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Organic Spectroscopy

Second Year, Michaelmas term, 8 lectures: Dr TDW Claridge & Prof BG Davis

Lectures 1–4 highlight the importance of spectroscopic methods in the structural elucidation of
organic molecules starting with an introduction to the NMR phenomenon; these four lectures will
enable you to interpret 1H and 13
C spectra of simple organic molecules and to identify simple organic
structures from their NMR spectra.

Content: (1) Organic absorption spectroscopy, nuclear spin and resonance, chemical shifts; (2) factors
that influence 1H chemical shifts, spin-spin coupling, coupling patterns and resonance multiplicities,
coupling to chemically equivalent spins, weak and strong coupling; (3) chemical and magnetic
equivalence, 1H spin couplings and chemical structure—geminal, vicinal and long-range couplings,
13
chirality and NMR, chiral solvating agents; (4) C NMR spectroscopy, NMR instrumentation, Fourier
transform NMR, interpretation.

Lectures 5–7 will introduce those aspects of UV (0.5 lect.), IR (1.5 lect.) and MS techniques (1 lect.)
that you will need in order to suggest candidate structures given raw experimental data in each case.
Coverage of the underlying theory and instrumentation associated with each method will be kept to a
bare minimum since these aspects are covered elsewhere. In modern research laboratories, NMR
spectroscopy and MS are usually the first choice method for gaining structural information, with IR
information routinely acting in a supporting capacity and UV spectra only being required in specialised
circumstances (e.g. polymers, porphyrins). Lecture 8 will show how IR and MS data can be used in
combination with NMR spectra to assign structures in a selection of real examples.

Previous examination questions for practice

Part IA: 2004 (Q7), 2005 (Q2), 2006 (Q1), 2007 (Q8), 2008 (Q9), 2009 (Q1)

Bibliography

• Introduction to Organic Spectroscopy: LM Harwood & TDW Claridge

Basic text for this course
• Spectrometric Identification of Organic Compounds (7th ed): RM Silverstein, FX. Webster &
DJ. Kiemle
Comprehensive description of IR, MS and NMR with many problems: highly recommended
• Spectroscopic Methods in Organic Chemistry (5th Edn): DH Williams & I Fleming
Broad coverage of UV, IR, NMR and MS
• Organic Structures from Spectra: LD Field, S Sternhell & JR Kalman
Workbook of 1H and 13C NMR spectra of increasing complexity
• Structure Elucidation by NMR in Organic Chemistry: E Breitmaier
Workbook of example NMR spectra
• Experimental Organic Chemistry (2nd Edition): L M Harwood, C J Moody & J M Percy
Chapter 5 and Appendix 3 provide useful background and reference tables
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Nuclear Magnetic Resonance (NMR) Spectroscopy I-IV

These NMR lectures are aimed at providing a basic introduction to the NMR phenomenon. It should
enable you to interpret 1H and 13C spectra of simple organic molecules and to identify simple organic
structures from their NMR spectra.

Content
Organic Spectroscopy
Basics of Absorption Spectroscopy
Nuclear spin and resonance
Chemical shifts

Factors that influence 1H chemical shifts

Spin-Spin coupling
Coupling patterns and resonance multiplicities
Coupling to chemically equivalent spins
Weak and strong coupling

Chemical and magnetic equivalence

1
H Spin couplings and chemical structure
-geminal, vicinal and long-range couplings
Chirality and NMR
Chiral solvating agents

Carbon-13 NMR spectroscopy

NMR instrumentation & Fourier transform NMR
Interpretation
At the end of these lectures you should:

• Understand, in simple terms, the basic principles underlying NMR

• Understand the terms chemical shift and spin coupling
• Be able to interpret simple 1H spin coupling patterns
• Understand the concepts of chemical and magnetic equivalence
• Have a feel for the magnitudes of typical 1H-1H coupling constants and what influences these
• Understand the influence of chirality on NMR spectra
• Be able to interpret and assign 1H and 13C spectra of simple organic molecules

Absorption spectroscopy

Absorption
Intensity

λ→
←ν
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Electromagnetic spectrum

NMR Spectroscopy I

Why do Chemists use this technique?

