Spring 2014

CHEM 212 – NMR Spectroscopy

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Spectral Analysis – 1H NMR NMR Spectroscopy

NMR Spectral Analysis – Introductory 1H NMR

1. NMR is rarely used in a vacuum to do a “forensic” analysis of an unknown

2. NMR (all nuclei) is usually used:

– To analyze the product of a chemical reaction along with IR
– To elucidate the structures of natural products (like the spice lab
compounds in CHEM 213) in conjunction with mass spectrometry
(which gives molecular weights and formulas), IR and UV

3. In this course, you will be given one of three pieces of data with an 1H
NMR for consideration:
– A molecular formula
– An IR spectrum
– The first part of a chemical reaction – for example:
O

NaBH4
EtOH

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Spectral Analysis – 1H NMR NMR Spectroscopy

NMR Spectral Analysis – Introductory 1H NMR

Step 1: Do a quick assessment of the information you are given

Molecular formula – one of the most important pieces of information

Use the index of hydrogen deficiency (HDI) to determine the possible

number of rings, double and triple bonds in the molecule:

For a chemical formula: CxHyNzO (halogens count as Hs)

HDI = x – ½ Y + ½ Z + 1

Example: C4H8O -- HDI = 4 – ½ (8) + ½ (0) + 1

HDI = 1 This compound contains either one

double bond or one ring
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Spectral Analysis – 1H NMR NMR Spectroscopy

NMR Spectral Analysis – Introductory 1H NMR

Step 2: Do a quick assessment of the 1H NMR you are given

– Is the molecule simple or complex?

– Is the molecule aromatic, aliphatic or both?

– What are the total number of resonances that you observe

Be careful with overly simple spectra – remember a large molecule may

appear to be small and simple if it is highly symmetrical

Consider: Durene, C10H14

1H NMR spectrum consists of two singlets!

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Spectral Analysis – 1H NMR NMR Spectroscopy

NMR Spectral Analysis – Introductory 1H NMR

Example: 1H NMR for C4H8 (which has an HDI of 1)

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Spectral Analysis – 1H NMR NMR Spectroscopy

NMR Spectral Analysis – Introductory 1H NMR

Step 3: Use the integration along with the molecular formula to make sure
you can find all of the 1Hs (this is 1H NMR after all!)

If you do not have a molecular formula, use the integration to attempt to

tabulate the number of 1Hs in the formula (does it make sense?)

If one hydrogen appears to be “missing”, you may suspect it is acidic or

exchangeable with the dueterated NMR solvent

Remember, integration gives you the least common denominator of the

total number of protons of each type

Keep in mind organic molecules contain –C-H’s, -CH2- ’s, -CH3 ’s and
multiples of chemically equivalent ones!

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Spectral Analysis – 1H NMR NMR Spectroscopy

NMR Spectral Analysis

Continue our example:

For C4H8O we need to find 8 43

protons

The integral for the quartet

at d 2.5 measures 30 mm,
the singlet at d 2.2 measures 44
44 mm, the triplet at d 1.1
measures 43 mm

The ratio: 30
30:43:42 is roughly 2:3:3
2+3+3=8
We found all 8 protons

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Spectral Analysis – 1H NMR NMR Spectroscopy

NMR Spectral Analysis – Introductory 1H NMR

Step 4: Classify each of the proton resonances by using the general

correlation table

Reconsider the number of rings, double or triple bonds that are possible
given the HDI, and reconcile this data with what the 1H chemical shifts are
telling you

Some hints:
If you calculate an HDI > 4, you probably have an aromatic ring, and this
should show on the spectrum

If you calculate an HDI of 1 or 2 and see no protons that are part of an

alkene and alkyne – suspect rings if no oxygen's are present, carbonyls if
(C=O) they are

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Spectral Analysis – 1H NMR NMR Spectroscopy

NMR Spectral Analysis

Continue our example:

EWG CH3
For C4H8O we have 3 families
of chemically equivalent
protons in a ratio of 2:3:3 or
–CH2-, -CH3, -CH3

