description of Proton
CH3 1.8 allylic (C is next to a pi bond)
Ar CH3
Why are protons that
2.3 benzylic (C is next to benzene ring)
H are on pi bonds or
R2C CR 5-5.3 vinylic (H is attached to alkene C) adjacent to pi bonds
Ar H 7.3 aromatic (H is on a benzene ring) shifted downfield?

The external magnetic field causes the circulation of pi electrons which generates a ring current.
These anisotropic effects cause deshielding, so protons attached to the benzene ring ~7 ppm.

CH3
applied
magnetic H C H
field H

Estimate the integration and chemical shift for each unique proton:

O OH

see SkillBuilder 15.3

4) Shape of the Signal: splitting patterns and the n+1 rule (15.7) 15-6
Each proton acts like a tiny magnet, causing a splitting of its neighbors' signals. Neighboring protons
are said to be "coupled" and the size of the splitting is described by the coupling constant, J.
Exceptions: OH, NH and aldehyde (-CHO) protons typically do not couple with
neighboring protons and typically appear as a singlet (no splitting).

# of nonequivalent # peaks ratio of see SkillBuilder 15.5

neighboring H's (n) (n+1) peaks
0

Putting it all together: predicting a 1H NMR spectrum (15.8, 15.9)

proton #H, split (ppm)

CH2CH3

CH3 C O CH3

proton #H, split (ppm)

CH3 O

CH3 C CH2 CH2 C OH

see SkillBuilders 15.6, 15.7

Match the labeled peaks in the NMR with the protons on the given structure. 15-7

H H
H
H H O O

H3C O H
H H H

a
f

b d

O
OCH3

b d

a c e