Analytical Chemistry
• Chromatography (Separations)
• Mass Spectrometry
• Infrared (IR) Spectroscopy
• Nuclear Magnetic Resonance (NMR) Spectroscopy
• X-ray Crystallography (visual solid state molecular structure)
The Electromagnetic Spectrum
Scattering [X-ray Crystallography]
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Electronic Excitations [UV/Vis Spectroscopy]
Molecular Vibrations [IR]
Molecular Rotations [Rotational Spectroscopy]
Nuclear Spin "Flipping" [NMR]
Nuclear Magnetic Resonance
(NMR) Spectroscopy
• Identify the environment of hydrogen and
carbon atoms
• Identify atom connectivity
• Identify stereochemical relationships
Nuclear Magnetic Resonance
(NMR) Spectroscopy
The spin state of a nucleus is affected by an
applied magnetic field
Nuclear Magnetic Resonance
(NMR) Spectroscopy
β-state
Energy released
Add Energy (& detected)
B0
α-state
Effect of Field Strength
An NMR Spectrometer
H NMR of Acetone
1
H3C CH3
H NMR of Methyl Acetate
1
CH3
H3C O
Electron Density Maps
Electron Shielding
Electron Shielding
Common NMR Shifts
X H
X = N, O, S
H
H
X C H
H
X = N, O, S, halogen
O
H
O H
R C H
R H C C
H
R O H
H
C C H
12 10 8 6 4 2 0 ppm
Common NMR Shifts
aldehydes "aromatic" (benzene) near N,O,S, "alkyl" region
region "olefin" region halogen
acids
12 10 8 6 4 2 0 ppm
H NMR of Methyl Acetate
1
O
O
CH3
H3C O CH3
H3C O
H NMR of Neopentyl Bromide
1
H NMR of Neopentyl Bromide
1
H NMR of Ethyl Acetate
1
3 Integral
ratios
O
CH2
H3C O CH3
3
What are these strange signals?
Proton Coupling
Hydrogen nuclei will couple to each other if:
•They are not chemically equivalent
•They are 2 or 3 bonds apart
•Double bonds can cause coupling through 4
bonds
H H
H H
H H
2 bonds 3 bonds 4 bonds
coupling coupling no coupling
Proton Coupling
These 2 hydrogens will couple to the methyl group
These 3 hydrogens are identical - 1 signal
O H H
Me O CH3
Higher Beff
Lower Beff
Identical, no Split
B0 effect on Beff
Add to Beff Subtract from Beff CH3 CH3
Proton Coupling
These 2 hydrogens are identical - 1 signal
O H H
Me O CH3
These 3 hydrogens
will couple to the
methylene group
Split
CH2
CH2
B0 Add to Beff Subtract from Beff
Add to Beff
Subtract from Beff
H NMR of Ethyl Acetate
1
3
O
CH2
H3C O CH3
3
2
Multiplicity
Determining Hydrogen Atom
Relationships
The Substitution Test: For any pair of H’s, substitute
each separately with an X and compare the two
structures.
•If the structures are identical – Homotopic (no coupling)
•If the structures are enantiomers – Enantiotopic (no coupling)
•If the structures are diastereomers – Diastereotopic
(coupling is possible)
Determining Hydrogen Atom
Relationships
X
Cl
Cl H
H identical = homotopic
Cl
Cl H
H
Cl
Cl X
X Cl X
Me Me
Cl H H
H enantiomers = enantiotopic
Me
Cl H
H H
Me Me
Cl X Cl X
Determining Hydrogen Atom
Relationships
HO H
Me
Me
X H
HO H
diastereomers = diastereotopic
Me
Me
H H
HO H
Me
Me
H X
Me Me
Me Me
X H
diastereomers = diastereotopic
H H Me Me
H X
Coupling Constants
The coupling constant (J) is the distance between two adjacent peaks of a split
NMR signal in hertz (Hz)
Coupled protons have the same coupling constant
Useful Coupling Constants
H H
H H H H
H H
H H
H H
0-3 Hz 6-12 Hz 12-18 Hz 6-8 Hz 1-3 Hz 0-1 Hz
(usually not
observed)
Olefin Geometry Through Coupling
Constants
A Splitting Diagram for a Doublet of
Doublets
A Quartet Vs. A Doublet Of Doublets
Coupling With “Exchangeable”
Protons
Dry, ultra-pure ethanol
Ethanol with trace acid
Four Different (But Similar)
Compounds
Molecular Ion = 74 [C4H10O]
Unknown #1
9
1
Unknown #2
6
2
1
Unknown #3
3
2 1
4
Unknown #4
8
1
Putting It All Together -
Identifying Unknown Compounds
86
89 (5%)
Putting It All Together -
Identifying Unknown Compounds
Putting It All Together -
Identifying Unknown Compounds
6
3