The elucidation of chemical structures is a key step to progress in organic chemistry research and
nuclear magnetic resonance spectroscopy is the primary technique used by organic chemists to derive
such knowledge. It can provide detailed information on a molecule’s gross chemical structure, on its
stereochemistry and on its molecular conformation and dynamics and even its interactions with other
molecules.

NMR Spectra are characterised by three features:

1. Chemical shifts:
2. Spin-spin couplings:
3. Peak intensities (areas/integrals)

Hydrogen (1H) NMR spectrum of ethyl benzene:

CH3
H2C

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

Nuclear spin and resonance

• Most nuclei possess spin angular momentum (I) and all carry charge
• This “spin” is characterised by the nuclear spin quantum number, I, which may be zero (no spin)
or have half-integer or integer values, ½, 1, 3/2, etc
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• Nuclei with I >0 have an associated magnetic dipole moment, μ, (i.e. are themselves weakly
magnetic). Only these nuclei provide an NMR response. Those with I = ½ eg 1H may be viewed as
microscopic bar magnets:

Number of Number of I Example

protons neutrons nuclei
12
Even Even 0 C, 16O, 34
S

2
Odd Odd 1,2,3 … H, 10B, 14N

13
Even Odd 1/2, 3/2, 5/2… C, 17O, 29
Si

1
Odd Even 1/2, 3/2, 5/2… H, 11B, 19F, 31P

• The orientation of the nuclear spin is quantised and may take up 2I+1 possible values.

The Nuclear Magnetic

B0
Resonance condition:
β
ΔE = hν

ν = γB0/2π Hz
ΔE radiofrequency
radiation
γ : magnetogyric ratio
α
(μ = γ I)

• NMR population ratio given by the Boltzmann Distribution:

Nβ/Nα = e-ΔE/kT
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Natural Nuclear Spin Magnetogyric Resonant Relative
Nuclide Abundance % Quantum no. ratio frequency detection
(I) /107 rad T-1 s-1 @ 9.4T /MHz sensitivity
1
H 99.98 1
2
26.75 400 1.00
2
H .02 1 4.11 61 1.45x10-6
12
C 98.89 0 - - 0
13
C 1.11 1
2
6.73 100 1.76x10-4
14
N 99.63 1 1.93 29 1.01x10-3
15
N 0.37 1
2
-2.71 41 3.85x10-6
16
O 99.96 0 - - 0
17
O .04 5
2
-3.63 54 1.08x10-5
19
F 100.00 1
2
25.18 376 0.83
31
P 100.00 1
2
10.84 162 6.63x10-2

ν /H z ν /M H z δ / ppm
10 A ld e h y d ic

1022 N u c le a r 500 9
γ− rays e x c ita tio n
1020 8
X -ra y s A r o m a tic
1018 400
1
H 7
E le c tr o n ic
19
UV F
1 0 16 6
v is ib le O le f in ic
1014 300 5
V ib r a tio n a l
IR
1012 4
R o ta tio n a l
m ic r o w a v e A c e ty le n ic
1010 E le c tr o n S p in 200 3
31
108 P 2 A lip h a tic
r a d io w a v e N u c le a r s p in
13
106 100 C 1
29
Si
15 0 TMS
N
( @ 9 .4 T )

Nuclear shielding
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Chemical Shifts
Symbol: δ, Units: ppm
• Nuclear shielding
B = B0 (1-σ)
σ is the nuclear shielding constant

• Chemical shift scale (a relative scale!)

δ= (ν – νref) / νref
units of parts per million or ppm

• Reference material (for 1H & 13C) is Tetramethylsilane (TMS): inert, volatile, single
line away from most others, ∴ δ TMS = 0 ppm

Peak dispersion:

Nomenclature: high frequency low frequency

low field high field
deshielded shielded

increasing ppm
Typical proton shift ranges:

COOH
Ar-OH
R-OH
R-NH

O=CH
Ar-H
C=CH
C CH
CO-CHn
Ar-CHn
C=C-CHn

Hal-CHn
O-CHn
N-CHn
S-CHn TMS
n=2,3 C-CHn
Metal-CH3

10 9 8 7 6 5 4 3 2 1 0 -1

Aromatic Olefinic Aliphatic