EWG
Both the d 2.2 and 2.5
resonance correspond to R CH2
R CH3
protons on carbons next to
electron withdrawing groups

The d 1.1 resonance

corresponds to protons on
carbons bound to other
aliphatic carbons

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Spectral Analysis – 1H NMR NMR Spectroscopy

NMR Spectral Analysis

Continue our example:

EWG CH3
We found –CH2-, -CH3 and
–CH3, subtract these from
our original formula:

C4H8O - CH2 = C3H6O EWG

C3H6O – CH3 = C2H3O R CH2
R CH3
C2H3O – CH3 = CO

We needed an HDI of 1 and

there is no evidence for
1H-C=C on the 1H NMR, our

missing HDI, and EWG is a

C=O!

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Spectral Analysis – 1H NMR NMR Spectroscopy

NMR Spectral Analysis – Introductory 1H NMR

Step 5: Analyze the spin-spin coupling multiplets to elucidate the carbon

chains of the molecule

Hints:
• Singlets indicate you have protons on carbons that have no
chemically non-equivalent protons on any adjoining atom

• Multiplets mean you have chemically non-equivalent protons on

adjoining carbons (or atoms), use the n+1 rule in reverse to find
out how many

• Spin-spin coupling or splitting is MUTUAL, if you observe a multiplet

there must be another multiplet it is related to (split by)

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Spectral Analysis – 1H NMR NMR Spectroscopy

NMR Spectral Analysis

For our example, this is

EWG CH3
trivial; we have concluded
the C=O is the electron
withdrawing group

The –CH3 singlet at d 2.2

obviously has no 1Hs on EWG

adjoining carbons, as it is R CH2

R CH3
next to the carbonyl

The d 2.5 –CH2- quartet is

next to a –CH3 (n+1 = 4, so
n = 3, it is next to a –CH3)

The d 1.2 –CH3 is a triplet, so

it is next to a –CH2
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Spectral Analysis – 1H NMR NMR Spectroscopy

NMR Spectral Analysis – Introductory 1H NMR

Step 6: Construct the molecule and double-check consistency

• Does the HDI match? Have you accounted for all atoms in the
formula?

• From your constructed molecule, pretend you are trying to verify if

that spectrum matches, and quickly re-do the problem

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Spectral Analysis – 1H NMR NMR Spectroscopy

NMR Spectral Analysis

We concluded we have:

O H
2
H3C C C CH3

or 2-butanone

C4H8O, HDI = 1
3 proton resonances
2 mutually coupled (split)

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 2: C9H9BrO

HDI =

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 2: C9H9BrO

HDI = 9 – ½ (10) + 0 + 1 = 5

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 2: C9H9BrO

HDI = 9 – ½ (10) + 0 + 1 = 5

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 2: C9H9BrO O

HDI = 9 – ½ (10) + 0 + 1 = 5 Br

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 3: C4H10O

HDI =

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 3: C4H10O

HDI = 4 – ½ (10) + 0 + 1 = 0

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 3: C9H9BrO

HDI = 0

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 3: C4H10O HO

HDI = 0

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 4: C5H10O2

HDI =

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 4: C5H10O2

HDI = 5 – ½ (10) + 0 + 1 = 1

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 4: C5H10O2

HDI = 1

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 4: C5H10O2
O
HDI = 1 HO

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 5: C10H12O2

HDI =

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 5: C10H12O2

HDI = 10 – ½ (12) + 0 + 1 = 5

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 5: C10H12O2

HDI = 5

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 5: C10H12O2
O

OH
HDI = 5

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 6: C6H4ClNO2

HDI =

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 6: C6H4ClNO2

HDI = 6 – ½ (5) + ½ (1) + 1 = 5

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 6: C6H4ClNO2

HDI = 5

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Spectral Analysis – 1H NMR NMR Spectroscopy

Example 6: C6H4ClNO2 O O
N

HDI = 5
Cl

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