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15 DDD
Nuclear Magnetic Resonance
Spectroscopy

Lecture 2

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15 Chemical shift of OH and NH ?

Aliphatic and cyclic Amine

Alcohols
NH peak found between 0.5 and 3ppm
OH peak found between 0.5 and 5ppm
(Depending on degree of H bonding)
- Depends on concentration Aromatic amines
- Polarity of solvent used
NH peak found between 3 and 5ppm

Phenols (Depending on degree of H bonding)

- Depends on concentration
OH peak found between 4 and 7.5ppm - Polarity of solvent used
- depends on Conc. and solvents
- a carbonyl group in ortho position
can shift it to 10-12ppm ! Amide, pyrrole, indole
(intramolecular H bonding)
- NH peak is found between 5 and 8.5
- Effect of conc. snd solvent is smaller
than in the case of amines.

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15 Aromatic Systems
 π-system contains several electrons

- Circulation of electrons create a ring current that generate a

magnetic field
(opposes B0 field inside the ring and reinforce the field outside the ring)

So protons chemical shift is high

Aromatic Hs : δ 6.5 – 8.5

Induced magnetic field B

Ring current

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15
Aromatic H-H coupling

• In aromatic systems, bonds are shorter

• So the coupling effect experienced over more bonds, commonly, 3-bond
(3J) and 4-bond (4J) coupling
• Fewer bonds → larger J value

3J (7-8 Hz) 4J (2-3 Hz)

ortho meta

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15
Aromatic substitution patterns

• Integrals indicate how many aromatic H atoms present....

– Shows how many substituents

• Multiplicity and Coupling between aromatic H atoms depends on

their relative position on ring

•  Determination of the degree of substitution and exact

position of substituents on the ring

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15 How do we determine chemically and magnetically
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equivalent protons ?
In Aliphatic chains:

Protons borne by the same carbons are chemically and magnetically equivalent unless
there is a chiral centre or a rigid chain (ring). They couple with 3 bonds away
neighbouring protons in the first case scenario, with 2 bonds away protons in the
latter case.

In aromatic rings:

a) Plane of symmetry

b) No symmetry

Aspirin

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15 Aromatic substitution patterns

“Simplest” : para-disubstitution

 Plane of symmetry down middle of molecule :

 HA and HA’ are chemically and “magnetically” equivalents
So HA and HA’ resonate at the same frequency and do not couple to one
another
 Hx and Hx’ are chemically and “magnetically” equivalents
So HX and HX’ resonate at the same frequency and do not couple to one
another

 HA and HX are not chemically and magnetically equivalent so they do

couple to one another

Plane of symmetry

Method of “successive splitting” to predict

the multiplicity (or splitting pattern) of aromatic protons (and alkenes)

Do not use n+1 rule for aromatic (or alkenes)

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15 Para-disubstituted: C7H7ClO (p-chloroanisole)

HX HA

JXA Split by HA(Jortho) JAX Split by HX (Jortho)

8Hz 8Hz

2 Integration 2

• How do we assign the correct 2Hs to a doublet?

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15
Shielding through resonance

Overall:
Where carbons have d-, the
electron density is higher
→ shielding (↓ n and ↓ d)

2H ortho to EDG appear

at lower d value
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15
X is EDG: effect on H = shielding

Two kinds of EDG:

1. Electron donating through inductive effect
– An alkyl group donates electron density through allowing the electrons in the σ-
bond to lie closer to the atom at the other end of the bond
– Short range effect (no resonance)
e.g. : Alkyl groups

2. Electron donating through resonance

– An atom with a lone pair attached directly to the aromatic ring can share its
electrons with the π -system
– Long range effect involving resonance
e.g. : OH, OR, NH2, NHR, NR2 (SH, SR)

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15
Deshielding via resonance

Where carbons have d+, the

Overall:
electron density is lower
→ deshielding (↑ n and ↑ d)

2H ortho to EWG appear

at higher d value
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15 Y is EWG: effect on H = deshielding

Two kinds of EWG:
1. Electron withdrawing through inductive effect:
– The electrons in the σ-bond are pulled closer to Y than to the C.

– Short range effect (no resonance).

e.g. : halogens

2. Electron withdrawing through resonance

– A group that can accept π-electrons from π -system can engage in electron
resonance with the ring.

– Long range effect that involves resonance

e.g. : CO2H, -CO2R, -CHO, -SO3H, -SO2NHR, -NO2, -C≡N

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15 Meta-disubstituted: example of Aspirin

What signals should we expect in the NMR spectrum ?

1- Determine the number of protons that are chemically and

magnetically equivalents

2- For each proton, determine the multiplicity using the

method of successive splitting

3-Which protons will be the most shielded?

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1H NMR of ortho-disubstituted compound : Aspirin
15 H3

H5
H6 td
H4
td

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Monosubstituted aromatic ring : Ethylbenzoate ester…
15

 What mutiplicity should we expect for the aromatic protons ?

 What will be their relative position?

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Plane of symmetry :
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- 2 HA chemically and magnetically equivalents

- 2 HM chemically and magnetically equivalents

- 1 Hx

HM
HA
JMA
Split by HA(Jortho)
JAM
Split by HM (Jortho) JMX JMX
Split by HX (Jortho)
JAX JAX
Split by HX (Jmeta)

Triplet
Doublet of doublet 2 x HA 2 x HM (2H, t, 3J=8Hz)
(2H, dd, 3J=8Hz, 4J=2Hz)
1 x HX

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HX
15
JXM
Split by first HM (Jortho)

JXM JXM
Split by second HM (Jortho)

Split by HA (Jmeta) JXA JXA JXA

Split by second HA (Jmeta) JXA JXA JXA JXA JXA JXA

triplet of triplet
(1H, tt, 3J=8Hz, 4J=2Hz)

2 x HA 2 x HM

1 x HX

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15
• Carbonyl groups have deshielding cone due to C=O B
p-system:

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15 +
Alkenes:

• Alkenes relatively common in biological systems +

Where - = deshielded
• What region of NMR spectrum? + = shielded
– Chemical shift: δ 5.5 – 7
– Can be outside this range – depends on substituents

• Multiplicity and coupling constants

Chemically and magnetically not equivalent

gem=geminal =on same C

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15 Example : Styrene
(3JMX=18Hz) (3JAX=11Hz)
(2JAM=1Hz) (2JAM=1Hz)

HX

JAX
Split by HM (Jtrans=18Hz)

JAM JAM
Split by second HA (Jcis=11Hz)

HM
HA
HX

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15 2nd example : vinyl acetate

SDBS: d 7.26 (1H, dd, J 13.98 and 6.31), 4.88 (1H, dd, J 13.98 and 1.63),
4.56 (1H, dd, J 6.31 and 1.63), 2.13 (3H, s)

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