NMR Spectroscopy

Dr. SUPRIYO SAHA

M. Pharm, Ph.D.
(Pharmaceutical Chemistry)
 Integrals in Proton NMR Spectra
• The structure of toluene consist of two different types of hydrogen with different
environments such as C6H5 and CH3.
CH3
• The two peaks in toluene have relative areas with 5:3 ratio as 5 hydrogen
in C6H5 and 3 hydrogens in CH3.
• Here CH3 is more shielded than C6H5.
• So C6H5 is observed in far more than CH3.
• In the structure of 4-hydroxyl acetophenone eight different types of protons are present. 8 CH3

• C2 and C6 have same environment. C3 and C5 have same environment. 7 O

• C1, C4, C7 and C8 are same environment. Mostly shielded proton is from CH3 1

• Away from C=O group C3 and C5 are slightly deshielded than CH3. 6 2

5 3
• Followed by C1 as more deshielded than C3 and C5. Then peaks of C4 and C7.
4
• Smallest peak is C7 highly deshielded due to OH
presence of oxygen atom. So consider it as probe
of height.
• C4 is slightly higher than C7 due to one H atom
• C1 is slightly higher than C7 (aromatic ring)
• Presence of three hydrogen in CH3 its height
almost triple than C7.
• The number of hydrogens at C3 C5 C2 C6 are
same so both the peaks are equal in height.
 Spin-Spin Coupling and Spin-Spin Splitting
• The 1H NMR spectrum of trans-cinnamic acid, the aromatic protons five in number, give rise to the peaks at δ 7.4 and δ 7.55,
• and the carboxyl proton is at δ 12.5. Proton HA appears as two lines on the spectrum (centered on δ 6.45).
• Proton Hx appears as two lines (centered on
δ 7.8). Normally HC=CH group observed near
3.0 PPM. In presence of COOH group HA move
towards 6.45 more deshielded zone and HX also
move towards 7.8 PPM due to aromatic ring.
• Here both Hx and HA are observed with
doublet (two splited lines).
This spilting of lines known as multiplicity.

Hx

HA

HO O
 Multiplicity of peaks
• The number of lines (multiplicity) observed in the NMR signal for a group of protons is not related to the
number of protons in that group; the multiplicity of lines is related to the number of protons in neighboring
groups.
• The simple rule is: to find the multiplicity of the signal from a group of protons, count the number of neighbors
(n) and add 1. In short it is mentioned as n+1 rule. Where n= number of neighboring protons.
• In case of HA and HX both case neighboring hydrogen is 1 so observed peaks are (1+1=2) or doublet.
• X showed doublet due to presence of HA whereas
• HA showed triplet due to presence of CH2 group.
• Splitting of the spectral lines arises because of a
coupling interaction between neighbor protons,
and is related to the number of possible spin orientations
that these neighbors can adopt.
The phenomenon is called
either spin-spin splitting or spin-spin coupling.
 Pascal’s triangle
• Pascal’s Triangle : The nuclei having spin quantum number I = 1/2, relative intensities of the multiplet’s peak
are given by the coefficients of the binomial expansion, (1 + x)n, where n = number of nuclei interacting with
the specific nucleus emitting the signal ; or by Pascal’s Triangle as given below

So two peaks are equal in height (doublet), Three peaks are in 1:2:1 ratio (triplet), Four peaks are 1:3:3:1 ratio
(Quartet) and Five peaks are 1:4:6:4:1 ratio (Quintet).