B.Sc.

Semester-VI
Paper CC-XIV
Organic Chemistry-V

III. Nuclear Magnetic Resonance Spectroscopy

Dr. Rajeev Ranjan

University Department of Chemistry
Dr. Shyama Prasad Mukherjee University, Ranchi

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 Nuclear Magnetic Resonance Spectroscopy
1H NMR—Spin-Spin Splitting
•Consider the spectrum below:

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Ethyl Bromide
 Spin-Spin Splitting in 1H NMR Spectra
• Peaks are often split into multiple peaks due to magnetic interactions between
nonequivalent protons on adjacent carbons, The process is called spin-spin
splitting
• The splitting is into one more peak than the number of H’s on the adjacent
carbon(s), This is the “n+1 rule”
• The relative intensities are in proportion of a binomial distribution given by
Pascal’s Triangle
• The set of peaks is a multiplet (2 = doublet, 3 = triplet, 4 = quartet, 5=pentet,
6=hextet, 7=heptet…..)

1 singlet
1 1 doublet
1 2 1 triplet
1 3 3 1 quartet
1 4 6 4 1 pentet
1 5 10 10 5 1 hextet
1 6 15 20 15 6 1 heptet
 Rules for Spin-Spin Splitting
• Equivalent protons do not split each other

• Protons that are farther than two carbon atoms apart do not split each other
 1H NMR—Spin-Spin Splitting

If Ha and Hb are not equivalent, splitting is observed when:

Splitting is not generally observed between protons separated by more than

three  bonds.

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 The Origin of 1H NMR—Spin-Spin Splitting
• Spin-spin splitting occurs only between nonequivalent protons on the same
carbon or adjacent carbons.
Let us consider how the doublet due to the CH2 group on BrCH2CHBr2
occurs:

• When placed in an applied field, (B0), the adjacent proton (CHBr2) can be
aligned with () or against () B0. The likelihood of either case is about 50%
(i.e., 1,000,006 vs 1,000,000).
• Thus, the absorbing CH2 protons feel two slightly different magnetic fields—
one slightly larger than B0, and one slightly smaller than B0.
• Since the absorbing protons feel two different magnetic fields, they absorb at
two different frequencies in the NMR spectrum, thus splitting a single
absorption into a doublet, where the two peaks of the doublet have equal
intensity.

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 The Origin of 1H NMR—Spin-Spin Splitting
The frequency difference, measured in Hz, between two peaks of the doublet is
called the coupling constant, J.

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 The Origin of 1H NMR—Spin-Spin Splitting
Let us now consider how a triplet arises:

• When placed in an applied magnetic field (B0), the adjacent protons Ha

and Hb can each be aligned with () or against () B0.
• Thus, the absorbing proton feels three slightly different magnetic fields—
one slightly larger than B0(ab). one slightly smaller than B0(ab) and one
the same strength as B0 (ab).

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 The Origin of 1H NMR—Spin-Spin Splitting
• Because the absorbing proton feels three different magnetic fields, it absorbs at
three different frequencies in the NMR spectrum, thus splitting a single
absorption into a triplet.
• Because there are two different ways to align one proton with B0, and one
proton against B0—that is, ab and ab—the middle peak of the triplet is twice
as intense as the two outer peaks, making the ratio of the areas under the three
peaks 1:2:1.
• Two adjacent protons split an NMR signal into a triplet.
• When two protons split each other, they are said to be coupled.
• The spacing between peaks in a split NMR signal, measured by the J value, is
equal for coupled protons.

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The Origin of 1H NMR—Spin-Spin Splitting

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The Origin of 1H NMR—Spin-Spin Splitting
Common Splitting Patterns observed in 1H NMR

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 Nuclear Magnetic Resonance Spectroscopy
1H NMR—Spin-Spin Splitting
Whenever two (or three) different sets of adjacent protons are equivalent to
each other, use the n + 1 rule to determine the splitting pattern.

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 Nuclear Magnetic Resonance Spectroscopy
1H NMR—Spin-Spin Splitting
Whenever two (or three) different sets of adjacent protons are equivalent to
each other, use the n + 1 rule to determine the splitting pattern.

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 Nuclear Magnetic Resonance Spectroscopy
1H NMR—Spin-Spin Splitting
Whenever two (or three) different sets of adjacent protons are not equivalent to
each other, use the n + 1 rule to determine the splitting pattern only if the
coupling constants (J) are identical:
Free rotation around C-C bonds averages
coupling constant to J = 7Hz
a a c

Jab = Jbc
b

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 Nuclear Magnetic Resonance Spectroscopy
1H NMR—Spin-Spin Splitting
Whenever two (or three) different sets of adjacent protons are not equivalent to
each other, use the n + 1 rule to determine the splitting pattern only if the
coupling constants (J) are identical:
c

c
b

Jab = Jbc

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 Thank You

Dr. Rajeev Ranjan

University Department of Chemistry
Dr. Shyama Prasad Mukherjee University, Ranchi

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