Strategies for Solving Problems using IR, 1H-NMR and 13
C-NMR
1. First of all determine the Index of Hydrogen Deficiency (IHD)
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𝐼𝐻𝐷 = #𝐶 𝑎𝑡𝑜𝑚𝑠 − ; Note: For each halogen atom in the molecular formula add
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one to the total hydrogen atoms in the molecular formula; for each nitrogen atom present in the
molecular formula subtract one from the total hydrogen atoms. Example:
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C5H9O2Br 𝐼𝐻𝐷 = 5 − = 1
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C5H11N 𝐼𝐻𝐷 = 5 − = 1
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Cases where the IHD ≥ 4 there is the strong possibility of a benzene ring. Chemical shifts (δ ≥
6.5 ppm) on the 1H-NMR will confirm the presence of the aromatic ring.
2. If you are provided with the Infrared Spectrum (IR) of the compound
look for functional groups.
a) A molecule containing oxygen might show a broad signal
around the 3300 cm-1 which suggests the presence
of –OH due to an alcohol or carboxylic acid. C10H14
Hydrogen-bonding of the –OH stretch makes this peak
very broad. If, on the other hand, the molecule contains 14 − 2
𝐼𝐻𝐷 = 10 − = 4
nitrogen and there’s a medium intensity peak around 2
-1
3300 cm suspect an –NH stretch, i.e. the presence of
an amine or amide.
b) The very sharp absorption of the C=O around ~1625 to ~1750 cm-1 indicates the presence of a
carbonyl compound; aldehydes, ketones, carboxylic acids, esters, amides.
c) Functional groups like -C≡N (nitriles), -C≡C-H (alkynes) are easily identified in IR.
3. Use of 1H-NMR.
a) How many different sets of signal appear in the spectrum? (This can be determined by the
number of integrated peaks.)
b) What is the relative ratio of all the different hydrogen peaks present? Do they add to the total
number of hydrogen atoms in the molecular formula? See Example below.
The 1H-NMR of the compound with molecular C7H12O4 (shown above) has three different types
of hydrogen atoms (there are three different integrated peaks) and an IHD = 2. The ratio of
hydrogen atoms do not add to the total hydrogen atoms. This is highly suggestive of symmetry.
But multiplying by two the ratios becomes 4:2:6, which then add up to 12 total hydrogen atoms.
The chemical shift provides information into the chemical environment of the different hydrogen
atoms in the molecule. As a rule of thumb, a chemical shift seen at δ ≤ 1.0 ppm and an
integration of 3.0 most probably indicates an alkyl group whose terminal is a –CH3. An aldehyde
proton will show at ~9.0 ppm and a carboxylic acid ~11.0 ppm. Remember that electronegative
atoms tend to deshield hydrogen atoms moving their chemical shifts downfield by the inductive
effect.
C7H12O4
3.0
2.0
1.0
4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0
c) The splitting patterns of each signal are very important because they can help us understand
the hydrogen atoms attached to adjacent carbon atoms (about 3 bonds away).
1. Remember the n+1 rule for the splitting pattern.
2. An isolated ethyl group (-CH2CH3) will show a particular pattern. A triplet results
from the –CH3 (the neighbor is a -CH2-) and a quartet from the –CH2- (see 1H-NMR
above).
3. An isolated isopropyl group (-CH(CH3)2) will show a doublet from the methyl groups
and a septet from the methyne (-CH-).
4. The 1,4 di-substituted benzene is the simplest splitting pattern. It usually show up as a
pair of doublets each with an integration of 2.
4. After assigning partial structures on the 1H-NMR spectrum try to place them together to form the
compound. Next, try to generate a spectrum from the proposed structure and compare it to the
spectrum provided.
5. Use of 13C-NMR
a) The proton-decoupled 13C-NMR will show the different types of carbon atoms (non-equivalent
sets of carbons) in the molecule. If the number of carbon signals is less than the number of
carbon atoms in the molecule this is suggestive of symmetry in the molecule. (See sample
below) Signals in the 160 – 220 ppm range are indicative of a carbonyl functional group
(amides, ester, ketones, etc.)
C7H12O4
Answer to the 1H-NMR and 13C-NMR
above.
